Determination of iron in water samples by adsorptive

stripping voltammetry with a bismuth film electrode

in the presence of 1-(2-piridylazo)-2-naphthol
Rodrigo Segura a,∗ , Marı́a Inés Toral a , Verónica Arancibia b
a
Departamento de Quı́mica Analı́tica, Facultad de Quı́mica, Universidad de Chile,
Las Palmeras 3425, Casilla 653, Santiago, Chile
b Departamento de Quı́mica Inorgánica, Facultad de Quı́mica, Pontificia Universidad Católica de Chile,

Vicuña Mackenna 4860, Santiago 22, Chile

Abstract
An adsorptive stripping voltammetry method for the determination of iron has been developed. The procedure is based on the adsorptive collection
of a complex of iron with 1-(2-piridylazo)-2-naphthol (PAN) on a bismuth-coated glassy carbon electrode (BiFE). Factors affecting the stripping
performance, such as pH, PAN concentration (CPAN ), potential, accumulation time (Eads , tads ), and interference by other ions were also studied.
The optimum conditions were obtained in a 0.1 mol L−1 acetate buffer at pH 4.0, CPAN 5.0 ␮mol L−1 , tads 60 s, Eads −400 mV, pulse height 4.0 mV,
pulse amplitude 25 mV, and frequency 15 Hz. The detection limit was found to be 0.1 ␮g L−1 when a tads of 60 s was used, and the linear range
was from 0.4 to 60.0 ␮g L−1 . The proposed procedure was validated by determining of Fe(III) in CRM-MFD, QCS-19 and CRM-SW certified
reference materials and applied in seawater samples with satisfactory results.

Keywords: Adsorptive stripping voltammetry; Iron; 1-(2-Piridylazo)-2-naphthol (PAN); Seawater samples; Bismuth film electrode

