Microchemical Journal 164 (2021) 106058

Contents lists available at ScienceDirect

Microchemical Journal
journal homepage: www.elsevier.com/locate/microc

Indirect determination of aluminum (III) in water samples by in-electrode

coulometric titration
Jakub Masac , Jan Lovic , Ernest Beinrohr , Frantisek Cacho *
Institute of Analytical Chemistry, Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, Radlinskeho 9, Bratislava 812 37. Slovakia

A R T I C L E I N F O A B S T R A C T

Keywords: A new procedure has been developed for indirect determination of aluminium(III) in water through in-electrode
Aluminum coulometric titration in a porous reticulated vitreous carbon electrode. It was determined through different
Fluoride complexes aluminium fluoride and ferric fluoride complex stabilities. The ferric fluoride complex thereby formed was
Indirect determination
decomposed with Al(III) from the sample and an aliquot of the released Fe(III) was determined electrochemi­
In-electrode coulometric titration
cally. It was measured with an EcaFlow GLP 150 electrochemical flow analyser, while 0.2 mol L− 1 sodium
chloride solution was used as the electrolyte to flush the system. Calibration solutions and samples were modified
in a mixed solution medium of 0.2 mol L− 1 NaCl + 10 mg L− 1F(I-) + 10 mg L− 1Fe(III). All working parameters for
electrochemical determination were optimised. The detection limit and precision were found to be 0.02 mg L− 1
and 1.9% respectively. The linear concentration range was 0.05 – 8.5 mg L− 1 of aluminium. After having been
complexed with sodium cyanide, the iron’s interference effect was suppressed by removing it with an ion-
exchange resin. Among the other influences studied, only the interference from thorium, zirconium and
cerium was significant. The method was applied for the analysis of various water samples. The results were in
good agreement with data from high resolution atomic absorption spectrometry.

1. Introduction (chromatography, extraction, etc.) either to detect trace aluminium

Aluminium (Al) is a low density metal and the third most abundant
element in the earth’s crust (8%). It is produced industrially from
electrolysing molten bauxite and cryolite. Aluminium is used in various
industries, with the automotive and aerospace industries taking
advantage of the low density of its compounds. It is often utilised in
everyday items such as antiperspirants, food foils, kitchen utensils, etc.
Despite its high presence in the earth’s crust, aluminium is not part of
any living tissue. The World Health Organisation (WHO) has indicated a
possible link between aluminium and Alzheimer’s disease. The
maximum permitted concentration of aluminium in drinking water,
which does not reduce the water’s sensory quality, is 200 µg L− 1 [1].
Spectral methods are most commonly used to determine aluminium
in various types of samples. Examples of such methods include graphite
furnace atomic absorption spectrometry (GF-AAS) [2,3] flame atomic
absorption spectrometry (FAAS) [4] inductively coupled plasma atomic
emission spectrometry (ICPAES) [5] inductively coupled plasma mass
spectrometry (ICP-MS) [5,6] spectrofluorimetry [6,7] and spectropho­
tometry [8,9]. They are often combined with separation techniques
concentrations or to separate and determine the various forms of
aluminium [6,10–12]. Although these methods offer adequate sensi­
tivity and selectivity, photometric methods for treating samples are
often very difficult and time-consuming. Atomic spectrometry methods
are problematic because of the high thermal stability of aluminium
atoms.
Direct electrochemical determination of aluminium through its
reduction in water is almost impossible due to the significantly negative
redox potential (− 1.75 V vs. Ag/AgCl), which is close to the potential for
generating hydrogen and reducing alkali metal ions [13]. Anodic
stripping voltammetry (ASV) is the most common electrochemical
method for determination of aluminium. Electrodes with ligand (com­
plexing agents) treated surfaces are mostly used. The presence of a
ligand forming a complex with aluminium shifts the potential to more
positive values, due to the adsorption of the complex on the working
electrode. Stripping voltammetry, applied after complexation, is the
most sensitive method because it allows pre-concentration of the
aluminium on the electrode surface before measurement. The best-
known reagents used include Alizarin-S [14,15] Alizarin violet [16]

* Corresponding author.
E-mail address: frantisek.cacho@stuba.sk (F. Cacho).

https://doi.org/10.1016/j.microc.2021.106058
Received 16 September 2020; Received in revised form 23 November 2020; Accepted 25 December 2020
Available online 15 February 2021
0026-265X/© 2021 Elsevier B.V. All rights reserved.
