Food Control 66 (2016) 116e129

Contents lists available at ScienceDirect

Food Control
journal homepage: www.elsevier.com/locate/foodcont

Electrical impedance measurements for detecting articial chemical

additives in liquid food products
Anna Nakonieczna a, b, *, Bartosz Paszkowski a, Andrzej Wilczek a, Agnieszka Szypowska a,
Wojciech Skierucha a
a
The Bohdan Dobrzan  ski Institute of Agrophysics of the Polish Academy of Sciences, ul. Doswiadczalna 4, 20-290 Lublin, Poland
b
Institute of Physics, Maria Curie-Skodowska University, Plac Marii Curie-Skodowskiej 1, 20-031 Lublin, Poland

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

Article history: Analyzing the content of articial chemical additives in food products is important due to their twofold
Received 28 November 2015 role in food processing and consumption, i.e., their positive impact on the shelf life or sensory properties
Accepted 5 January 2016 of food products and possible negative effect on human health. The objective of the research was to
Available online 2 February 2016
evaluate the usefulness of the impedance spectroscopy technique in food quality control by testing its
potential for determining the additives content in liquid food products. The impedance readings of one-
Keywords:
and two-component solutions of twelve common food additives and six natural juices, both pure and
Articial food additives
with additions of selected chemical additives, were collected within the frequency range from 20 Hz to
Natural juices
Impedance spectroscopy
2 MHz. The resulting spectra were interpreted with the use of the equivalent electrical circuit approach.
Equivalent electrical circuit An optimal circuit which allowed to describe electrical properties of the investigated samples was
Food quality control selected. It was characterized by four physical parameters, two of which may be used for the differen-
tiation among food additives. The impedance spectroscopy technique has a potential to become an
Selected chemical compounds studied in this effective method for food quality and safety control in the context of the articial additives content,
article:
because it allows to describe the content in a relatively simple manner when the compounds of interest
Potassium chloride (PubChem CID: 4873)
Sodium benzoate (PubChem CID: 517055)
are present in small quantities in chemically complex materials such as foods.
Trisodium citrate (PubChem CID: 6224) 2016 Elsevier Ltd. All rights reserved.
Potassium sorbate (PubChem CID:
23676745)
Potassium nitrate (PubChem CID: 24434)
Trisodium phosphate (PubChem CID:
24243)
Potassium iodide (PubChem CID: 4875)
Sodium sulphate (PubChem CID: 24436)
Calcium chloride (PubChem CID: 5284359)
Ascorbic acid (PubChem CID: 54670067)

1. Introduction
The food analysis is crucial primarily from the viewpoint of
human nutrition and health concerns, which are constantly
growing in increasingly demanding societies. Food engineering is
focused on striking a balance between extending the shelf life of
foods by employing preservation techniques and the maintenance
ndez-Herrero, Guamis, and
of their quality Evert-Arriagada, Herna
Trujillo (2014). The reasons for performing food analyses are the
 ski Institute of Agrophysics of the
* Corresponding author. The Bohdan Dobrzan
Polish Academy of Sciences, ul. Doswiadczalna 4, 20-290 Lublin, Poland.
E-mail address: a.nakonieczna@ipan.lublin.pl (A. Nakonieczna).
need for high quality assurance and providing the desired sensory
properties, both of which require introducing specic control dur-
ing food production and processing. Other issues, partially related
to these outlined above, which are pursued during developing the
food science methodology, are checking food adulteration de
rio, Paim, and Lavorante (2014); Geana et al.
Souza, da Silva, Leote
(2016) or the pattern recognition, i.e., determining the geograph-
ical and plant or animal origin of the particular food product Link,
Lemes, Marquetti, Scholz, and Bona (2014); da Silva, Filardi, Pepe,
Chaves, and Santos (2015); Jandri c et al. (2015).
There are several paths in analytical treatment of foods. They
concentrate on testing the natural composition Arcari, Chaves,
Vanderlinde, Rosier, and Bordignon-Luiz (2013), identifying and
quantifying chemical and biological additives introduced either

