Food Chemistry 180 (2015) 32–41

Contents lists available at ScienceDirect

Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Development of a simple, sensitive and inexpensive ion-pairing cloud

point extraction approach for the determination of trace inorganic
arsenic species in spring water, beverage and rice samples by UV–Vis
spectrophotometry
Ramazan Gürkan, Ufuk Kır, Nail Altunay ⇑
University of Cumhuriyet, Faculty of Sciences, Department of Chemistry, TR-58140 Sivas, Turkey

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

Article history: The determination of inorganic arsenic species in water, beverages and foods become crucial in recent
Received 24 October 2014 years, because arsenic species are considered carcinogenic and found at high concentrations in the sam-
Received in revised form 29 January 2015 ples. This communication describes a new cloud-point extraction (CPE) method for the determination of
Accepted 29 January 2015
low quantity of arsenic species in the samples, purchased from the local market by UV–Visible Spectro-
Available online 10 February 2015
photometer (UV–Vis). The method is based on selective ternary complex of As(V) with acridine orange
(AOH+) being a versatile fluorescence cationic dye in presence of tartaric acid and polyethylene glycol
Keywords:
tert-octylphenyl ether (Triton X-114) at pH 5.0. Under the optimized conditions, a preconcentration fac-
Arsenic speciation
Beverages and rice samples
tor of 65 and detection limit (3Sblank/m) of 1.14 lg L1 was obtained from the calibration curve con-
Acridine orange structed in the range of 4–450 lg L1 with a correlation coefficient of 0.9932 for As(V). The method is
Cloud point extraction validated by the analysis of certified reference materials (CRMs).
Spectrophotometry Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction
Arsenic (As) is a ubiquitous element in the environment origi-
nating from natural sources as well as human activities. Major
anthropogenic sources of As include wood preservatives, agricul-
tural uses as pesticide and herbicide, industrial uses, mining and
smelting. Due to its natural and anthropogenic occurrence, the
entire population is exposed to low levels of arsenic through foods,
beverages, water and air. The toxicity of arsenic highly depends on
its inorganic and organic chemical forms. It is implied in literature
(Seiler, Sigel, & Sigel, 1994) that As(III) is several hundred times
more toxic than organic arsenic and 25–60 times more toxic than
As(V). Therefore, arsenic speciation in food and beverages is an
important analytical task.
Due to be carcinogenic of As and As compounds being carcino-
genic to humans (International Agency for Research on Cancer
(IARC) group 1) (IARC, 1987), one’s intake should be limited. Due
to the greater toxicity of inorganic arsenic (i-As) than organic
arsenic compounds, the Joint FAO/WHO Expert Committee on Food
Additives (JECFA, 2006) also established a provisional tolerable
weekly intake (PTWI) for i-As as 15 lg kg1 body weight, adding
⇑ Corresponding author.
E-mail address: naltunay@cumhuriyet.edu.tr (N. Altunay).
‘the margin between the PTWI and intakes reported to have toxic
effects in epidemiological studies was narrow’. In the case of
organic bound arsenic, organic arsenicals intakes of about
50 lg kg1 body weight day1 seemed not to be associated with
adverse effects. However, it is not always possible to distinguish
clearly the form of As detected in food. Thus, some risk managers
apply the regulatory value to total As in some food. For example,
an Australian food standard established the maximum total As
content for cereals as 1 mg kg1, and i-As for crustacean and fish
as 2 mg kg1 and for mollusk’s and seaweed as 1 mg kg1 (FSANZ,
2006). According to the Turkish Food Codex (TFC) (TFC, 2002),
the maximum contaminant levels of As may not exceed
0.1 mg kg1 in soft drinks. Many responsible authorities around
the world set various guideline levels for some commodities
according to the given conditions of each country. Due to the
highly toxic nature of i-As, As(III) and As(V) especially, there is a
great need to develop an accurate and reliable method for specia-
tive determination and continuous monitoring of trace levels of
i-As species in water, beverage and rice based foods.
Speciation analysis of toxic i-As and nontoxic organic As species
usually involves two steps: (1) separation of different forms and
(2) their subsequent quantification. A wide variety of chromato-
graphic techniques, based on (i) on line quantitative or only rapid
qualitative screening possibilities such as gas chromatography