1. Introduction 2000 and December 2002. The exercise was conducted as a

rigorously “blind” comparison of seven analytical techniques
Total dissolved iron in surface waters of oceanic regimes by 24 international laboratories. For the complete dataset of 45
can range from less than 0.05 to greater than 10 nmol L−1 results (after excluding three outliers not passing the screen-
[1–3]. However, in some beaches near populated or indus- ing criteria), the mean concentration of dissolved iron in the
trial areas iron concentration can be higher. The analysis of ironages samples was 0.59 ± 0.21 nmol L−1 , with a coefficient
iron in seawater is difficult due to both the low concentrations of variation of 36% [4]. Higher values were found in acidi-
and the seawater matrix. Therefore, shipboard determination fied samples from Monterey Bay by a flow injection method
of iron in seawater requires a sensitive analytical technique combined with inductively coupled plasma sector field mass
and trace-metal clean sample handling to obtain meaningful, spectrometry (ICP-SFMS) using the NTA superflow resin in
oceanographically consistent results. The presence of iron in the preconcentration step (average 2.89 nmol L−1 ) [5]. Iron can
research vessels, laboratories and many manufactured materi- be determined by several methods such as inductively coupled
als poses a risk of contamination during sampling, filtration, plasma mass spectrometry (ICP-MS) [6], electrothermal atom-
storage and analysis. The first large-scale international inter- ization atomic absorption spectrometry (ETAAS) [7], cathodic
comparison of analytical methods for the determination of stripping voltammetry (CSV) [8–10], luminescence [11], and
dissolved iron in seawater was carried out between October spectrophotometry [12], preceded sometimes by column precon-
centration. However, most of the sensitive and selective methods
available are expensive to be used in routine analysis (ICP-MS
∗ Corresponding author. Tel.: +56 29787262. and ETAAS). Electroanalytical techniques like anodic stripping
E-mail address: [email protected] (R. Segura). voltammetry (ASV), cathodic stripping voltammetry (CSV),
and adsorptive stripping voltammetry (AdSV) have important Certified reference material of seawater (CRM-SW), trace met-
advantages including high sensitivity, accuracy and precision, als in mixed food diet (CRM-MFD) reference materials, and
as well as the low cost of instrumentation. AdSV is based on quality control standards (QCS-19) obtained from high-purity
prior accumulation of the analyte on a suitable working electrode standards (Charleston, SC, USA) were used for validation
by potential controlled adsorption and subsequent electrochem- measurements.
ical oxidation or reduction of the preconcentrated species. For
decades, due to several electrochemical advantages, mercury 2.3. Preparation of BiFE electrode
electrodes have been widely used in stripping analysis. How-
ever, the well-known toxicity and handling inconveniences of The glassy carbon electrode (GCE) was polished with 0.3-␮m
mercury have recently declined considerably the popularity of alumina powder, then, washed with deionized water in an ultra-
mercury electrodes. The bismuth film electrode (BiFE) was sonic bath. Bismuth was deposited on the GCE from 10.0 mL of
introduced as an extremely promising alternative, based in that a 100 mg L−1 Bi(III) solution containing 0.1 mol L−1 of acetate
no present toxic character in relation to with those mercury buffer (pH 5.0) at an applied potential of −1000 mV vs. Ag/AgCl
electrodes [13–22]. BiFE has been used principally in anodic for 5 min with stirring. The modified electrode was rinsed with
stripping voltammetry (Fe(III) [23]; Sn [24]; U [25]; Co [26–28]; water and was ready for use.
Ni [29]; Mo [30]; Cr [31,32]; V [33]) and over the last years
(2003–2007), a few selected application of AdSV on the BiFE 2.4. Procedure
have also been reported with promising results (Cr with DTPA
[34]; Co-DMG [35–37]; Ni-DMG [38]; Co and Ni with DMG All bottles and containers used for standards and samples
[39–41]; U-Cupferron [42]; Al-Cupferron [43]). were thoroughly cleaned with 5% nitric acid before use. Fil-
The aim of this study was to optimize the determination of tration was done through 0.45-␮m membrane filters. Seawater
iron using the bismuth film electrode. The metal was accumu- samples were obtained from five different beaches of Viña del
lated as the Fe(III)-1-(2-piridylazo)-2-naphthol (PAN) complex. Mar (Chile) in a highly populated zone and near copper and oil
This ligand has been widely used as chomophore reagent in industries.
spectroscopic techniques for the determination of several metal All voltammetric measurements were carried out in
ions at trace level, but there are no reports on adsorptive strip- 0.10 mol L−1 acetate buffer solution (pH 4.0) at room temper-
ping voltammetry with BiFE. The method was validated using ature (23 ± 2 ◦ C) containing 5.0 ␮mol L−1 PAN as complexing
certified reference material (CRM-MFD mixed food diet and agent. The solution was purged with nitrogen for at least 5 min.
QCS-19 standard solution) and was applied to the analysis of A deposition potential of −400 mV vs. Ag/AgCl was applied to
seawater samples obtained from five beaches in highly populated the working electrode. During the deposition step, the solution
zones. was stirred, and after an equilibration period of 10 s the voltam-
mogram was recorded by applying a negative-going potential
2. Experimental scan between −300 and −1100 mV. Square wave voltammo-
grams were obtained with an amplitude of 25 mV, a frequency
2.1. Instruments of 15 Hz, and a potential step of 4 mV.

Square wave adsorptive stripping voltammograms 3. Results and discussion

(SWAdSV) were obtained with a CV50W Voltammetric
analyzer (Bioanalytical Systems, Inc., BAS, USA). A 10 mL 3.1. Cyclic voltammetry
capacity cell was equipped with Ag/AgCl/KCl 3 mol L−1
reference electrode, a glassy carbon working electrode (3-mm Two successive cyclic voltammograms of a solution contain-
diameter, BAS, USA) and auxiliary platinum electrode. A ing PAN in the presence and absence of Fe(III) are shown in
mechanical mini-stirrer, and a capillary to supply an inert gas Fig. 1 (scan between −300 and −1250 mV). In the absence of
were also used. An Orion pH meter was used to determine the Fe(III) a cathodic peak was obtained at −470 mV (solid line
pH of the solutions. in Fig. 1), attributed to the reduction of free PAN. In the pres-
ence of Fe(III) the voltammograms show two peaks at −470 and
2.2. Reagents −670 mV (dotted line in Fig. 1). The second peak is attributed
to the reduction of the Fe(III)–PAN complex. In the back scan
All solutions were prepared with ultra pure water from a Mil- no peaks were observed, suggesting that the reduction of the
lipore Milli-Q system (Milford, MA, USA). Bismuth and iron free PAN and the reduction of the complex are irreversible pro-
standard solutions (1000 mg L−1 ) were obtained from Merck cesses.
(Darmstadt, Germany). Acetic acid buffers (pH 3.0–6.0) were
prepared by mixing 5.7 mL of acid and diluting to 1 L with 3.2. Effect of pH
water. The pH was adjusted with sodium hydroxide solution.
A 1 mmol L−1 solution of PAN (Sigma) was prepared by dis- The formation of the complexes and their stability are
solving 0.2493 g of solid compound in 100 mL of ethanol. strongly dependent on the pH of the solution. The influence
ASTM D 665 synthetic seawater was obtained from Aldrich. of pH on the peak current of the Fe(III)–PAN complex was
Fig. 1. Cyclic voltammograms of a solution containing 10.0 ␮mol L−1 PAN Fig. 3. Effect of accumulation potential on the peak current of the Fe–PAN
(solid line) plus 20.0 ␮g L−1 Fe(III) (dotted line) in 0.1 mol L−1 acetate buffer, complex. Conditions: Fe(III) 10.0 ␮g L−1 ; PAN 5.0 ␮mol L−1 ; supporting elec-
pH 4.0, with Eads −400 mV, tads 60 s, and a scan rate of 100 mV s−1 . trolyte 0.1 mol L−1 acetate buffer, pH 4.0; tads 60 s; amplitude 25 mV; frequency
15 Hz; step potential 4 mV, and stirring speed in the accumulation step 700 rpm.