http://dx.doi.org/10.1016/j.foodcont.2016.01.044
0956-7135/ 2016 Elsevier Ltd. All rights reserved.
 A. Nakonieczna et al. / Food Control 66 (2016) 116e129
deliberately or accidentally, e.g., during packaging or transport Wu
et al. (2015), and on temporal changes, to which foods are subjected
due to natural or human-induced processes Ananingsih, Sharma,
and Zhou (2013); Toydemir et al. (2013). Food additives can origi-
nate from the raw food material preparation, e.g., pesticides, vet-
erinary drugs or environmental contaminants may appear in the
nal food products Marques et al. (2011). Food can also contain
desirable or undesirable compounds excreted by microorganisms,
such as bacteria or fungi Oco n et al. (2013); D'Ostuni et al. (2016);
Ferre (2016). During the preparation for sale stage of food pro-
duction, articial preservatives can be added to foods to extend
their storage time and other chemical additives can be introduced
in order to improve their taste or texture.
Quality assessment in food industry is mainly based on sensory
panel control, because a vast amount of food quality indicators is
subjective and impossible to capture by measurable physical pa-
rameters. Moreover, even if the particular product property is
quantiable through a physical variable, sensors appropriate for
food control are rarely available Ortega-Rivas (2010). One of quality
and safety indexes, which is physicochemically quantiable, is the
amount and types of articial contaminants and additives con-
tained in food products. Their determination is of crucial impor-
tance for testing food quality and in the context of controlling the
safety of food. It is also a challenging task, because the content of
food products is complex, diversied and not uniform even for the
particular product type. The currently employed control methods
in this respect include the infrared (IR) and Raman Sun (2009);
Yang and Ying (2011); Sivam, Sun-Waterhouse, Perera, and
Waterhouse (2013); Li and Church (2014), as well as uorescence
decka
Sa  and To thova (2007), UVeVIS Nawrocka and Lamorska
(2013), atomic Baker, Miller-Ihli, Fodor, and Woller (2006), nu-
clear magnetic resonance (NMR) Belton and Wood (2012); Zhao
et al. (2013), terahertz time-domain Baek, Lim, and Chun (2014)
and dielectric Guo, Zhu, Liu, Yue, and Wang (2010); Jha et al.
(2011) spectroscopies, atomic absorption spectrometry (AAS)
Knapek, Herman, Buchtova , and Vosmerov a (2009); Mahabir and
Verma (2012), liquid and gas chromatography Lehotay and
Hajslova (2002); Sardella et al. (2013), sometimes supported by
mass spectrometry Chowdhury et al. (2013); DUrso, dAquino,
Pizza, and Montoro (2015); Kus and van Ruth (2015).
The most effective determination techniques are expected to be
fast and non-destructive in order to reduce the need for expensive
and time-consuming laboratory analyses. Due to low additives
content in materials under consideration, the techniques should
also be capable of dealing with small amounts of the chemical
compounds of interest in the investigated specimens. Electrical
measurements at low frequencies meet the above requirements
and hence they may provide valuable information in an efcient
way. Because of the measurement specics, these techniques have a
potential to become especially useful in investigations of foods of
low conductivity, e.g., honey Paszkowski, Wilczek, Szypowska,
Nakonieczna, and Skierucha (2014), as well as milk and dairy
products such as ker and yogurt, avored natural and mineral
waters and other liquid, semi-liquid or even solid food products
after dilution.
Impedance spectroscopy (IS) is an experimental technique
based on analyzing changes of the electrical impedance of the
examined sample-electrode system, which appear due to fre-
quency variations of an applied voltage Barsoukov and Macdonald
(2005). It is successfully used in various and diversied elds of