http://dx.doi.org/10.1016/j.foodchem.2015.01.142
0308-8146/Ó 2015 Elsevier Ltd. All rights reserved.
 R. Gürkan et al. / Food Chemistry 180 (2015) 32–41
(GC), capillary electrophoresis (CE) and liquid chromatography (LC)
interfaced with atomic spectrometric techniques, known as
hyphenated techniques such as HPLC–ICP-MS (Coelho, Coelho, De
Lima, Pastor, & De la Guardia, 2005; Conklin & Chen, 2012;
Ellingson, Zywicki, & Sullivan, 2014; Moreira et al., 2011;
Pearson, Greenway, Brima, & Haris, 2007) with and without
hydride generation including HPLC–HG-AAS (Niedzielski, Siepak,
& Novotny, 2004), HPLC–AFS (Moreno, Cámara, Corns, Bryce, &
Stockwell, 2000; Parrilla et al., 2003; Stibilj, Slejkovec, & van
Elteren, 2002) with and without hydride generation, GC-ICP-MS
(Wahlen & Catterick, 2004), CE-ICP-MS (Hsieh, Liu, Chen, & Jiang,
2010), and (ii) off line alternative techniques such as TXRF-XANES
(Meirer et al., 2007), TLC-TXRF (Mihucz et al., 2006) and TLC-LA-
ICP-MS (Resano, García Ruiz, Mihucz, Móricz, & Záray, 2007) have
been proposed for the speciation of hydride-forming As species
and extensively reviewed. The primary advantage of this
approaches is the unequivocal species separation and specific
online detection. However, most of these techniques have signifi-
cant disadvantages: increased complexity, co-elution of species
of the same element, problems associated with the stability of
plasma due to the use of organic solvents, signal drifts arising from
become clogged of sampler and skimmer cones when the difficult
matrices with high salts (NaCl) and total dissolved solids analyzed,
and interference arising from polyatomic ions in conventional ICP–
MS (Xie, Kerrich, Irving, Liber, & Shakra, 2002). Additionally, these
types of hyphenated instruments are not standard equipment in
most laboratories engaged in quality monitoring of water, bever-
ages and foods. Further considerations to be taken into account
are the acquisition and running costs, analysis time, and ease of
handling, especially for routine analysis. Also, direct determination
and/or speciation of total As or i-As species, As(III) and As(V) in
water, beverage and foods is generally conducted with non-chro-
matographic techniques such as electroanalytical techniques, CSV
(Ferreira & Barros, 2002; Teixeira et al., 2014), DP-CSV (De
Carvalho & Leandro, 2012; He, Zheng, Ramnaraine, & Locke,
2004); atomic spectrometric techniques, ET-AAS (Husakova,
Cernohorsky, Sramkova, & Vavrusova, 2007), HG-AAS (Cervera,
1994; Korenovska, 2006; Tasev, Karadjova, & Stafilov, 2005), capil-
lary gas chromatography with atomic emission detection
(Campillo, Penalver, Vinas, Lopez-Garcia, & Hernandez-Cordoba,
2008), HG-AFS (Karadjova, Lampugnani, Onor, D’Ulivo, & Tsalev,
2005), HG-ICP-AES (Boutakhrit, Claus, Bolle, Degroodt, &
Goeyens, 2005), conventional ICP-MS (Mihucz et al., 2007), XRF
spectrometry (Zucchi, Moreira, Salvador, & Santos, 2005), flow
injection FT-IR and UV–Vis spectrophotometric method with
hydride generation (Arbab-Zavar, Chamsaz, & Heidari, 2010;
Gallignani, Ayala, Brunetto, Burguera, & Burguera, 2002).
Among these sensitive detection techniques, spectrophotome-
try in UV–Visible region is a tool that is most widely used in
developing countries due to its low cost, easy operation, high
accuracy and precision, good selectivity and sensitivity particu-
larly when a suitable chelating or ion-pairing reagent for analyte
is used. However, the direct determination of i-As by spectropho-
tometry can be problematic since its sensitivity is not sufficient
for samples with low levels of As. For this reason, a separation
and preconcentration step such as solid phase extraction (Sugár,
Tatár, Záray, & Mihucz, 2013), dispersive liquid–liquid microex-
traction (DLLME) (Sasan, Mozhgan, & Britta, 2013), liquid–liquid
extraction (LLE) (Amjadi, Manzoori, & Taleb, 2010), coprecipita-
tion (Murata, Shimizu, & Uehara, 2005), ultrasound-assisted
emulsification of solidified floating organic drop microextraction
(USAE-SFODME) (Mehdi et al., 2014), single-drop extraction
(SDE) (Khley, Kihwan, Jihye, In, & Doo, 2013) and cloud point
extraction (CPE) (Ulusoy, Akcay, & Gürkan, 2011a; Ulusoy,
Akcay, Ulusoy, & Gürkan, 2011b) is often required prior determi-
nation of the analyte.
33
Cloud point extraction (CPE), a micelle mediated process, has
become one of the most preferred preconcentration and separation
methods improving the sensitivity in determination of trace met-
als, acting as an alternative to liquid–liquid extraction, owing to
several advantages including high extraction efficiency and
preconcentration factor, low cost, safety, eco-friendly nature and
versatility offered by this particular technique (Samaddar & Sen,
2014). When this procedure as a separation and preconcentration
is combined with UV–Vis spectrometry having poor sensitivity, it
has successfully been applied to determination of essential and
toxic metals such as copper, cadmium and mercury by our research
group (Gürkan & Altunay, 2013a,b; Gürkan & Ufuk Kir, 2013).
In the existing study, we describe a validated method for the
determination of i-As species in drinking water, soft drinks, alco-
holic beverages and rices. The method is based on the selective
ion-pairing complex formation of As(V) with Acridine orange,
AOH+ using Triton X-114 in the presence of tartaric acid at pH
5.0. For the first time, a new ion-pairing CPE approach coupled
with UV–Vis spectrophotometry at 494 nm has been reported for
speciative analysis of i-As species in especially beverage and rice
samples. The method was applied successfully to the speciative
determination of i-AS species after preconcentration of trace
As(V) in selected samples including two CRMs with CPE.
2. Experimental
2.1. Instrumentation
Absorbance measurements at the selected wavelength, 494 nm
before and after CPE respectively were conducted on a double
beam UV–Visible Spectrophotometer (Shimadzu UV-1800 PC,
Kyoto, Japan) equipped with the 1.0-cm quartz cells. A centrifuge
(Universal-320, Hettich Centrifuges, England) was used to acceler-
ate the phase separation process. A thermostatic water bath (EPC
4420, Termal, Istanbul, Turkey) was used to maintain the temper-
ature in CPE experiments. The pH measurements were carried out
with a pH meter (pH-2005, JP Selecta, Spain). An ultrasonic cleaner
(UCS-10 model, Jeio Tech, Co., Ltd., Seoul, Korea) was used to degas
and digest the rice and beverages with and without alcohol. A
refrigerator was used to keep all samples fresh and cool till the
analysis. Eppendorf vary-pipettes (10–100 and 200–1000 lL) were
used to deliver accurate volumes.
2.2. Reagents and solutions
All chemicals and reagents used were of analytical-reagent
grade or higher purity. Ultra-pure water with a resistivity of
18.2 MX cm at 25 °C was prepared using a Labconco (USA) water
purification system. All solutions were prepared with this ultra-
pure water. Stock solutions of As(III) and As(V) (1000 mg L1) were
prepared by dissolving appropriate amounts of As2O3 and Na2-
HAsO4 (Merck, Darmstadt, Germany) in 1 mol L1 NaOH and
3 mol L1 HCl solution, and then completing to 1000 mL with
ultra-pure water, respectively. The standard working solutions
used for establishment of calibration curves, were prepared by
stepwise dilution of the stock As(III) and As(V) solutions with
ultra-pure water just before use. A 0.04 mol L1 of Britton-Robin-
son (BR) buffer were used to keep pH of the solutions. The buffer
consists of a mixture of 0.04 mol L1 H3PO4 (Merck), 0.04 mol L1
H3BO3 (Merck) and 0.04 mol L1 CH3COOH (Merck) that has been
titrated to the desired pH with 0.2 mol L1 NaOH. The solutions
of 5.0 (v/v)% of Triton X-114 (Sigma, St. Loius, MO, USA) were pre-
pared by dissolving appropriate amount 1.0 mL of surfactant with
100 mL of the water. A 1.0  104 mol L1 of AOH+ (Sigma) solution
was prepared fresh daily by dissolving the reagents in ethanol
34 R. Gürkan et al. / Food Chemistry 180 (2015) 32–41
(Merck) and diluting with the water. All the prepared stock solu-
tions were stored in polyethylene bottles in a refrigerator at 4 °C.
All vessels, glassware and PTFE bottles were kept firstly with 10%
(w/v) HNO3 solution and then with 7.5% (w/v) HCl solution. Lastly,
they were washed with the water before experiments.
2.3. Sampling and sample preparation
All water, beverage and rice samples were purchased randomly
from the local markets in Sivas, Turkey. Before preconcentration
procedure, all water samples were filtered using a 0.45 lm mem-
brane filter. The water samples were stored at 4 °C until analyzed.
50 mL of the samples were concentrated by evaporation to final
volume of 5 mL. Then, the preconcentrated water samples were
submitted to CPE procedure. Before analysis, rice samples were
dried in an oven at 55 °C until constant weight, homogenized in
a stainless blender, ground in agate mill to obtain particle sizes
lower than 100 lm in diameter. The pre-treated samples were
placed in polyethylene flasks and kept at 4 °C in a dark environ-
ment until use. The speciation analysis of inorganic As was carried
about using these samples.
The total i-As content of the selected samples and the CRMs (N:
3) was determined by the developed method after two digestion
processes under ultrasonic power (300 watt, 40 kHz) as follows:
aliquots of 0.2 g and 3 mL of rice and beverage samples or the
CRMs respectively were delivered in the digestion flasks of
50 mL, and (a) sequentially 3 mL of 3.0 mol L1 HCl, 2 mL of
0.2 mol L1 HNO3 solution, and 1.0 mL of 2.0 mol L1 H2O2 solution
(3:2:1, v/v), and (b) 3 mL of 3.0 mol L1 HCl, 2 mL of 0.2 mol L1
HNO3 solution, and 1.0 mL of 2.0 mol L1 H2SO4 solution (3:2:1,
v/v) for quantitative oxidation of As(III) to As(V) was added. The
mixtures have been submitted to ultrasonic effect at 60 °C for
30 min until a clear solution is obtained. After cooling to room
temperature, the digested clear samples were diluted in water up
to 25 mL. For the final measurements, further dilution was carried
out when necessary depending composition of matrix and concen-
tration levels of As in samples. The samples were quantified by
means of an external calibration curve from As(V) standards. For
quality control purposes, the standards of the calibration curve
were run before and after each sample series to control a possible
matrix effect. From slopes of calibration curves, it has been
observed that a significant matrix effect is not available with
acceptable slope difference.
The i-As speciation was carried out on the extracts by using the
proposed method. The extraction procedure of i-As species is based
on the study of (Matosreyes, Cervera, Campos, & De la Guardia,
2007; Raab, Baskaran, Feldmann, & Meharg, 2009) with slight mod-
ifications. For speciation analysis, 0.2 g aliquots of the powdered
rice products were weighed in the two separate digestion flasks
in parallel, and then mixed by adding 3 mL of 0.3 mol L1 HCl
and 2 mL of 0.2 mol L1 HNO3 with and without addition of 1 mL
of 0.5 mol L1 H2O2 or 1 mL of 0.5 mol L1 H2SO4 solutions (3:2:1,
v/v) in order to control inter-conversion of As species, As(III) and
As(V) in ultrasonic assisted digestion system. The mixtures were
submitted to ultrasonic effect at 35 °C for 45 min. Samples were
cooled to room temperature and centrifuged at 3500 rpm for
15 min. The supernatant was filtered through membrane filters
of 0.45 lm. The extracts were kept at 4 °C in a refrigerator until
analysis. Total iAs in the extracts was determined by UV–Vis spec-
trophotometry at 494 nm after preconcentration with CPE, and in a
similar way, As speciation was carried out on the extracts by using
a method under the optimized conditions. External calibration
curves were used to quantify As(III) and As(V) against the corre-
sponding standards. For total i-As and speciation of As species,
both the digestion blanks and quality control standard solutions
at three concentration levels were also measured to obtain accu-
rate and reliable results.
2.4. General procedure for CPE
In a recommended procedure, 2.5 mL of 1.0  104 mol L1
AOH+ solution in a centrifuge tube (50 mL) was added to 2.0 mL
of sample solution containing As(V) in the range of 4–450 lg L1,
5.0 mL of 0.04 mol L1 pH 5.0 BR buffer, 0.75 mL of 0.1 mol L1 tar-
taric acid, 0.6 mL of 20% (w/v) NaCl and 3.0 mL of 5.0% (w/v) Triton
X-114, respectively. Then, the total volume was made up to 50 mL
with the water. The solution was kept in a thermostatic water-bath
at 50 °C for 5 min. The As(V) as analyte was efficiently extracted
and preconcentrated as ternary complex, [AOH]AsO2(Tar) or
[AOH]3AsO2(Tar)2 in aqueous micellar solution. Then, in order to
separate the phases, the turbid solution was centrifuged at
4000 rpm for 5 min. Then, resulting mixtures were cooled in an
ice-bath for 5 min in order to increase the viscosity of the surfac-
tant-rich phase and facilitate the removal of the aqueous phase.
After that, the aqueous phase was easily separated from surfac-
tant-rich phase by inverting the tube. The surfactant-rich phase
was dissolved and diluted to 0.75 mL with tetrahydrofuran (THF)
and transferred into a quartz cell prior to spectrophotometric
detection. Finally, the amount of arsenic in a 0.75 mL aliquot of
the resulting solution was determined by UV–Vis spectrophotom-
etry. After that, As(III) in the mixing solution was oxidized to As(V).
For oxidation experiments, the samples were prepared in alkaline
media, approximately pH 12, and 12 mL of 0.01 mol L1 H2O2
was added to the known solutions of As(III) and allowed to react
up to 10 min at room temperature. Then, the procedure was
applied to determination of total i-As content. The concentration
of As(III) was calculated by subtracting the content of As(V) from
total i-As content.
3. Results and discussion
3.1. General considerations
Acridine orange (AOH+), which is a resonance stabilized cationic
dye with planar structure, forms a complex with both As(III) and
As(V) at pH 5.0, but As(V) complex, [AOH]AsO2(Tar) or [AOH]3-
AsO2(Tar)2 is more appropriate for UV–Vis measurements due to
the formation of a more sensitive and selective ion-pairing complex
in presence of tartaric acid. It has usually a positive charge that is
delocalized over the whole p-system at the molecule, with the lar-
gest electron densities placed on the nitrogen atoms. At optimal pH
5.0, As(III) is in neutral form of H3AsO3 with an acidic ionization
constant of pKa: 9.29, whereas As(V) is in ionic forms of H2AsO 4
and HAsO2 4 with an acidic ionization constants of pKa1: 2.24,
pKa2: 6.96 and pKa3: 11.50 (Dario, Mariano, Alicia, & Juana, 2002).
From prior studies conducted for isomolar concentrations of As(V)
and As(III) at pH 5.0, it has been observed that the absorbance
obtained from As(V) complex, [AOH]AsO2(Tar) or [AOH]3AsO2(Tar)2
is higher than those of As(III) complex, [AOH]AsO(Tar) as a measure
of calibration sensitivity. This fact is a clear evident of a more stable
complex formation with As(V). Additionally, for ion-pairing com-
plex formation, As(V) needs to electrostatically interact with
AOH+ at 1:1 and 1:3 metal–ligand ratios depending on pH and tar-
taric acid concentration as a result of increasing negative charge
while As(III) needs to interact with it at 1:1 ratio. Because the com-
plex formation mechanism is based on the electrostatic interaction
of As-species with AOH+ in presence of tartaric acid at pH 5.0, As(III)
will form a more weak ion-pairing complex at hydrophobic charac-
ter than those of As(V) with AOH+. Due to form a more stable com-
plex of As(V) with AOH+ in presence of tartaric acid, the proposed
 R. Gürkan et al. / Food Chemistry 180 (2015) 32–41 35