J. Masac et al.
Morin [17,18] and many others.
This paper describes a new procedure for indirect electrochemical
determination of aluminium(III) in water. The determination is possible
because of the different stabilities of ferric fluoride and aluminium
fluoride complexes and also the different electrochemical properties of
the free ferric ions and the ferric ions bound with the fluoride in the
complex. Here a flow-through laboratory system was used, with in-
electrode coulometric titration in a reticulated vitreous carbon
electrode.
2. Experimental
The process discussed in this paper is based on the different fluoride
complex stabilities of Al(III) and Fe(III) in solution. A similar principle
was used by Cernanska et al. to determine fluorides in toothpastes [19].
Electrochemical reduction of Fe(III) on Fe(II) is a well-known process
that works on most electrode materials. Adding fluorides to a solution
containing Fe(III) immediately forms ferric fluoride complexes (pK3 =
12.06), which are electro-inactive at the reduction potential of free Fe
(III) ions. As fluoride ions are gradually added to the solution, the Fe(III)
reduction signal decreases to the level of the background signal. If a
solution of Al(III) ions is added to such a [Fe(III) + F(I-)] mixture, the
ferric fluoride complexes decompose and preferential aluminium fluo­
ride complexes are formed (pK6 = 19.84). The Fe(III) bound in the
complex is released into the solution, enabling its reduction on the
electrode. The detected signal from the reduction of free Fe(III) thus
increases as the concentration of Al(III) in the analysed solution in­
creases. Competing reactions are only possible with thorium and zir­
conium ions with their higher pK3 values. However, their occurrence in
real samples is unlikely.
2.1. Instrumentation
All the measurements were performed with an EcaFlow GLP-150
electrochemical analyser, manufactured by IstranLtd., Bratislava,
Slovakia. It is equipped with two solenoid inert valves, a peristaltic
pump and a computer controlled potentiostat/galvanostat [20]. Fig. 1
shows the flow diagram for the flow measuring cell device. All PTFE
tubes used in the analyser have an internal diameter of 1 mm. The
system allows measurements to be made in both calibration and
calibration-free mode. In calibration mode, results are calculated from
the calibration curve. When the calibration-free mode is used, a
Fig. 1. Block diagram of the flow-through analyser EcaFlow with the Flow-
through cell: V – solenoid valve, PP – peristaltic pump, 1- working electrode, 2 –
reference electrode, 3 – auxiliary electrode, 4 – membrane, 5 – packing, 6 –
screw, 7 – cell body, 8 – space for reference electrolyte (saturated KCl).
2
Microchemical Journal 164 (2021) 106058
computer automatically calculates the outcome according to Faraday’s
laws of electrolysis. Individual measurements are recorded by memory
mapping [21,22]. The graph itself resembles a derived chro­
nopotentiogram in shape, but it is actually recorded by filling the indi­
vidual channels in the built-in channel counter. Therefore, the displayed
record is not derived from the chronopotentiogram, but from gradually
plotting dt/dE counts depending on the gradual change in the potential.
Thus, it is primary coulometric thin-film titration and not derivative
chronopotentiometry, as it might seem. The working electrode (defined
below) used in the system consists of a large number of regularly con­
nected small cavities. These create a thin film of solution above the
surface of the electrode material, with the entire electrode serving as a
single coulometric vessel. Formally, the “counts” have a dimension of
V− 1, where the measurement always consists of two steps. First, the
background signal is measured from an analysis of a blank sample before
the standard or sample signal in the second step. The background signal
is then subtracted from the sample signal to obtain a clear record with no
background influence.
The measurement step involves filling the electrode with the ana­
lysed solution, reducing the Fe(III) to Fe(II) in the electrode’s pores. The
area of the reduction peak from the obtained record corresponds to the
time required to reduce Fe(III) in the electrode volume (i.e. the transi­
tion time τ from Faraday’s laws of electrolysis). Since the volume is
finite, the size of the peak area corresponds both to the amount of Fe(III)
in the electrode and the concentration of Fe(III) in the analysed solution,
and in this case also to the concentration of Al(III) there, too. Between
each measurement, the working electrode and the flow cell are washed
with the primary electrolyte.