science such as electrochemistry and materials science Maddala,
Sambath, Kumar, and Ramanathan (2010); Ahmed and Reifsnider
(2011), biophysics Tura, Sbrignadello, Barison, Conti, and Pacini
(2007), pharmacology Shervedani, Mehrjardi, and Zamiri (2006);
Guitia n, Novoa, and Puga (2011) and geophysics Koelemeijer,
117
Peach, and Spiers (2012). In the case of sufciently wide fre-
quency range the impedance spectrum, which is a result of the IS
measurement, incorporates the whole information about electric
properties of an analyzed system which consists of an electric
sensor and the tested material Harrington and van den Driessche
(2011). In a realistic case, selecting an appropriate limited range
of frequencies for conducting investigations requires initial deter-
mination of the considered material characteristics such as con-
ductivity and, if desired, the scope of processes and phenomena,
which are of special interest and thus should be given a careful
consideration. In the case of the solutions of ionic food additives
and natural juices examined in this paper, low radio frequencies
from the range 20 Hze2 MHz were proven to be optimal.
The most straightforward way of interpreting the IS result is to
construct an equivalent electrical circuit (EEC) with the same
impedance spectrum as the one obtained during the experiment
Harrington and van den Driessche (2011). Although the interpre-
tation of the EEC components and their connections is usually
ambiguous, in some cases the structure may suggest what kinds of
phenomena or processes occur in the corresponding system
Macdonald (2006). The EEC-based elaboration on the IS results has
a potential for complex systems assessment oriented to their se-
lective chemical composition, because it allows to describe them
using only a few parameters and thus avoid complicated and
overdetailed analyses.
The aim of this paper is to discuss results on the subject whether
the IS technique offers a possibility of determination of the articial
additives content in food products. The rst stage of the research
was investigating electrical properties of aqueous solutions of
electrolytes being common food preservatives, which consist of
multiple types of ions. The analysis was done on the basis of a set of
physical quantities and parameters characterizing the impedances
of particular elements of various EECs suitably tted to the inves-
tigated samples. The second research phase involved IS measure-
ments of diluted sole juices and their samples with the addition of
selected chemical food additives.
2. Materials and methods
2.1. Investigated food additives
Aqueous solutions of twelve salts being common articial food
additives were investigated during the rst stage of the research.
Systematic names of the compounds of interest and their E-
numbers are presented in Table 1. From now on, the particular
chemical compound will be identied by the respective compound
number. The analytically pure compounds of interest were dis-
solved in deionized water of the average conductivity equal to
0.136 mS/m. The concentrations of the obtained solutions were
equal to 0.1 mM. Five independent samples of each solution were
prepared.
In the following research phase, nine selected two-component
mixtures of the above compounds were examined. The mixtures
consisted of the combinations presented in Table 1. The solutions
were multi-ionic and they contained three (mixtures 1e5) or four
(mixtures 6e9) different types of ions. The partial concentrations of
the studied mixtures were equal to 0.05 and 0.1 mM regarding each
of the compounds. Five independent samples of each of them were
measured. The solvent was deionized water of the previously
described characteristics.
2.2. Investigated natural juices
The examined food products were six pure natural juices, i.e.,
black elder, plum, sea-buckthorn, chokeberry, nettle and cranberry
118 A. Nakonieczna et al. / Food Control 66 (2016) 116e129

