Microchemical Journal 164 (2021) 106058

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Microchemical Journal

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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:
Aluminum A new procedure has been developed for indirect determination of aluminium(III) in water through in-electrode
Fluoride complexes coulometric titration in a porous reticulated vitreous carbon electrode. It was determined through different
Indirect determination aluminium fluoride and ferric fluoride complex stabilities. The ferric fluoride complex thereby formed was
In-electrode coulometric titration decomposed with Al(III) from the sample and an aliquot of the released Fe(III) was determined electrochemi-
—
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 L1
—
—
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
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,
— electrochemical method for determination of aluminium. Electrodes
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
(chromatography, extraction, etc.) either to detect trace aluminium
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
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: f r a n t i s e k . c a c h o @ s t u b a . s k (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. Microchemical Journal 164 (2021)
106058

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 (pK 6=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 pK 3 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
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
End potential (mV) * 200
Reduction current (µA) 10
Fig. 1. Block diagram of the flow-
through analyser EcaFlow with the
Flow- through cell: V – solenoid valve,
Constant current is applied and potential
monitored
Switched to the regeneration potential
Regeneration
500 potential
Regeneration of
the electrode
PP – peristaltic pump, 1- working
electrode, 2 – reference electrode, 3 –
auXiliary electrode, 4 – membrane, 5 –

2
J. Masac et al.
packing, 6 – screw, 7 – cell body, 8
– space for reference electrolyte
(saturated KCl).
— electrode.
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
— 1
exactly
( 1.0000 g L Al(III) was
prepared
) from aluminium
nitrate nonahydrate (.Al NO3
3⋅9H2O, ⩾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⋅9H2O, ⩾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
—1
0.0054 mol L 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 the range of 0.1 – 1 mol L 1. The
(designated A1)
— limit, even in the described case,
was prepared from 2 mol L 1 + observed from
— chloride (NaCl) concentration
NaCl 100 mg L 1Fe(III) 100 mg
— of 0.2 mol L . The
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
Standby potential (mV) * 100
—1
Flow rate (mL min ) 6
Sample volume (mL) 3
*vs. saturated Ag/AgCl reference
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
— which was why the measured
maximum signal intensity was
a sodium
—1
increased NaCl concentration in
the electrolyte no longer
increased the
signal, therefore an aqueous
solution of NaCl with a
— the solution continued to
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
3
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
= of 0.1–10 mg L 1, LOD
(RSD = 2.3%) and
+ —
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
—
0.03
—1
mg= L , 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
1
Fe(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,
signal did not drop to the zero
—
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
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
J. Masac et al. Microchemical Journal 164 (2021)
106058
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 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
1
F(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.

4
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.

— the
ranging from 0.1 to 10 mg L 1. An electrochemical analyser in
solution. Aluminium does not complex with cyanide, so it flowed
calibration-free mode measured the signal from free Fe (III) in all of
through the column unchanged. The central part of the sample eluate
the solutions. As Fig. 3C shows, the free Fe(III) signal increased
linearly in 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
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- pipetted. Afterward, the solution was analysed. The HR-CS-GFAAS
— — confirmed the iron in all samples to have been completely removed
formed with fluoride concentrations of 5 mg L 1 and 15 mg L 1. In the
—1 —1 from the remaining eluates. The anion-exchange resin was recycled
first case [10 mg L Fe(III) + 5 mg L F(I -)], a linear increase in the with
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
3—
the sample. All the iron in the solution was bound to the [Fe(CN)6]
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
 (sulphates, nitrates, nitrites, chlorides, bromides and bicarbonates) from
3 mol per litre of sodium chloride. During the recycling, the cyanide the samples. Only Th(IV), Zr
eluate was collected in a KMnO4 solution. (IV) and Ce(IV) ions increased the analytical signal by 15%, even in a
WARNING: KCN is a lethal poison. Whenever working with it, the twofold excess, due to competing reactions. The added fluorides
necessary safety precautions should be taken! The procedure is only formed more stable complexes with these ions than with aluminium.
applicable to waters with a neutral pH. Notwith- standing, their occurrence in real water samples is unlikely.
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 3.5. Analysis of real samples
used as the blank.
Preparation of samples for HR-CS GFAAS: Concentrated nitric An analysis of ten real samples verified the method’s accuracy. All
acid (50 µL per 50 mL sample) was added to the samples prior to of the samples were treated as described to remove the iron. The
analysis. results obtained from the calibration curve and standard addition
correlated between each other and with the reference values obtained
3.4. Analytical figures of merit 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
Table 2 lists the main metrological determination parameters. The the reference
limit of detection (LOD) and limit of quantification (LOQ) were calcu-
lated from the calibration dependence using the ULA-2 method [24]. Table 2
The repeatability of the measurement was determined from making Metrological data.
twenty measurements in rapid succession of the same solution at an Parameter Value
aluminium concentration of one milligram per litre. The duration of —1
Linear range (mg L ) 0.05–8.5
—1
the measurement corresponds to the analysis itself (no sample Limit of detection (mg L ) 0.02
—1
treatment). The effect of selected ions commonly found in water was Limit of quantitation (mg L ) 0.05
—1
studied. No effect on the determination outcome was detected from Repeatability at 1 mg L , n = 20, [RSD %] 2.5
Duration of a measurement (min) 3
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