A commercial compact flow-through electrochemical cell (type 104)
with Pt auxiliary and Ag/AgCl reference electrodes was used (Istran Ltd.,
Slovakia). The cylindrical working electrode was a reticulated vitreous
carbon plug of 100 ppi (pores per inch) porosity (Electrosynthesis Co.
Inc., Lancaster, New York, USA) of 4 mm and 10 mm in length and
diameter, respectively. All operating parameters required for measure­
ment are summarised in Table 1. These values were entered into a
control program in the personal computer that controlled the electro­
chemical analyser. The instrumentation allowed the measurement itself
to be fully automated. All potential values were reported against the
silver/silver chloride (Ag/AgCl) reference electrode built into the flow
cell [23].
High-resolution continuum source graphite furnace atomic absorp­
tion spectrometry was used as the reference method. A ContraAA HR-CS
GFAAS spectrophotometer, MPE 60 auto-sampler and a pyrolytically
coated cuvette with a PIN-platform were all used to determine the
aluminium in the water samples (wavelength: 309.2713 nm, calibration
curve range: 0.5–50 µg L− 1).
The same device was used to monitor the efficiency of the separation
of ferric ions from real water samples (wavelength: 425.0762 nm, cali­
bration curve range: 0.3–20 µg L− 1).
Table 1
Working parameters of the flow-through analyser.
Parameter Value Note
Potential at filling (mV) * 900 Filling the system
Starting potential (mV) * 900 Constant current is applied and potential
monitored
End potential (mV) * 200 Switched to the regeneration potential
Reduction current (µA) − 10
Regeneration potential 500 Regeneration of the electrode
(mV) *
Standby potential (mV) * 100
Flow rate (mL min− 1) 6
Sample volume (mL) 3
*vs. saturated Ag/AgCl reference electrode.
J. Masac et al.
2.2. Reagents and solutions
Analytical-reagent grade chemicals were used in all experiments.
The solutions were prepared in demineralized and boiled water
(NANOpure, Wilkem Werner GmBH, Germany).
Mass concentration was used for all the solutions since it is preferred
over molar concentration.
Aluminium(III) standard: The bulk standard solution of exactly
1.0000 g L− 1 Al(III) was prepared from aluminium nitrate nonahydrate
(.Al(NO3 )3 ⋅9H2 O, ⩾99.997\% trace metals basis, Sigma-Aldrich) in
water.
Iron(III) standard: The bulk standard solution of exactly 1.0000 g L− 1
Fe(III) was prepared from iron(III) nitrate nonahydrate
(Fe(NO3 )3 ⋅9H2 O, ⩾99.999\% trace metals basis, Sigma-Aldrich) in
water.
Fluoride standard: Fluoride standard for IC (TraceCERT®, 1000 mg/
L fluoride in water, Sigma-Aldrich) was used.
KCN: The bulk solution of 0.0054 mol L− 1 KCN was prepared from
KCN(KCN, BioUltra, ≥98.0%, Sigma-Aldrich) in water.
Carrier electrolyte: 0.2 mol L− 1 NaCl was prepared from NaCl(NaCl,
ACS grade, Sigma-Aldrich)
HNO3 (Suprapur, 65%, Merck KGaA, Darmstadt, Germany)
Preparation of standards for calibration: A solution (designated A1)
was prepared from 2 mol L− 1 NaCl + 100 mg L− 1Fe(III) + 100 mg L− 1F
(I-). Five millilitres of A1 with the required amount of standard Al(III)
was added into a fifty-millilitre volumetric flask, which was afterward
filled with water.
Samples: 10 samples were analysed of underground, surface, drink­
ing and waste water gathered across Slovakia. The pH of every sample
was found to be approximately 7.
3. Result and discussion
The first step was to optimise and validate the determination of Fe
(III) using EcaFlow. The optimal concentration of fluoride was deter­
mined in the second step. The procedure for determining Al(III) was
validated in the third step and the process for removing iron from the
real samples was tested. LOD, LOQ, linear range, and the repeatability of
the determination were defined and several types of water samples were
analysed. The samples were subsequently analysed again using the
reference method.