Table 1
Examined food additives and their multi-ionic mixtures.

No. Systematic name of the compound E-number Mixture composition

1 sodium chloride e (salt) potassium chloride, potassium iodide

2 potassium chloride E508 potassium chloride, potassium benzoate
3 sodium benzoate E211 sodium chloride, sodium benzoate
4 potassium benzoate E212 sodium chloride, sodium sulphate
5 trisodium citrate E331 sodium chloride, trisodium phosphate
6 potassium sorbate E202 potassium chloride, sodium benzoate
7 potassium nitrate E252 potassium chloride, sodium sulphate
8 sodium nitrate E251 potassium chloride, trisodium citrate
9 trisodium phosphate E339 potassium chloride, trisodium phosphate
10 potassium iodide e
11 sodium sulphate E514
12 calcium chloride E509

juices. They were delivered by a company, which specializes in
producing juices without any articial chemical additives. In order
to obtain conductivities, which were appropriate for the IS mea-
surements with the employed sensor (whose construction and
performance will be briey explained in Sec. 2.3), the juices were
mixed with deionized water of the average conductivity equal to
0.136 mS/m in a volume ratio of 1:250. Apart from the diluted pure
juices, their samples with trisodium citrate and ascorbic acid as
low-concentrated additives, were examined. The concentrations of
the added compounds were within their maximal permissible
amounts in fruit juices when articially preserved, i.e., 0.25 and
0.6 g per liter of juice, respectively.
2.3. Measuring system and measurement conditions
The basic component of the experimental setup for IS mea-
surements is shown in Fig. 1. The measurement cell consisted of a
multi-rod sensor connected to the Agilent E4980A LCR meter
(Santa Clara, CA, USA) and immersed in the examined liquid, which
tightly lled the container of volume approximately equal to
120 ml. The sensor was designed and calibrated for the measure-
ments at low radio frequencies Szypowska et al. (2013). It was
made of passivated acid resistant steel and remained chemically
passive in the prepared solutions.
The readings of impedance were taken within the voltage signal
frequency range from 20 Hz to 2 MHz, which is appropriate for the
studies regarding the conductivities of the investigated media. The
signal amplitude was equal to 100 mV. During the measurements
ambient temperature and humidity were stabilized by a climatic
chamber, within which the temperature was equal to 25.0 0.1+ C
and humidity was equal to 50 1%. The impedance spectrum for
further analysis was collected after approximately 3 h of the sample
thermal stabilization when time variability of both real and imag-
inary parts of impedance at all applied frequencies remained con-
stant at least within 0.01% and 0.1%, respectively.
The impedance measurements were supplied by independent
electrical conductivity readings of each of the solutions. They were
collected after the thermal stabilization of the sample and before
the impedance measurement using the Radiometer Analytical
CDM210 conductivity meter (Villeurbanne Cedex, France) and the
Elmetron CX-701 multipurpose measuring device (Zabrze, Poland).
They served for reference and control purposes of the tested sam-
ples concentration variations.
2.4. Electrical impedance spectra interpretation
The obtained frequency spectra of impedance of the tested so-
lutions were elaborated with the use of the equivalent electrical
circuit approach Harrington and van den Driessche (2011). The
initial step in analyzing the obtained IS data was the construction of

Fig. 1. The IS experimental setup, which was (a) a measurement cell with (b) the sensor.
 A. Nakonieczna et al. / Food Control 66 (2016) 116e129 119

Fig. 2. Equivalent electrical circuits for modeling the IS spectra of the examined liquid samples, (a) EEC1, (b) EEC2 and (c) EEC3.

an EEC with an impedance spectrum, which reproduced the one

collected during the measurements of the investigated sample.
Table 2
After a sequence of attempts to t an optimal EEC to the experi-
Parameters of the EECs tted to the spectrum of the compound 1, presented in Fig. 3.
mental data, a set of most appropriate EECs for modeling the
electrical properties of the measured samples were selected. They EEC parameter EEC1 EEC2 EEC3

are presented in Fig. 2. Their constructions were based on capaci- C$1011 or C1$1011 [F] 8.1337 8.1257 8.1461
tors (C), resistors (R) and constant phase elements (CPE). The CPEs C2$105 [F] e e 1.0268
R [ U] 5072.1 5071.5 5080.3
provided an opportunity to adequately reproduce the complicated
Q$105 or Q1$105 [U
1$sn] 5.0334 8.5066 10.4081
IS response of real-world systems, often related to complex inter- n or n1 0.7641 0.8693 0.5067
facial phenomena occurring on the phase boundary nearby the Q2$105 [U
1$sn] e 9.9816 e
electrode, where the double electrical layer forms. EEC1 was a n2 e 0.7111 e
parallel connection of a capacitor and a resistor connected in series
with a constant phase element. EEC2 had another constant phase