method was considered and optimized for only As(V) species for of cationic AOH2+ +
2 and/or AOH species to neutral form, AO or
further studies. As a result, the complex formation mechanism increase in analyte blank depending on increase in pH as a result
occurred between anionic As(V)-tartrate complex and AOH+ in of complex formation between anionic tartrate and cationic ion-
presence of tartaric acid at pH 5.0 may be postulated as follows: pairing reagent in absence of As(V) or As(III). At lower pHs, the
cause of decrease in sensitivity may be dimerization of ion-pairing
AsOðOHÞ þ HTar !AsOðTarÞ þ H2 O for AsðIIIÞ ð1Þ ligand, AOH+ in form of (AOH)2+2 (Anisha & Robin, 2013). So, a pH of
5.0 for As(V) as analyte was chosen as optimal value for further
AsO2 ðOHÞ2 þ 2HTar !AsO2 ðTarÞ3
2 þ 2H2 O for AsðVÞ or studies due to the higher analytical signal that was produced.
ð2Þ
AsO2 ðOHÞ2 þ HTar !AsO2 ðTarÞ þ H2 O þ OH After the optimum pH was chosen, the concentration of buffer
solution as a function of volume of buffer solution at a fixed con-
centration was also studied in the range of 1.0–10.0 mL in final vol-
AsOðTarÞ =AsO2 ðTarÞ or AsO2 ðTarÞ3
2 þ AOH
þ
ume of 50.0 mL. The highest analytical signal was observed by
!½AOHAsOðTarÞ=½AOHAsO2 ðTarÞ or½AO3 AsO2 ðTarÞ2 ð3Þ using 5.0 mL of 0.04 mol L1 BR buffer solutions in Fig. 1(b). Thus,
a BR buffer concentration of 4.0  103 mol L1 at pH 5.0 was
selected as optimal value for further studies.
3.2. Optimization of variables affecting CPE efficiency