3.1. Determination of Fe(III)
Free Fe(III) was determined from its reduction to Fe(II) on the sur­
face of the working electrode. The effect from the electrolyte’s pH is very
important for the determination. For best results, an electrolyte with a
pH in the range of 6–7 is appropriate (although some authors recom­
mend a pH of 5–7 [19]). A pH lower than the range reduces the
complexation efficiency of fluorides with Fe(III) and Al(III), while the
intensity of the measured free Fe(III) reduction signals drops at a higher
pH (of 8 and more). An aqueous NaCl solution was selected as the
suitable electrolyte because of its neutral pH and sufficient ionic
strength. The concentration of this electrolyte was optimised at the
range of 0.1 – 1 mol L− 1. The maximum signal intensity was observed
from a sodium chloride (NaCl) concentration of 0.2 mol L− 1. The
increased NaCl concentration in the electrolyte no longer increased the
signal, therefore an aqueous solution of NaCl with a concentration of 0.2
mol L− 1 was used as the electrolyte. In addition, the current required to
reduce Fe(III) to Fe(II) on the surface of the working electrode was
optimised to determine Fe(III). The reduction current ranged between
− 5 and 50 µA. As the current shifted toward zero, the intensity of the
measured signals (reduction time, i.e. transient time τ) gradually
increased. A current of − 10 µA was accepted as the optimal value.
Intense signals were obtained at this value while the repeatability of the
measurements had a satisfactory metrological quality (RSD = 2.3%) and
3
Microchemical Journal 164 (2021) 106058
the measurement was rapid enough (three minutes per analysis). Table 1
summarises all the parameters for determining Fe(III)- The following
basic validation parameters were used to determine Fe(III): linear range
of 0.1–10 mg L− 1, LOD = 0.03 mg L− 1, LOQ = 0.1 mg L− 1, relative
standard deviation (RSD) repeatability = 2.3%. The ULA-2 statistical
method was used to determine LOD and LOQ [24]. Fig. 2 shows the Fe
(III) reduction by the measuring device, while the calibration curve for
the determination of iron (0.1–10 mg L− 1) is displayed in Fig. 3A. All
measurements were made in calibration-free mode.
3.2. Determination of fluorides
To determine the most suitable fluoride concentration, a set of so­
lutions was prepared with a sodium chloride concentration of 0.2 mol
L− 1 + 10 mg L− 1Fe(III) and F(I-) concentrations in the range of 0.1–15
mg L− 1. After mixing, the solutions were immediately analysed ac­
cording to the conditions for determining free Fe(III) in the calibration-
free measuring mode. As the concentration of F(I-) increased in solution,
the measured signal of free Fe(III) decreased linearly at a range of
0.1–10 mg of L− 1fluorides. Fluorides do not react in an aqueous medium
with Fe(III) ions at a 1:1 ratio by mass, which was why the measured
signal did not drop to the zero limit, even in the described case, after the
solution of 10 mg of L− 1 of Fe(III) and 10 mg of L− 1 of fluorine(I-) had
been prepared. When the concentration of fluoride rose further, the free
Fe(III) signal in the solution continued to gradually decrease. But this
decline showed a non-linear dependence. Fig. 3B displays the wave­
forms for the decrease in the concentration of free Fe(III) in the solution,
depending on the added fluorides (up to a concentration of 15 mg L− 1F
(I-)). At this point, the described procedure can obviously be used to
indirectly determine soluble fluorides in water. Unusually, the calibra­
tion dependence would have a negative slope in this case.
3.3. Determination of Al(III)
A solution comprised of 0.2 mol L− 1 NaCl + 10 mg L− 1Fe(III) + 10
mg L− 1F(I-) was selected as the basic working solution for Al(III) addi­
tions. In this solution, the concentration of free Fe(III) decreased linearly
after complexation with the fluorides. The first assumption was that the
addition of even a minimal amount of free Al(III) would displace the Fe
(III) from the Fe(III)-fluoride complex to form an Al(III)-fluoride com­
plex. The second assumption was that a gradual linear increase in the
concentration of Al(III) in a solution would cause the concentration of
free Fe(III) in the solution to increase linearly, too. To verify these as­
sumptions, a set of solutions was prepared containing 0.2 mol L− 1 NaCl
+ 10 mg L− 1Fe(III) + 10 mg L− 1F(I-), adding Al(III) in a concentration
Fig. 2. Chronopotentiometric signals of a standard with 1 mg L− 1
Fe(III). Pa­
rameters listed in Table 1.