Fig. 3. Nyquist plots of the impedance spectrum of a 0.1 mM aqueous solution of the compound 1 for (a) EEC1, (b) EEC2 and (c) EEC3. Experimental data are marked by green
diamonds and the tted spectra are black solid lines. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)
120 A. Nakonieczna et al. / Food Control 66 (2016) 116e129

Table 3 impedance, Z. The green diamonds correspond to the discrete

Mobilities of hydrated ions in diluted solutions relative to potassium ion mobility at experimental IS spectrum of the solution, while the black solid lines
25+ C Barry and Lynch (1991); Kok (2000); Costa, Perfeito, Tavares, and Micke (2008).
are the simulated spectra of the EECs, whose schemes are pre-
Ion Symbol/Formula Relative ion mobility sented in Fig. 2, tted to the experimental data with the normalized
Sodium Na 0.682 tting errors for the amplitude weighted complex function below
Potassium K 1.000 10
5. The exact values of parameters characterizing the tted
Chloride Cl
1.039 spectra are gathered in Table 2. The visualization of impedance
Benzoate C6 H5eCOO
0.441
spectra along with their interpretation based on the IS methods
Citrate C(OH)(COO
)e(CH2eCOO
)2 0.318
Sorbate CH3e(CH)4eCOO
0.438 was performed using the EISanalyser software Bondarenko and
Iodide I
1.045 Ragoisha (2005); EIS (2008).
Nitrate NO3
0.972
Sulphate SO2
0.544
4
Phosphate PO3
0.918 3. Theoretical electrical conductivity of electrolytes
4
Calcium Ca2 0.405
Resistance is one of the parameters, which characterize the
tted impedance spectra. In the case of one-component solutions,
element connected in series with the circuit analogous to EEC1. whose spectra are modeled by EEC1, it can be related to electrical
EEC3 had a parallel connection of a capacitor and a constant phase conductivity of the measured sample through a standard reciprocal
element instead of a CPE in EEC1. relation Szypowska et al. (2013). Since the calculated values of the
The impedances Z of the individual EEC elements may be related EEC resistances corresponding to particular solutions may be
to a set of physical quantities and parameters in the following way: potentially linked to their electrical conductivities, they are ex-
pected to exhibit adequate relations with regard to ionic compo-
sition of the electrolyte. In order to check whether the discussed

1 1
ZC ; ZR R; ZCPE ; (1) relations actually exist for the currently studied conductive liquids,
2pifC Q 2pif n theoretical conductivities of the solutions were collated with the R-
parameter values. The theoretical values of the investigated solu-
where C [F] is capacitance, R [U] e resistance, Q [U
1$sn] and tions conductivities k [S,m
1] were calculated according to the
dimensionless n are free CPE parameters, f [Hz] stands for fre- relation
quency and i is the imaginary unit. The CPE mathematically dened
by two parameters Q and n reduces to pure inductor, resistor and k F$c$uK $a$z u z
u
; (2)
capacitor in the case of n equal to 1, 0 and 1, respectively.
The experimental spectrum of a 0.1 mM aqueous solution of the where F 96485.3 C$mol
1 is the Faraday constant, c [M] e molar
compound 1, which is representative for all investigated solutions, concentration, uK 7.62$10
8 m2$V
1$s
1 is potassium ion
with the tted spectra of the used EECs is presented in Fig. 3. The mobility at 25+ C, a is the degree of dissociation, z are the amounts
spectrum is pictured on the Nyquist plot, which presents the of ions of particular type in the solute's molecule and u are relative
relation between real and imaginary parts of the sample's mobilities of these ions Atkins and de Paula (2002). Since all the