3.2.1. Effect of pH and buffer concentration

Separation and preconcentration of arsenic ions by CPE involve 3.2.2. Effect of complexing agents concentration
previous formation of ion-pairing complex, which needs to present Acridine orange, which was chosen as ion-pairing reagent, can
sufficient hydrophobicity to be extracted into the small volume of exist in mono-cationic, AOH+ and di-cationic form, AOH2+ 2 depend-
the surfactant-rich phase. Thus, the pH is a critical factor affecting ing on pH of medium (pKa: 10.4). The cationic forms are dominant
both the reaction between ligand molecules and metalloid ions, below pH 10 while the completely deprotonated form, AO exists at
and the extractability of hydrophobic complex into the surfac- higher pHs than 10 (Ulusoy, Aksoy, & Akcay, 2013). At low pHs (pH
tant-rich phase for CPE. In order to determine the optimal pH, ini- 6), AOH+ or AOH2+ 2 exists in mono-cationic or di-cationic form, and
tially the effect of different buffers such as acetate, phthalate, hydrogen bonding, acid-base and electrostatic interactions is
formate in the range pH 2.0–6.0 including universal BR buffer in occurred between AOH+ and arsenic ions. Under the present exper-
the range pH 2.0–9.0 on the CPE were studied for the extraction imental conditions (pH 5.0), -NMe2 groups of AOH+ act as an elec-
and determination of As(III) and As(V) at levels of 100 lg L1. How- tron acceptor behaving as Lewis acid. Because As(III) and As(V) ions
ever, the best signal was obtained with universal BR buffer for both exist as AsO(OH) and AsO2(OH)-2 at these conditions, they form a
species. Therefore, for further optimization studies the BR buffer at ion-association complex with AOH+ in the presence of tartaric acid
0.04 mol L1 was considered in speciation analysis of As(V) and (Ulusoy et al., 2013). However, As(V)–tartaric acid-AOH+ complex
As(III). From the results in range of pH 2.0–9.0 in Fig. 1(a), the max- is more sensitive, selective and effective for measurements with
imum signal for As(V) with a sensitivity difference of 5-fold has UV–Vis spectrophotometry. Tartaric acid (H2L) is a weak hydroxy
been obtained by using a BR buffer of 0.04 mol L1 at pH 5.0 while organic acid with pKa values of 2.89 and 4.40. It is a natural preser-
the best signal for As(III) is obtained at pH 6.0. At higher pHs, the vative/conservative, and is used to add an acidic or sour taste to
extraction efficiency for both As(V) and As(III) is low complex for- foods and beverages such as wine. It also determines the ability
mation rate. The main cause of decrease in extraction efficiency of Fe to catalyze wine oxidation by controlling the reduction
may be disassociation of ion-pairing complex due to deprotonation potential of the Fe(III)/Fe(II) redox couple (John, 2014).

0,35 0,32

0,30 As(V)
0,30
As(III)

0,25
0,28
Absorbance at 494 nm
Absorbance at 494 nm

0,20

0,26

0,15

0,24
0,10

0,22
0,05

0,00 0,20
0 2 4 6 8 10 0 2 4 6 8 101 2

-1
0.04 mol L BR buffer volume at pH 5.0, m
pH

(a) (b)
Fig. 1. Effect of pH (a) and buffer concentration (b) on CPE efficiency. Other experimental conditions are described in Section 2.
36 R. Gürkan et al. / Food Chemistry 180 (2015) 32–41

0,32 0,35

0,30 0,30

0,28 0,25

Absorbance at 494 nm
Absorbance at 494 nm

0,26 0,20

0,24 0,15

0,22 0,10

0,20 0,05

0,18 0,00
0 1 2 3 4 0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5
-4 -1 -1
1.0x10 mol L Acridine Orange volume, mL 0.1 mol L Tartaric acid volume, mL

(a) (b)
Fig. 2. Effect of concentration of acridine orange (a) and tartaric acid volume (b) on CPE efficiency. Other experimental conditions are described in Section 2.