studied in the range of pH 3.0–6.0 in acetate buffer media 3.4. Effect of accumulation time
(Fig. 2). It was found that at pH 4.0 the peak current of
the Fe(III)–PAN complex was maximum. At higher pH val- The effect of accumulation time on the Fe(III)–PAN com-
ues the peak current decreases and then remains constant. plex peak current was studied in the 0–400 s range in solutions
This profile indicates that about pH 4.0 offers the most favor- containing 0.5, 0.9 and 10.0 ␮g L−1 of Fe, as illustrated in
able performance, and this value was used in all succeeding Fig. 4. It is seen that the peak current of the Fe(III)–PAN com-
measurements. plex increases linearly as accumulation time increases, up to
80 s (10.0 ␮g L−1 ), 120 s (0.9 ␮g L−1 ), and 200 s (0.5 ␮g L−1 ).
3.3. Effect of adsorptive potential At longer times the peak current for higher concentration
(10.0 ␮g L−1 ) decreased notoriously and for 0.5 and 0.9 ␮g L−1
The adsorption of a complex on BiFE depends strongly not concentration became almost constant, probably due to sat-
only on the potential at which the accumulation process is car- uration of the film electrode. For succeeding studies an
ried out, but also on both the complex and the electrode charge. accumulation time of 60 s was chosen.
Complexes with positive charge will be adsorbed strongly on
surfaces with a negative charge. The effect of adsorptive poten- 3.5. Effect of PAN concentration
tial on the peak current of the Fe(III)–PAN complex was studied
in the range between −300 and −1100 mV (Fig. 3). The peak PAN concentration affects greatly the voltammetric peak
current due to the Fe–PAN complex increased from −300 to height. Fig. 5 shows the effect when PAN concentration was var-
−400 mV and then decreased to zero. The peak current was ied from 1.0 to 17.0 ␮mol L−1 . The peak current of the complex
obtained at about −400 mV, and this value was used in all later was maximum between 3.8 and 5.0 ␮mol L−1 of ligand concen-
measurements. tration; for higher values a significant decrease was seen due to

Fig. 4. Effect of accumulation time on the peak current of the Fe–PAN complex.
Fig. 2. Effect of pH on the peak current of the Fe–PAN complex. Conditions: Conditions: Fe(III) 0.5, 0.9, and 10.0 ␮g L−1 ; PAN 5.0 ␮mol L−1 ; supporting
Fe(III), 10.0 ␮g L−1 ; PAN, 5.0 ␮mol L−1 ; supporting electrolyte, 0.1 mol L−1 electrolyte 0.1 mol L−1 acetate buffer, pH 4.0; Eads −400 mV; amplitude 25 mV;
acetate buffer; Eads −400 mV; tads 60 s; amplitude 25 mV; frequency 15 Hz; step frequency 15 Hz; step potential 4 mV, and stirring speed in accumulation step
potential 4 mV, and stirring speed in the accumulation step 700 rpm. 700 rpm.
 Table 1
Analytical results of Fe determination in synthetic seawater, in certified reference
material and in seawater samples
Sample Fe found (␮g L−1 ) Fe certified (␮g L−1 )