Fig. 4. Parameters of EEC1 for the investigated solutions of food additives no. 1e12.
 A. Nakonieczna et al. / Food Control 66 (2016) 116e129
Fig. 5. Parameters of EEC2 for the investigated solutions of food additives no. 1e12.
electrolytes of interest were strong, the degree of dissociation was
in all cases equal to 1. The solutes were of 1:1 composition and their
z were equal to 1, apart from compounds 5, 9, 11 and 12. The salts
5 and 9 were of the ionic composition 3:1, which resulted in z and
z
equal to 3 and 1, respectively. The ionic compositions of com-
pounds 11 and 12 were 2:1 and 1:2, and hence their respective z
and z
values were equal to 2, 1 and 1, 2. The relative mobilities of
hydrated ions of the investigated solutions are presented in Table 3.
Since the calculated degree of hydrolysis of the compounds 3, 4
and 6, which are salts of weak acids and strong bases, was less than
1% in all cases, it was assumed that it did not inuence their
theoretical conductivities. The values of theoretical conductivity of
the compounds 5 and 9 were burdened with signicant error due to
complicated nature of the process of reaching the equilibrium state
in the solution. The role of multiple coexisting processes such as
hydrolysis and dissociation of the resulting acid, both of which
occur in stages, were hard to assess theoretically.
121
4. Results
4.1. Electrical parameters of the one-component food additives
solutions
The arithmetic means of parameters which characterize the
selected EECs for the measured solutions of compounds 1e12,
calculated out of ve independent measurement repetitions, are
presented in Figs. 4e6. The error bars on the plots are standard
deviations of the average. Since each sample was prepared inde-
pendently of others, the error of a particular average includes the
one connected with random deviations from the assumed con-
centration, appearing due to the human error introduced during
the preparation process of the solutions. The errors calculated by
the EISanalyser software and connected with the spectrum tting
for the C parameter were about 11%. For R and n the errors did not
exceed 5.2% and 4.5% for all EECs. The errors corresponding to Q
were higher, but did not exceed 17% for all the EECs. The errors
increased with a number of tted parameters, which was
122 A. Nakonieczna et al. / Food Control 66 (2016) 116e129

Fig. 6. Parameters of EEC3 for the investigated solutions of food additives no. 1e12.

Table 4
Average capacitances, C (C1 for EEC3), and average resistances, R, of the tted EECs for the examined one-component solutions of compounds no. 1e12.

Compound no. C$1011 [F] C1$1011 [F] R [ U]

EEC1 EEC2 EEC3 EEC1 EEC2 EEC3

1 8.13570 8.13258 8.13588 4840.46 5349.86 4939.70

2 8.13344 8.13062 8.13556 4654.68 5143.50 4714.04
3 8.14104 8.13882 8.14136 8745.68 8293.34 8623.96
4 8.14246 8.13312 8.14264 7342.16 7138.22 7341.16
5 8.14044 8.12748 8.14054 2448.56 2579.16 2448.30
6 8.14182 8.13480 8.14208 7481.26 7185.12 7479.88
7 8.13668 8.13704 8.13686 5240.00 5239.40 5239.60
8 8.13714 8.13740 8.13732 5622.42 5621.64 5621.52
9 8.13304 8.13310 8.13316 2188.12 2187.90 2187.86
10 8.13554 8.13574 8.13566 4916.48 4915.72 4915.90
11 8.13416 8.13422 8.13428 2957.20 2956.96 2956.98
12 8.12998 8.13302 8.13004 2805.46 2805.66 2804.76

consistent with predictions, as the accuracy of the tting process
decreases with an increase of the number of unknown variables.
Average capacitances and resistances were similar for all the
investigated EECs. Their values are gathered in Table 4 (for EEC3 the
capacitance of C1 was listed). The agreement between EEC1 and
EEC3 was within 0.03% for C and 2% for R, while the results for EEC2
differed from the rest at about 0.16% and 10%, respectively.
Fig. 7 presents the relation between average values of
resistances of the EECs tted to analyzed solutions, which are
gathered in Table 4, and theoretical values of the solutions con-
ductivities calculated according to (2). Since due to the causes
explained in Sec. 3, the results for the compounds 5 and 9 diverge
signicantly from the expected linear dependence, they were
omitted during performing the linear regression. The parameters of
the t and the coefcient of determination, CoD, are presented on
the plots. The slope represents the cell constant, because all the
 A. Nakonieczna et al. / Food Control 66 (2016) 116e129 123

1 , versus theoretical conductivity, k, for (a) EEC , (b) EEC and (c) EEC . The numbers indicate the
Fig. 7. The average of the resistance reciprocals of the investigated solutions, Rav 1 2 3
particular solute. CoD is the coefcient of determination of a linear t.