The effect concentration of AOH+ as a function of volume of ion-
pairing reagent at a fixed concentration (1.0  104 mol L1) on
analytical signal intensity of As(V) was studied in range of (0.0–
3.5) mL and the results are shown in Fig. 2(a). It can be seen that
the signal intensity of As(V) strongly depends on the concentration
of AOH+ in CPE system. Also, the highest signal was obtained in
2.5 mL of 1.0  104 mol L1 AOH+. The cause of decrease in signal
intensity at the higher concentrations may be dimerization of dye.
Thus, a concentration of 5.0  106 mol L1 in a final volume of
50 mL was selected for further studies.
The variation of the analytical signal as a function of the con-
centration of tartaric acid as primary ligand in the range (0.0–
3.0 mL) of 0.1 mol L1 in the presence of 100 lg L1 As(V) was
studied, and the results in Fig. 2(b) indicate that the signal inten-
sity of the analyte linearly increased by tartaric acid concentration
up to 0.75 mL of 0.1 mol L1. The maximum signal intensity line-
arly decreased with increasing slope at the higher concentrations.
The cause of the decrease in signal may be complexation of tartaric
acid with AOH+ in absence of As(V) due to increase in blank signal.
X-100 and X-114 series) are those most widely employed for metal
analysis with CPE. Triton X-114 as an extracting agent was chosen
as a surfactant owing to its high density of surfactant-rich phase,
relatively non-toxic reagent and low cloud point temperature, this
facilities phase separation by centrifugation. The effect of the non-
ionic surfactant concentration on CPE of ion-pairing complex in
presence of tartaric acid was studied in the range of (0.2–5.0) mL
at a fixed surfactant concentration. The variation of absorbance of
ion-pairing complex is shown as a function of the concentration
of Triton X-114. According to our results, a 3.0 mL of concentration
of 5.0% (w/w) Triton X-114 can be chosen as optimum value for
As(V). At lower concentrations, the extraction efficiency of complex
0,35
0,30
Absorbance at 494 nm

Thus, a tartaric acid concentration of 1.5  104 mol L1 was 0,25
selected as optimal value for further studies.
0,20
3.2.3. Effect of ionic strength
In the case of extraction methods, the solubility of many ana-
0,15
lytes in aqueous solutions decreases with increasing ionic strength.
Because ionic strength increases, cloud point temperature
decreases because of dehydration of the poly (oxyethylene) chains. 0,10
Moreover, inorganic salts increase the hydrophobic interactions
among surfactant aggregates and analytes, thus favoring their
0,05
extraction from the aqueous to the micellar phase. The influence
0 2 4 6 8 10 12 14 16 18 20 22
of ionic salts strength such as NaCl, KCl and Na2SO4 on extraction
-1
efficiency was studied in the range of (0.1–1.0) mL at a fixed inor- Oxidant agent volume at 0.01 mol L, mL
ganic salts concentration (0.01 mol L1) under the optimized -
With IO3 in weak acidic media at 25 C
o

reagent conditions. When 0.6 mL of 0.01 mol L1 NaCl is used, With H2O2 in alkaline media at 25 C
o

the best signal increase obtained. So, a volume of 0.6 mL was o

With H2O2 in alkaline media at 35 C
selected as optimal value for further studies. o
With H2O2 in alkaline media at 45 C

3.2.4. Effect of amount of non-ionic surfactant Fig. 3. Effect of oxidizing agents’ volume at 0.01 mol L1 on the analytical signal
Up to now, non-ionic surfactants (mainly polyoxyethylenated intensity for quantitative conversion of 100 lg L1 As(III) to As(V). Other experi-
alkylphenols, from Ponpe 7.5 and Triton such as Triton X-45, mental conditions are described in Section 2.
 R. Gürkan et al. / Food Chemistry 180 (2015) 32–41 37

Table 1
The simultaneous determination and/or speciation of inorganic arsenic species (total As, As(V), As(III)) in artificially prepared binary mixtures.
b c
Added (lg L1) Found (lg L1) *
Recovery% RSD% RE%
a a
As(V) As(III) Total As As(V) As(III) Total As As(V) As(III) Total As As(V) Total As As(V) As(III)
50 0 50.4 ± 0.9 49.3 ± 2.3 – 100.8 98.6 – 0.2 0.4 1.9 1.0 –
40 5 44.3 ± 1.1 40.6 ± 2.1 4.8 98.4 101.5 96.0 0.3 0.5 1.8 1.3 4.9
30 10 39.7 ± 1.3 29.4 ± 1.9 9.7 99.3 98.0 97.0 0.3 0.6 1.2 1.5 2.7
20 20 40.8 ± 1.4 19.7 ± 0.7 20.6 102.0 98.5 103.0 0.4 3.6 1.3 3.3 2.1
10 30 41.0 ± 1.6 9.6 ± 0.4 29.3 102.5 96.0 97.6 0.4 4.2 1.7 4.0 1.5
5 40 45.6 ± 1.7 4.9 ± 0.3 41.0 98.4 101.3 102.5 0.5 6.1 2.2 5.6 1.2
0 50 50.8 ± 1.9 – 50.5 101.6 – 101.6 0.4 – 1.9 – 1.1
a
The average values and standard deviations of three replicate measurements for total As and As(V).
b
The relative standard deviation of three replicate measurement.
c
The relative error of three replicate measurements.
*
The recovery rates obtained for three replicate measurements of each species.