Synthetic seawatera 11.0 ± 1.0 10.0 spiked

Synthetic seawatera 41.0 ± 2.5 40.0 spiked
CRM-MFD mixed food 823.0 ± 0.3 800.0
dietarya
QCS-19 quality controla 109.3 ± 4.0 mg L−1 100.0 mg L−1
CRM-SWa 23.0 ± 1.2 20.0
1b 58.0 ± 1.9 60.0 ± 0.2c
2b 41.0 ± 1.3 40.0 ± 0.2c
3b 6.0 ± 0.8 5.0 ± 0.2c
4b 42.0 ± 1.5 40.0 ± 0.2c
Fig. 5. Effect of PAN concentration on the peak current of 10.0 ␮g L−1 Fe(III). 5b ND NDc
Conditions: supporting electrolyte 0.1 mol L−1 acetate buffer, pH 4.0; Eads a n = 8.
−400 mV; tads 60 s; amplitude 25 mV; frequency 15 Hz; step potential 4 mV b n = 3.
and stirring rate in accumulation step 700 rpm. c Values obtained with ICP-MS.

competitive adsorption between free PAN and the Fe(III)–PAN ation of 3.8% (tads 60 s). These results were obtained without
complex on the electrode. A PAN concentration of 5.0 ␮mol L−1 an electrochemical cleaning period, using the same bismuth
was used in all succeeding measurements. electrode surface, indicative of total desorption of the complex.

3.6. Construction of calibration curves and determination 3.7. Interferences

of detection limits and linear range
High sensitivity and reproducibility are coupled with high
For the evaluation of the analytical parameters, a study of selectivity. The possible interference of various trace metals
the influence of the concentration of the Fe(III)–PAN complex was investigated to test for selectivity. When a solution con-
was made in aqueous solution under the optimal conditions taining Ag(I), Al(III), As(III), Bi(III), Cu(II), Cd(II), Cr(III),
mentioned above. Measurements were made with successive Mo(VI), Ni(II) and Zn(II) at 100 ␮g L−1 concentration contains
additions of aliquots of Fe(III) solution, with increments of 20.0 ␮g L−1 of Fe(III) in the presence of 5.0 ␮mol L−1 of PAN
about 0.9 ␮g L−1 . An accumulation time of 60 s and an accu- (pH 4.0), the peak current of the Fe(III)–PAN complex was not
mulation potential of −400 mV were applied. Fig. 6(A) shows affected. This agrees with literature reports, because these met-
the voltammograms and Fig. 6(B) calibrate curve obtained. The als form complexes with PAN at pH higher than 4.0, and their
peak current increased linearly with metal concentration in the reduction peaks were not observed in this potential zone.
range of 0.9–60.0 ␮g L−1 (Y = 3.591x + 11.138; R2 = 0.998). The
detection limit was 0.10 ␮g L−1 as Fe(III) [44]. A series of
3.8. Validation of the methodology
repetitive measurements with 20.0 ␮g L−1 of Fe(III) solution
produced a very stable response with a relative standard devi-
The usefulness of the present method was evaluated by exam-
ining the analysis of Fe(III) in CRM-MFD mixed food diet,
seawater CRM-SW certified reference material, and QCS-19
quality control standards using an ex situ plated bismuth film
electrode. A standard addition method was used for Fe(III)
quantitation. Three replicate analyses were carried out for each
sample. The results are given in Table 1, indicating that the
proposed method is applicable to the analysis of seawater sam-
ples containing more than 0.1 ␮g L−1 of Fe(III). The proposed
method was successfully applied to the determination of iron
in synthetic seawater (ASTM D665) spiked with 10.0 and
40.0 ␮g L−1 of Fe(III).

3.9. Application of the proposed method

Fig. 6. (A) Adsorptive voltammograms of PAN solution in the presence of
increasing amounts of Fe(III). Conditions: Eads −400 mV; tads 60 s; amplitude Direct measurements of the samples were not possible due
25 mV; frequency 15 Hz; step potential 4 mV, and stirring speed in accumu- to lack of reproducibility. For that reason, 10.0 mL aliquots of
lation step 700 rpm (a) supporting electrolyte 0.1 mol L−1 acetate buffer, pH
the samples were previously digested with concentrated nitric
4.0; (b) PAN 5 ␮mol L−1 ; (c–i) Fe(III) 10.0, 20.0, 29.9, 39.8, 49.8, 59.6 and
69.5 ␮g L−1 . (B) Dependence of peak current of Fe(III)–PAN complex on Fe(III) acid and warmed on a hot plate almost to dryness. The pH was
concentration. then adjusted to 4.0, the volume was made up to 10.0 mL with
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