J. Masac et al.
Fig. 3. A- Concentration dependence of the Iron(III) signal. Regression line: y = 16.7305x + 0.8025; R2 = 0.9997. B- Dependence of free Fe(III) concentration in a
solution on fluoride concentration. Regression line: y = -13.8957x + 171.0011; R2 = 0.9998. End of the linear decrease in the signal indicated at a concentration of
10 mg L-1F(I-). C- Dependence of the concentration of free Fe(III) in a solution for different concentrations of Al(III) and a different concentration of fluorides. ■
Regression line: y = 101,2466 + 14,04937x, R2 = 0,9997/● Regression line: y = 32,4754 + 15,9965x, R2 = 0,9998/▴ Regression line: y = 1,5541 + 17,6668x, R2
= 0,9998.
ranging from 0.1 to 10 mg L− 1. An electrochemical analyser in
calibration-free mode measured the signal from free Fe (III) in all of the
solutions. As Fig. 3C shows, the free Fe(III) signal increased linearly in
the range of 0.1 – 8.5 mg L− 1 according to the assumptions. For the
completeness of outcomes, two more identical experiments were per­
formed with fluoride concentrations of 5 mg L− 1 and 15 mg L− 1. In the
first case [10 mg L− 1Fe(III) + 5 mg L− 1F(I -)], a linear increase in the
signal of free Fe(III) was observed as Al(III) was gradually added to the
solutions. The linear range of the calibration curve was only 0.1 to 4.5
mg L− 1 Al(III). The direction of the calibration curve did not change
compared to the system [10 mg L− 1Fe(III) + 10 mg L− 1F(I-)]. It only
shortened the linear range of the calibration curve. In the second case
[10 mg L− 1Fe(III) + 15 mg L− 1F(I-)], the dependence of the signal from
the free Fe(III) in the solution on the concentration of added Al(III) was
divided into two parts. The dependence was nonlinear at the concen­
tration range of 0.1 – 1.5 mg L− 1 Al(III). The linear increase in the signal
could be observed at the concentration range of 1.5 – 9.5 mg L− 1 Al(III).
In certain circumstances, such an arrangement could be used to deter­
mine Al(III) concentrations in a sample, but only to determine higher
concentrations and just at a relatively narrow range of them. These
experiments confirmed [10 mg L− 1Fe(III) + 10 mg L− 1F (I-)] to be the
model most suitable for indirect electrochemical determination of Al(III)
in water. Fig. 3C shows the measured signal waveforms from the Al(III)
concentration plotted for all three monitored systems. The correspond­
ing equations for the calibration lines of the linear areas are also given.
All of the experiments were repeated three times.
Preparation of samples for analysis: During determination, it was
crucial to control the concentration of iron in the sample. All iron was
first removed from the analysed samples and then an exactly known
amount of Fe(III) was added. A cyanide process was used to remove the
iron. Iron concentrations in the range of 0.5 – 10 mg per litre are com­
mon in water, but concentrations of 50 mg L− 1 have also been reported
[25]. In our samples, the iron concentration was determined by the HR-
CS-GFAAS method at the range of 0.5 – 5 mg L− 1. Fifty millilitres of KCN
solution at a concentration of 0.0054 mol L− 1 (about 350 mg L− 1, suf­
ficient for a concentration of 5 mg per litre iron) was added to 50 ml of
the sample. All the iron in the solution was bound to the [Fe(CN)6 ]3−
complex. The solution then flowed through a column made of Dowex®
1-X8 (a strongly basic anion exchanger in Cl− form by Merck). Both the
iron (as an anionic complex) and excess cyanides were removed from the
solution. Aluminium does not complex with cyanide, so it flowed
through the column unchanged. The central part of the sample eluate
was then collected in a glass beaker. It was then added to a 50-millilitre
volumetric flask, to which five millilitres of the A1 solution had been
pipetted. Afterward, the solution was analysed. The HR-CS-GFAAS
confirmed the iron in all samples to have been completely removed
from the remaining eluates. The anion-exchange resin was recycled with
4
Microchemical Journal 164 (2021) 106058
3 mol per litre of sodium chloride. During the recycling, the cyanide
eluate was collected in a KMnO4 solution.
WARNING: KCN is a lethal poison. Whenever working with it, the
necessary safety precautions should be taken! The procedure is only
applicable to waters with a neutral pH.
Preparation of the blank sample: Five millilitres of the A1 solution
was diluted with water to a volume of 50 ml in a volumetric flask and
used as the blank.