is low probably because of the inadequacy of the assemblies to
entrap the hydrophobic complex quantitatively. At higher concen-
trations of Triton X-114 the signal decreases because of the incre-
ment in the volumes and the viscosity of the surfactant phase.
Therefore, this value was chosen as the optimum for further studies.
3.2.5. Effect of equilibration temperature and time, and centrifugation
time
Optimal equilibration temperature and time are necessary to
complete reactions, and achieve an easy and efficient phase sepa-
ration and preconcentration. The effects of equilibration tempera-
ture and time on the analytical signal were studied in the range of
30–70 °C and 0–20 min, respectively. Since, it is desirable to
employ the shortest equilibration time and the lowest possible
equilibration temperature, a temperature of 45 °C and an equili-
bration time of 10 min were chosen for further studies. Centrifuge
time and rates are very necessary to preconcentrate trace amounts
of As(V) with high efficiency in a short time. Thus, under optimal
reagent conditions obtained, the effect of the centrifuge time and
rate were studied in rage of 1–20 min and 250–4000 rpm, respec-
tively. The results showed that centrifugation for 5 min at
4000 rpm and cooling for 10 min in an ice-bath leads to the max-
imum recovery and sensitivity for As(V).
3.2.6. Effect of diluting agent
The surfactant-rich phase obtained after CPE was very viscous
and small for detection by UV–Vis spectrophotometry at 494 nm.
Thus, before detection by UV–Vis spectrophotometry the volume
of the surfactant-rich phase can be decreased using diluting agents.
It is very important to choose the suitable solvent for maximum
extraction efficiency. The effect of various solvents such as metha-
nol, acetone, acetonitrile, ethanol and THF in range of 0.5–2.5 mL
were examined to obtain the maximum analytical signal after
CPE. The best regression coefficient, r2 and analytical sensitivity,
m/sm, in which m and m/sm respectively are slope of calibration
curve and ratio of slope to its standard deviation for three replicate
measurements, was obtained in the existence of 0.75 mL of THF
from calibration curves established for As(V) concentrations of
25, 50 and 100 lg L1.
4. Analytical performance properties of the proposed method
Analytical capabilities of the proposed method for As(V) were as
follows. The calibration curve was obtained by preconcentration of
50 mL of sample under the optimized conditions. The calibration
curve for As(V) was highly linear in the range of 4–450 lg L1 with
correlation coefficients of 0.9932. The relative standard deviation
(RSD) as a measure of precision for 10 replicate determinations
of 50, 100 and 250 lg L1 of As(V) with a recovery ranging from
97.4% to 102.2% were in the range of 2.15% and 4.35%, respectively.
Because the amount of arsenic in 50 mL of sample solution is mea-
sured in 1.0 mL of THF after preconcentration by CPE, the precon-
centration factor was calculated by a factor of 66.7. The sensitivity
enhancement factor (EF) was 48.2 which was calculated by using
the ratio of direct calibration curves’s slopes obtained with and
without preconcentration. Also, the limits of detection and quanti-
fication defined as 3rblank/m and 10rblank/m (N: 12) (where rblank is
the standard deviation of twelve replicate measurements of the
blank and m is the slope of the calibration curve) were found to
be 1.14 and 3.8 lg L1, respectively.
5. Effect of matrix ions
In this context, the matrix ions present in real samples may
cause to a decrease or increase in the signal of As(V). Thus, interfer-
ence effects of the common cations and anions in water, beverage
and rice samples on determination of 50 lg L1 of As(V) was
assessed by independently submitting samples containing interfer-
ing species to CPE procedure under the optimized conditions. An
ion was considered as an interfering ion when it caused an error
greater than ±5.0% in the determination of arsenic. According to
the results, the common cations and anions in real samples do
not cause interference in determination of trace of arsenic species
that can be owing to selectivity tendency of AOH+ to As(V) in pres-
ence of tartaric acid in micellar media at pH 5.0. The most serious
interference has been observed from Cu2+, Sb3+, Sb5+, Fe3+, MoO2 4 ,
CrO2 
4 and NO2 ions. The interference caused by Cu(II), Sb(III; V),
Fe(III), Mo(VI) and Cr(VI) may be due to complexation with tartaric
acid. The interference of nitrite may be due to either reduce As(V)
tor As(III) or electrophilic addition to unsaturated C-atom available
on 9 position according to hetero O-atom in dye molecule so as to
give nitrosyl addition product. The interference of nitrite was elim-
inated up to a tolerance ratio of 125-fold by using 0.1 mL of
3.0  103 mol L1 sulfamic acid solution prior to CPE. The interfer-
ences of Cu(II) and Sb(III) respectively were eliminated up to toler-
ance ratios of 150- and 100-folds by using 0.2 mL of 1.0  103
mol L1 Na2S2O3 solution. The interferences of Fe(III), Sb(V), Cr(VI)
and Mo(VI) respectively were eliminated to tolerance ratios of 100-
and 150-folds after pre-reduction with 0.3 mL of 0.01 mol L1
ascorbic acid solution. Similarly, the interference of Cr(VI) could
be eliminated to a tolerance ratio of 150-fold after pretreatment
with 0.2 mL of 1.0  103 mol L1 Na2SO3 solution.
6. Optimization of oxidation of As(III) to As(V), and
determination of total i-As
Initially, two oxidizing agents with different advantages and dis-
advantages at 25 °C, 35 °C and 45 °C were studied for pre-oxidation
of As(III) to As(V). Hydrogen peroxide (H2O2) in alkaline media is a
suitable and reliable oxidant in alkaline media, which allows rapid
38 R. Gürkan et al. / Food Chemistry 180 (2015) 32–41

Table 2(a)
The total As, As(V) and As(III) contents of CRMs obtained by using the proposed CPE-spectrophotometric method.
* a b,c
CRMs Certified value Observed value Recovery% RSD% iAS% The
experimental
Total iAs As(V) As(III)
t-and F-values
1 ** ***
CRM 1568a rice flour (lg kg ) 280 ± 7, 104.3 ± 4.4 103.5 ± 4.2 32.5 ± 1.2 70.6 99.2 4.1, 3.7 37.0 0.43 and 1.1
CRM 1643e simulated fresh water-trace elements 58.98 ± 0.70 57.5 ± 1.5 54.8 ± 1.2 2.70 97.5 2.6, 2.2 – 0.64 and 4.6
(lg L1)
a
The critical F(4,4) value is 6.39 for 95% confidence level and four degrees of freedom.
b
The experimental t-values calculated by using l = xaverage ± tSD/N1/2 for five replicate measurements at confidence interval of 95% in which the critical t-value is 2.78 for 4
degrees of freedom at confidence interval of 95%.
c
The critical F(4,4) value is 6.39 for 95% confidence level and four degrees of freedom.
*
The averages and its standard deviations of five replicate measurements for total As and As(V) at confidence interval of 95%.
**
The certified value of total As (N: 11) with uncertainty expressed as confidence interval of 95%.
***
The certified value of total inorganic As, As(V) plus As(III) (N: 11) with uncertainty expressed as confidence interval of 95%.

Table 2(b)
The total As, As(V) and As(III) contents of some selected waters, beverages with and without alcohol (sample volumes of 3 mL for all water and beverage samples, N: 5).