Fig. 8. Parameters of EEC1 for the investigated multi-ionic solutions 1e9 of the compounds concentration equal to 0.05 mM.

readings were taken in identical measuring units. The cell constant
is equal to 1.928, 1.882 and 1.924 cm for EEC1, EEC2 and EEC3,
respectively.
4.2. Electrical parameters of the investigated mixtures
The arithmetic means of parameters which characterize EEC1
and EEC2 for the measured 0.05 and 0.1 mM solutions of mixtures
1e9, calculated out of ve independent measurement repetitions,
are presented in Figs. 8e11. Error bars on the plots are standard
deviations of the average. Similarly to the case of one-component
solutions, each sample was prepared independently of others and
thus the error of the particular average includes the one connected
with random deviations from the assumed concentration. The er-
rors of C calculated by EISanalyser software and connected with the
spectrum tting did not exceed 11%. The errors of R, Q and n were
smaller than 5.1%, 22.0% and 15.4% for both EECs. Just as in the
previously discussed case, the errors increased with a number of
124 A. Nakonieczna et al. / Food Control 66 (2016) 116e129
Fig. 9. Parameters of EEC2 for the investigated multi-ionic solutions 1e9 of the compounds concentration equal to 0.05 mM.
tted parameters. They were also bigger for solutions of higher
concentration. The results of the impedance spectrum tting with
the use of EEC3 were burdened with the normalized tting errors
for the amplitude weighted complex function of the order of tens of
percent and for this reason they are not presented.
Average capacitances and resistances were similar for both
tted EECs. Their values are gathered in Tables 5 and 6. The
agreement between the two EECs was within 0.014% for C and 2.1%
for R.
Figs. 12 and 13 present the relation between average values of
resistances of the EECs tted to analyzed solutions, which are
gathered in Tables 5 and 6, and measured values of the solutions
electrical conductivities. The parameters of the t and the coef-
cient of determination, CoD, are presented on the plots. The slope
represents the cell constant, because all the readings were taken in
identical measuring units. Regarding the 0.05 mM solutions, the
cell constant is equal to 1.494 cm for both EECs, while for the
0.1 mM solutions its respective values are 1.392 and 1.382 cm for
EEC1 and EEC2, respectively.
4.3. Electrical parameters of sole and enriched dissolved natural
juices
The EEC1 parameters for the examined solutions of pure juices
and their samples with trisodium citrate and ascorbic acid are
presented in Fig. 14. The errors of C calculated by EISanalyser
software and connected with the spectrum tting were smaller
than 15%. The errors of R, Q and n did not exceed 3.9%, 18.0% and
9.4%. The results of the impedance spectrum tting with the use of
EEC2 and EEC3 are not presented, because the overall normalized
tting errors for the amplitude weighted complex function excee-
ded tens of percent making the results unreasonable.
The reciprocal of resistance of the EEC1 tted to analyzed solu-
tions of juices as a function of their measured electrical conduc-
tivities is presented in Fig. 15. The parameters of the t and the
coefcient of determination, CoD, are presented on the plot. The
slope represents the cell constant, because all the readings were
taken in identical measuring units. It is equal to 1.119 cm.
 A. Nakonieczna et al. / Food Control 66 (2016) 116e129
Fig. 10. Parameters of EEC1 for the investigated multi-ionic solutions 1e9 of the compounds concentration equal to 0.1 mM.
5. Discussion
The physicochemical interpretation of C and R parameters
within all investigated EECs is the following. The former corre-
sponds to the total capacity of the sensor immersed in the liquid
sample, while the latter may be linked to electrical conductivity of
the bulk of electrolyte, through a reciprocal relation. These mean-
ings of the EEC capacitance and resistance parameters hold dis-
regarding the content of the examined liquid sample. They seem to
be independent of the complexity of the solution content, as they
are valid for aqueous solutions of juices and electrolytes. This
property is especially promising in the context of investigations of
such composite materials as foods.