Preparation of samples for HR-CS GFAAS: Concentrated nitric acid
(50 µL per 50 mL sample) was added to the samples prior to analysis.
3.4. Analytical figures of merit
Table 2 lists the main metrological determination parameters. The
limit of detection (LOD) and limit of quantification (LOQ) were calcu­
lated from the calibration dependence using the ULA-2 method [24].
The repeatability of the measurement was determined from making
twenty measurements in rapid succession of the same solution at an
aluminium concentration of one milligram per litre. The duration of the
measurement corresponds to the analysis itself (no sample treatment).
The effect of selected ions commonly found in water was studied. No
effect on the determination outcome was detected from ions of Na(I), K
(I), Ca(II), Mg(II), Zn(II), Cu(II) and Ni(II) even in 100-fold excess. The
anion-exchange resin removed all anions (sulphates, nitrates, nitrites,
chlorides, bromides and bicarbonates) from the samples. Only Th(IV), Zr
(IV) and Ce(IV) ions increased the analytical signal by 15%, even in a
twofold excess, due to competing reactions. The added fluorides formed
more stable complexes with these ions than with aluminium. Notwith­
standing, their occurrence in real water samples is unlikely.
3.5. Analysis of real samples
An analysis of ten real samples verified the method’s accuracy. All of
the samples were treated as described to remove the iron. The results
obtained from the calibration curve and standard addition correlated
between each other and with the reference values obtained from HR-CS-
GFAAS (p = 0.05), according to Student’s t-test for a 95% confidence
interval. Table 3 shows the outcome of the analyses and the reference
Table 2
Metrological data.
Parameter Value
Linear range (mg L− 1) 0.05–8.5
Limit of detection (mg L− 1) 0.02
Limit of quantitation (mg L− 1) 0.05
Repeatability at 1 mg L− 1, n = 20, [RSD %] 2.5
Duration of a measurement (min) 3
J. Masac et al. Microchemical Journal 164 (2021) 106058

Table 3 References
Analysis of water samples.
[1] WHO, Aluminium in drinking-water, Background document for development of
Sample Linear calibration Standard addition Reference value
WHO guidelines for drinking-water quality, WHO/HSE/WSH/10.01/13, (2010).
(µg L− 1) (µg L− 1) (µg L− 1) [2] G. Dravecz, L. Bencs, D. Beke, A. Gali, Determination of silicon and aluminum in
1. Drinking water ≤ LOD ≤ LOD 15.3 ± 0.3 silicon carbide nanocrystals by high-resolution continuum source graphite furnace
2. Drinking water ≤ LOD ≤ LOD 9.8 ± 0.2 atomic absorption spectrometry, Talanta 147 (2016) 271–275, https://doi.org/
10.1016/j.talanta.2015.09.067.
3. Waste water 29.0 ± 0.5* 29.2 ± 0.8* 29.2 ± 0.7*
[3] L.A. Pereira, I. Gonçalves de Amorim, J.B. Borba da Silva, Development of
4. Waste water 22.6 ± 0.5* 22.7 ± 0.9* 22.6 ± 0.8*
methodologies to determine aluminum, cadmium, chromium and lead in drinking
5. Waste water*2 134.0 ± 3.0* 133.7 ± 4.6* 133.7 ± 2.4* water by ET AAS using permanent modifiers, Talanta 64 (2) (2004) 395–400,
6. Groundwater 89.1 ± 2.4 88.3 ± 3.0 90.5 ± 1.8 https://doi.org/10.1016/j.talanta.2004.02.026.
7. Groundwater 112.4 ± 3.8 110.9 ± 4 112.9 ± 2.1 [4] A. Safavi, S. Momeni, N. Saghir, Efficient preconcentration and determination of
8. Surface water 240.5 ± 3.6 141.3 ± 4.7 142.0 ± 2.7 traces of aluminum ion using silica-bonded glycerol sorbent, J. Hazard. Mat. 162
9. Surface water 190.1 ± 4.3 189.8 ± 5.5 189.7 ± 2.8 (1) (2009) 333–337, https://doi.org/10.1016/j.jhazmat.2008.05.044.
10. Surface water 304.8 ± 7.5 305.1 ± 7.7 305.1 ± 4.8 [5] M. Frankowski, A. Zioła-Frankowska, I. Kurzyca, K. Novotný, T. Vaculovič,
V. Kanický, M. Siepak, J. Siepak, Determination of aluminium in groundwater
*Dimension is mg L− 1. samples by GF-AAS, ICP-AES, ICP-MS and modelling of inorganic aluminium
*Neutralized waste water from aluminum production. complexes, Environ. Monit. Assess. 182 (1-4) (2011) 71–84, https://doi.org/
10.1007/s10661-010-1859-8.