As(V) Total As As(III)

a
Samples Dilution ratio Added (lg L1) Found (lg L1) RSD% *
Recovery% Found (lg L1) RSD% Recovery% Added (lg L1) Found (lg L1)
Hot spa water 1/5 – 1.90 ± 0.09 4.7 – 2.90 ± 0.12 4.1 – – 1.0
10 11.5 ± 0.4 3.5 96.0 22.4 ± 0.8 3.6 97.8 10 9.5
50 51.2 ± 1.5 2.9 98.6 102.1 ± 2.3 2.3 99.2 50 49.2
150 151.1 ± 2.5 1.7 99.5 301.8 ± 4.5 1.5 99.6 150 148.9
– 0.90 ± 0.04 4.4 – 1.50 ± 0.06 4.0 – – 0.6
Cold spa water 1/5 10 10.7 ± 0.4 3.7 98.0 20.4 ± 0.8 3.9 94.5 10 8.9
50 50.5 ± 1.6 3.2 99.2 100.5 ± 2.3 2.3 99.0 50 49.0
150 150.5 ± 2.5 1.7 99.7 300.2 ± 4.5 1.5 99.6 150 148.7
– 0.80 ± 0.04 5.0 – 1.10 ± 0.05 4.5 – – 0.3
Drinking water 1/5 10 10.3 ± 0.4 3.9 95.0 21.3 ± 0.8 3.6 101.0 10 10.2
50 49.6 ± 1.5 3.0 97.6 101.6 ± 2.1 2.1 100.5 50 50.5
150 149.5 ± 2.5 1.7 99.1 300.4 ± 4.8 1.6 100.1 150 149.3
– 2.90 ± 0.12 4.1 – 4.6 ± 0.2 4.3 – – 1.7
Efes Pilsen beer 1/25 10 12.6 ± 0.4 3.2 97.0 23.5 ± 0.8 3.4 94.5 10 8.9
50 51.3 ± 1.4 2.7 96.8 103.2 ± 2.5 2.4 98.6 50 48.6
150 151.0 ± 2.5 1.7 98.7 302.7 ± 5.0 1.7 99.4 150 148.1
– 3.5 ± 0.18 5.1 – 6.1 ± 0.3 4.9 – – 2.6
Red wine 1/25 10 13.0 ± 0.5 3.8 95.0 25.6 ± 1.5 3.6 97.5 10 9.5
50 52.5 ± 1.5 2.9 98.0 104.7 ± 2.5 2.4 98.6 50 48.6
150 152.1 ± 2.5 1.6 99.1 303.7 ± 4.5 1.5 99.2 150 147.6
– 1.6 ± 0.07 4.4 – 2.8 ± 0.12 4.3 – – 1.2
Cherry Juice 1/15 10 11.2 ± 0.4 3.6 96.0 22.3 ± 0.8 3.6 97.5 10 9.5
50 50.7 ± 1.2 2.4 98.2 100.9 ± 2.5 2.5 98.1 50 48.1
150 149.8 ± 2.5 1.7 98.8 300.7 ± 4.3 1.4 99.3 150 147.9
– 2.2 ± 0.1 4.5 – 3.7 ± 0.2 4.1 – – 1.5
Apricot juice 1/15 10 11.7 ± 0.4 3.4 95.0 23.1 ± 0.8 3.5 97.0 10 9.4
50 51.3 ± 1.5 2.9 98.2 102.3 ± 2.5 2.5 98.6 50 48.6
150 150.1 ± 3.5 2.3 98.6 301.2 ± 4.7 1.6 99.1 150 147.5
– 0.7 ± 0.04 5.7 – 1.0 ± 0.05 5.0 – – 0.3
Peach juice 1/15 10 10.2 ± 0.4 3.9 95.0 20.1 ± 0.9 4.0 95.5 10 9.1
50 48.5 ± 1.5 3.1 95.6 98.6 ± 2.5 2.5 97.6 50 47.6
150 147.8 ± 3.5 2.4 98.1 297.4 ± 4.5 1.5 98.8 150 146.4
a
The average values plus their standard deviations of five replicate measurements based on standard addition calibration curves with three point above the method
detection limit.
*
The percent recoveries obtained for five replicate measurements.

and complete oxidation of As(III) to As(V) at room temperature out
of any interfering of excess amount of H2O2 in total As determina-
tion step. Suitable aliquots of As(III) plus As(V) mixtures (preferably
at ratios; 50:0, 8:1, 3:1, 1:1, 1:3, 1:8 and 0:50) were taken in a 50 mL
of conical flask. Five mL of H2O2 (3 mol L1) was added to samples
for oxidation of As(III) to As(V). Then, the resulting solution was
allowed to stand at room temperature at 10 min to ensure complete
oxidation. After the oxidation of As(III) to As(V), pH of the solutions
was adjusted to 7.0 with diluted NaOH solution (1.0 mol L1). Then,
the proposed method was applied for the determination of the total
As as As(V). The mixtures were analyzed by proposed method to
determine the total i-As levels. The conditions of the oxidation pro-
cess are shown in Fig. 3. The same procedure was also conducted
without oxidation with H2O2 in alkaline medium for the aforemen-
tioned binary mixtures. The As contents were calculated by using a
calibration curve. However, the amount of As(III) ions were calcu-
lated from the difference between the amounts of As(V) and total
As before and after oxidation due to give more accurate and precise
results. The recovery experiments of the speciation procedure were
carried out by the analysis of samples spiked. The speciation results
 R. Gürkan et al. / Food Chemistry 180 (2015) 32–41 39

are extensively given in Table 1. The same procedure was applied to

3.1,
RSD%

5.2
4.1

1.7

4.1
2.9

5.6
4.2
3.1
1.5
4.4
3.4
2.2
1.4
5.0

2.0
determine the inorganic arsenic species in real samples.

5.4,
3.3,
2.9,
1.6,
5.2,
4.9,
2.7,
1.8,
5.1,
4.3,
2.5,
1.2,
4.8,
3.4,
2.4,
1.3,
a,b

7. Accuracy and analytical applications of the proposed CPE

Recovery%

method

98.9,102.2
99.5, 99.3

98.4, 98.2
99.1, 99.4

101, 99.4
98.6,98.2

98, 97.4
97, 97.2
95, 98

96, 95

97, 98

95, 94
–, – In order to control the accuracy of the proposed method, the
a,b

–
method was applied into two CRMs: CRM 1568a rice flour and
The experimental t- and F-values

CRM-1643e simulated fresh water-trace elements. From experi-

mental data, it has been found that the recoveries are quantitative
in range of 97.5–103.4% with a RSD in range of 2.6–4.0% for total i-
As equivalent to As(V). Accuracy and precision parameters are
summarized in Table 2(a). The results obtained are in good agree-

average values and their standard deviations obtained after ultrasonic assisted digestion with a mixture of HCl-HNO3-H2SO4 (3:2:1, v/v) prior to detection with CPE/UV–Vis.
average values and their standard deviations obtained after ultrasonic assisted digestion with a mixture of HCl-HNO3-H2O2 (3:2:1, v/v) prior to detection with CPE/UV–Vis.
ment with the certified values.
Also, we have investigated the applicability of the CPE method-
ology using preconcentration with AOH+ ligand in presence of tar-
1.2

1.2, 1.2

1.4, 1.3

1.3, 1.1

taric acid and Triton X-114 for the determination of amounts of

**
1.3,

arsenic speciation in different real samples such as water, beverage

*,c

–
–

–
–
–

–
–
–
*

and rice samples. The samples were pre-treated with wet diges-
tion, according to procedure explained in Section 2.3. Three mL
Found, lg kg1 after ultrasonic assisted digestion with a

of the prepared solution samples were transferred into volumetric

tubes of 50 mL individually. Then, the method in range of 10–
As(III)
1.20

1.50

2.20

150 lg L1 As(V) and As(III) was applied to determine the amounts
1.0
mixture of bHCl/HNO3/H2SO4 (3:2:1, v/v) (N: 3)

–
–
–

–
–
–

–
–
–

–
–
–

of As(V) and As(III) by using the standard addition method. After

oxidation of As(III) to As(V), the method was applied to determine
the amount of total As. The amount of As(III) was determined by
calculating the difference between total i-As and As(V). The results
The total As, As(V) and As(III) contents of rice samples after preconcentration by UV–Vis/CPE (sample amount of 0.2 g for all rices, N: 3).