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
—1 —1 —1 WHO guidelines for drinking-water quality, WHO/HSE/WSH/10.01/13, (2010).
(µg L ) (µg L ) (µg L ) [2] G. Dravecz, L. Bencs, D. Beke, A. Gali, Determination of silicon and aluminum in
1. Drinking water ≤ LOD ≤ LOD 15.3 ± 0.3
method for removing the ions. The determination itself is very fast, the
2. Drinking water ≤ LOD ≤ LOD 9.8 ± 0.2 solutions easy to prepare and, as confirmed, the process is applicable to
3. Waste water 29.0 ± 0.5* 29.2 ± 0.8* 29.2 ± 0.7* different types of water samples.
4. Waste water 2 22.6 ± 0.5* 22.7 ± 0.9* 22.6 ± 0.8*
5. Waste water* 134.0 ± 3.0* 133.7 ± 4.6* 133.7 ± 2.4*
6. Groundwater 89.1 ± 2.4 88.3 ± 3.0 90.5 ± 1.8
CRediT authorship contribution statement
7. Groundwater 112.4 ± 3.8 110.9 ± 4 112.9 ± 2.1
8. Surface water 240.5 ± 3.6 141.3 ± 4.7 142.0 ± 2.7 Jakub Masac: Data curation, Writing - original draft. Jan Lovic: Data
9. Surface water 190.1 ± 4.3 189.8 ± 5.5 189.7 ± 2.8 curation. Ernest Beinrohr: Supervision. Frantisek Cacho: Visu-
10. Surface water 304.8 ± 7.5 305.1 ± 7.7 305.1 ± 4.8
alization, Writing - review & editing.
—
*Dimension is mg L 1.
*Neutralized waste water from aluminum production. Declaration of Competing Interest

values. Mean values and confidence intervals (95%) were calculated The authors declare that they have no known competing financial
from five measurements. The standard deviations were used to deter- interests or personal relationships that could have appeared to
mine confidence intervals. The regression equation of the calibration influence the work reported in this paper.
graph was τ = 15.997c + 32.475, coefficient of determination R2
0.9998, where τ is the measured
= transition time in seconds and c denotes Acknowledgements
—1
the Al(III) concentrations in mg L .
This work was supported by the Slovak Research and Development
Agency under the contract No. APVV-15-0355 and by the grant agency
4. Conclusions
VEGA (project No. 1/0159/20) and by the Competence Center for
SMART Technologies for Electronics and Informatics Systems and Ser-
This paper describes a new alternative method for the indirect
vices, ITMS 26240220072 and by STU Grant Scheme for Support of
electrochemical determination of aluminium in water. The unique
Young Researchers (project ALMAS).
process enables an electrochemically inactive element to be
determined in different water samples. It is suitable for all
electroanalytical systems. Working electrodes made of reticulated
vitreous carbon are adequate for measurement with no further treatment
required. Since these electrodes have a long life, it is a very inexpensive
analysis. RVC electrodes have proven quite suitable for the analysis.
Notwithstanding, there is no known reason for the process not to work
with other carbon electrodes. The disadvantage of the process is the
requirement to control the con- centration of Fe(III) in the samples.
The use of potassium cyanide (KCN) to completely remove the iron
from the original samples was verified. Where necessary, the KCN
concentration can be adjusted according to the iron concentration in
the samples. Of course, this does not rule out any other suitable
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