[6] B. Fairman, A. Sanz-Medel, P. Jones, E.H. Evans, Comparison of fluorimetric and
values. Mean values and confidence intervals (95%) were calculated inductively coupled plasma mass spectrometry detection systems for the
from five measurements. The standard deviations were used to deter­ determination of aluminium species in waters by high-performance liquid
mine confidence intervals. The regression equation of the calibration chromatography, Analyst 123 (1998) 699–703, https://doi.org/10.1039/
A707999K.
graph was τ = 15.997c + 32.475, coefficient of determination R2 = [7] S.M.Z. Al-Kindy, A. Al-Hinai, N.K. Al-Rasbi, F.E.O. Suliman, H.J. Al-Lawati,
0.9998, where τ is the measured transition time in seconds and c denotes Spectrofluorimetric determination of aluminium in water samples using N-((2-
the Al(III) concentrations in mg L− 1. hydroxynaphthalen-1-yl)methylene) acetylhydrazide, J. Taibah Univ. Sci. 9 (4)
(2015) 601–609, https://doi.org/10.1016/j.jtusci.2015.03.009.
[8] P. Norfun, T. Pojanakaroon, S. Liawraungrath, Reverse flow injection
4. Conclusions spectrophotometric for determination of aluminium (III), Talanta 82 (1) (2010)
202–207, https://doi.org/10.1016/j.talanta.2010.04.019.
[9] O.D. Renedo, A.M. Navarro-Cuñado, E. Ventas-Romay, M.A. Alonso-Lomillo,
This paper describes a new alternative method for the indirect Talanta 196 (2019) 131–136, https://doi.org/10.1016/j.talanta.2018.12.048.
electrochemical determination of aluminium in water. The unique [10] M. Frankowski, Simultaneous determination of aluminium, aluminium fluoride
process enables an electrochemically inactive element to be determined complexes and iron in groundwater samples by new HPLC–UVVIS method,
Microchem. J. 101 (2012) 80–86, https://doi.org/10.1016/j.microc.2011.11.002.
in different water samples. It is suitable for all electroanalytical systems. [11] P. Matúš, I. Hagarová, M. Bujdoš, P. Diviš, J. Kubová, Determination of trace
Working electrodes made of reticulated vitreous carbon are adequate for amounts of total dissolved cationic aluminium species in environmental samples by
measurement with no further treatment required. Since these electrodes solid phase extraction using nanometer-sized titanium dioxide and atomic
spectrometry techniques, J. Inorg. Biochem. 103 (11) (2009) 1473–1479, https://
have a long life, it is a very inexpensive analysis. RVC electrodes have
doi.org/10.1016/j.jinorgbio.2009.08.004.
proven quite suitable for the analysis. Notwithstanding, there is no [12] P. Matúš, Evaluation of separation and determination of phytoavailable and
known reason for the process not to work with other carbon electrodes. phytotoxic aluminium species fractions in soil, sediment and water samples by five
The disadvantage of the process is the requirement to control the con­ different methods, J. Inorg. Biochem. 101 (9) (2007) 1214–1223, https://doi.org/
10.1016/j.jinorgbio.2007.06.014.
centration of Fe(III) in the samples. The use of potassium cyanide (KCN) [13] S. Thomas, D. Davey, D. Mulcahy, C.K. Chow, Determination of aluminum by
to completely remove the iron from the original samples was verified. adsorptive cathodic stripping voltammetry with 1,2-dihydroxyanthraquinone-3-
Where necessary, the KCN concentration can be adjusted according to sulfonic acid (DASA): effect of thin mercury film electrode, Electroanalysis 18 (22)
(2006) 2257–2262, https://doi.org/10.1002/(ISSN)1521-410910.1002/elan.v18:
the iron concentration in the samples. Of course, this does not rule out 2210.1002/elan.200503629.
any other suitable method for removing the ions. The determination [14] J. Zuziak, M. Jakubowska, Voltammetric determination of aluminum-Alizarin S
itself is very fast, the solutions easy to prepare and, as confirmed, the complex by renewable silver amalgam electrode in river and waste waters,
J. Electroanal. Chem. 794 (2017) 49–57, https://doi.org/10.1016/j.
process is applicable to different types of water samples. jelechem.2017.04.009.