51.1 ± 1.3
150.7 ± 2.3

50.7 ± 1.2
151.7 ± 2.3

52.2 ± 1.5
151.8 ± 2.2

52.8 ± 1.2
151.3 ± 2.1
1.30 ± 0.1
11.1 ± 0.4

1.60 ± 0.2
11.3 ± 0.4

2.80 ± 0.3
12.3 ± 0.5

3.20 ± 0.3
12.6 ± 0.5

obtained for beverage samples are shown at Tables 2(b) and 2(c).
As(V)

Tables 2(b) and 2(c) show that the recoveries are quantitative for
As(V) analysis, in range of 95.0–99.7% with a RSD of 1.6–5.1%,
and for total As analysis in range of 94.5–101.0% with a RSD of
1.4–5.0%.
recoverr rates and RSDS obtained for three replicate measurements by two different digestion procedures.

According to literature data, a sensitivity improvement has

2.30 ± 0.12

2.60 ± 0.13

4.30 ± 0.24

5.40 ± 0.24
51.4 ± 1.6
151.3 ± 2.5

51.7 ± 1.5

55.7 ± 1.7
153.6 ± 2.2

54.1 ± 1.2
151.2 ± 2.1
12.1 ± 0.5

12.1 ± 0.5

151.7 ± 3.0

14.1 ± 0.6

14.8 ± 0.5

been achieved by the method when compared to previously

experimental t- and F-values calculated by using xaverage, 2  xaverage, 1 = ± tSDpooled /(N1 + N2/N1N2)1/2.
Total As

reported works using HG-FT-IR, FAAS, HG-AAS, FI-HG-AAS, IC-

HG-AFS, ET-AAS, ICP-OES and ICP-MS with and without preconcen-
tration using CPE. The detection limit, LODs and preconcentration
tabulated Student’s t-value is 2.78 for 95% confidence level and four degrees of freedom.

factor, PF obtained in this study is better than or comparable to

Found, lg kg1 after ultrasonic assisted digestion with a

those of the reported other detection methods (Azhar, Zuhair, &

Kasim, 2014; Gallignani et al., 2002; Hsieh et al. 2010;
As(III)

critical F(4,4) value is 6.39 for 95% confidence level and four degrees of freedom.
1.10

1.20

1.50

2.10

Korenovska, 2006; Moreno et al., 2000; Tang, Ding, & Yan, 2005;
mixture of aHCl/HNO3/H2O2 (3:2:1, v/v) (N: 3)

–
–
–

–
–
–

–
–
–

–
–
–

Ulusoy et al., 2011a,b; Zhan, Yu, Jing, & Lumei 2013) for except
those of hyphenated techniques based separation with CE and LC
as well as DP-CSV and TRXRF (Barros, Parra, Bennun, & Greaves,
51.2 ± 1.3
150.8 ± 2.3

50.9 ± 1.3
150.4 ± 2.3

52.0 ± 1.4
151.6 ± 2.5

52.6 ± 1.3
151.5 ± 2.3
1.30 ± 0.1
11.1 ± 0.4

1.50 ± 0.2
11.3 ± 0.4

2.60 ± 0.3
12.3 ± 0.5

3.10 ± 0.3
12.5 ± 0.5

2010; Coelho, Carmen, Cervera, Pastor, & Guardia, 2003; De

Carvalho & Leandro, 2012; Coelho et al., 2005; Moreira et al.,
As(V)

2011). Also, it has relatively a wider working range and good pre-
cision at low concentrations. Moreover, the RSDs as a measure of
precision is better than to previous results with CE and LC separa-
tion including TRXRF, DP-CSV and detection techniques with
hydride generation. As a result, the method provides advantages
2.40 ± 0.13

2.70 ± 0.14

4.10 ± 0.21

5.20 ± 0.25
51.7 ± 1.5
151.7 ± 2.5

51.9 ± 1.4
151.4 ± 2.7

53.5 ± 1.3
155.7 ± 1.9

54.2 ± 1.3
11.9 ± 0.4

12.3 ± 0.6

13.8 ± 0.6

14.7 ± 0.5

150.7 ± 2.0

of wider linear range, low detection limit, high selectivity, good

Total As

precision, adequate accuracy, quantitative recovery and compara-

ble preconcentration factor for the spectrophotometric detection
of trace i-As species in water, rice and beverage samples. So, it
Added As(V) (lg kg1)

can locally be considered as very useful analytical tool for accurate

and precise monitoring of trace As in the samples.

8. Conclusions
–
10
50

–
10
50

–
10
50

–
10
50
150

150

150

150

Because the As in real samples is present at low amounts, it usu-

ally needs either a separation/preconcentration step or sensitive
Samples

Sample

Sample

Sample

Sample
Table 2(c)

and element selective detection techniques such as ETV-ICP OES,

The
The
The
The
The
The

FI-VG-ICP-MS, HG-ICP-OES, which are very expensive and com-

1

c
b
a

**
a,b

plex. Thus, in the present study, an innovative CPE approach based

40 R. Gürkan et al. / Food Chemistry 180 (2015) 32–41
on ion-pairing complex formation was efficiently developed as a
separation and preconcentration tool to detect the amounts of
inorganic arsenic species in drinking water, soft drinks, alcoholic
beverages and rice with the main analytical capabilities. In this
context, the AOH+ as selective and sensitive As(V) binding reagent
in presence of tartaric acid at pH 5.0 was successfully used for the
first time for their speciative determination of i-As species present
in the selected samples by UV–Vis spectrophotometry. The cloud
point methodology using Triton X-114 as extracting agent is easy
to use, rapid, cost-effective and eco-friendly. Also, the CPE proce-
dure combined with UV–Vis spectrophotometry can efficiently be
used in accurate and reliable analysis of i-As species contents of
more complex matrices with sufficient sensitivity and selectivity
in a wide linear range without needing any expensive instrument.
Acknowledgments
This study has been supported by Cumhuriyet University Scien-
tific Research Projects Commission as the research projects with
the F-417 code.
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