[15] J. Zuziak, W. Reczyński, B. Baś, M. Jakubowska, Voltammetric determination of
CRediT authorship contribution statement aluminum(III) as Al-Alizarin S complex in tea leaves and infusions, Anal. Biochem.
558 (2018) 69–79, https://doi.org/10.1016/j.ab.2018.08.008.
[16] P. Deng, J. Fei, J. Zhang, Y. Feng Determination of trace aluminum by anodic
Jakub Masac: Data curation, Writing - original draft. Jan Lovic: adsorptive stripping voltammetry using a multi-walled carbon nanotube modified
Data curation. Ernest Beinrohr: Supervision. Frantisek Cacho: Visu­ carbon paste electrode Anal. Lett., 44 (2011), pp. 1521-1535, https://doi.org/
10.1080/00032719.2010.520382.
alization, Writing - review & editing.
[17] O. Domínguez-Renedo, A.M. Navarro-Cuñado, E. Ventas-Romay, M.A. Alonso-
Lomillo, Determination of aluminium using different techniques based on the Al
Declaration of Competing Interest (III)-morin complex, Talanta 196 (2019) 131–136, https://doi.org/10.1016/j.
talanta.2018.12.048.
[18] A. Alonso-Mateos, M.J. Almendral-Parra, Y. Curto-Serrano, F.J. Rodriguez-Martin,
The authors declare that they have no known competing financial Online monitoring of aluminium in drinking water with fluorimetric detection, J.
interests or personal relationships that could have appeared to influence Fluoresc., 18 (2008), pp. 183-192 https://doi.org/10.1007/s10895-007-0262-5.
the work reported in this paper. [19] M. Čerňanská, P. Tomčík, Z. Jánošíková, M. Rievaj, D. Bustin, Indirect
voltammetric detection of fluoride ions in toothpaste on a comb-shaped
interdigitated microelectrode array, Talanta 83 (5) (2011) 1472–1475, https://doi.
Acknowledgements org/10.1016/j.talanta.2010.11.026.
[20] E. Beinrohr, M. Cakrt, J. Dzurov, L. Jurica, J.A.C. Broekaert, Simultaneous
calibrationless determination of zinc, cadmium, lead, and copper by flow- through
This work was supported by the Slovak Research and Development stripping chronopotentiometry, Electroanalysis 11 (15) (1999) 1137–1144,
Agency under the contract No. APVV-15-0355 and by the grant agency https://doi.org/10.1002/(SICI)1521-4109(199911)11:15<1137::AID-
VEGA (project No. 1/0159/20) and by the Competence Center for ELAN1137>3.0.CO;2-Z.
[21] J. Mortensen, E. Ouziel, H.J. Skov, L. Kryger, Multiple- scanning potentiometric
SMART Technologies for Electronics and Informatics Systems and Ser­ stripping analysis, Anal. Chim. Acta 112 (3) (1979) 297–312, https://doi.org/
vices, ITMS 26240220072 and by STU Grant Scheme for Support of 10.1016/S0003-2670(01)83557-1.
Young Researchers (project ALMAS). [22] A. Hu, R.E. Dessy, A. Graneli, Potentiometric stripping with matrix exchange
techniques in flow injection analysis of heavy metals in groundwaters, Anal. Chem.
55 (2) (1983) 320–328, https://doi.org/10.1021/ac00253a031.
[23] E. Beinrohr, M. Németh, P. Tschöpel, G. Tölg, Design and characterization of flow-
through coulometric cells with porous working electrodes made of crushed

5
J. Masac et al. Microchemical Journal 164 (2021) 106058

vitreous carbon, Fresenius J Anal. Chem. 343 (7) (1992) 566–575, https://doi.org/ Quantification: Application to Voltammetric and Stripping Techniques, Pure Appl.
10.1007/BF00324817. Chem. 69 (1997) 297-328 10.1351/pac199769020297.
[24] J. Mocak, A.M. Bond, S. Mitchell, G. Scollary, A Statistical Overview of Standard [25] WHO/SDE/WSH/03.04/08: Iron in Drinking-water.
(IUPAC and ACS) and New Procedures for Determining the Limits of Detection and