Due to low obtained capacitances, which resulted from small
solutes amounts in the investigated samples and the geometry of
the sensor, random errors of impedance readings strongly affected
the values obtained during the EEC tting. For such a low concen-
tration that was investigated, signicant variations of the overall
capacitance among the solutions were not expected. The capaci-
tance values were determined by the electrical permittivity of so-
lutions, which in all cases was similar due to the prevalence of
water in all samples. The scattering of the results of capacitance
measurements was due to random variations of temperature dur-
ing the readings.
The remaining parts of the investigated EECs model the
complicated IS response of the examined specimens. The parame-
ters describing the CPE ought to be interpreted together, because
the unit of Q depends on the value of n. In EEC1, the values of n
exhibit specic variability, which may be related to the solute's
chemical composition. The performed analyses indicated that the
parameters characterizing CPE depend on types of ions present in
the liquid and for this reason may be the indicators for the
composition of the solution. It is connected with the fact that ionic
masses and spatial structures differ, which results in their different
behaviors nearby the electrode, where the electrical double layer
forms. The CPE parameters allow to describe the inuence of the
125
interfacial phenomena occurring on the electrode/liquid phase
boundary collectively and without details which are unnecessary
from the view of the intended purpose, i.e., a quick and effective
analysis of a complex sample. Since the interfacial phenomena
strongly depend on the chemical content of the sample, the inter-
pretation of the EEC part, which is responsible for their description,
has a potential to be linked to the chemical content of the particular
material. Thus, the EEC-based interpretation of the IS measure-
ments of complicated materials is a convenient and promising
treatment of food samples. It does not require detailed analyses and
understanding of the specic physicochemical system, but provides
an opportunity to analyze it cursorily in order to get the desirable
information, which is especially important in the context of food
control, e.g., during the production process or after the particular
product was released for sale.
The reliability of the impedance spectrum t increases when the
number of the tted parameters decreases. At the same time, our
research revealed that the t worsens as the number of compounds
in the solution increases. Thus, the simplest EEC, that is EEC1,
turned out to be most useful in the performed analyses. It is
convenient from the point of view of future programming an
application software supporting the sensor, which will be neces-
sary for online measurements. The errors of the ts to the EEC2 and
EEC3 spectra are high and the results for multi-ionic solutions are in
many cases unreliable or the errors of the particular parameters
values exclude the possibility of a robust interpretation, because
the uncertainties of the measurements overlap considerably.
6. Conclusions
The main aim of the research was to nd whether impedance
spectroscopy measurements offer a possibility of differentiation
among chemical compounds or their groups, especially when the
compounds of interest (which were articial chemical additives to
food products) are accompanied by other chemical compounds
(which constitute the particular complex material, such as a natural
126 A. Nakonieczna et al. / Food Control 66 (2016) 116e129

Fig. 11. Parameters of EEC2 for the investigated multi-ionic solutions 1e9 of the compounds concentration equal to 0.1 mM.

Table 5 Table 6
Average capacitances, C, and average resistances, R, of the EECs tted to the 0.05 mM Average capacitances, C, and average resistances, R, of the EECs tted to the 0.1 mM
multi-component solutions 1e9. multi-component solutions 1e9.

Mixture no. C$1011 [F] R [ U] Mixture no. C$1011 [F] R [ U]

EEC1 EEC2 EEC1 EEC2 EEC1 EEC2 EEC1 EEC2

1 8.12536 8.12568 5192.48 5211.66 1 8.11600 8.11608 2738.66 2738.46

2 8.12888 8.12922 6036.12 6035.08 2 8.12076 8.12090 3286.24 3285.90
3 8.13036 8.13076 6719.10 6857.74 3 8.12404 8.12420 3950.44 3949.92
4 8.12812 8.12838 4035.92 4035.24 4 8.12196 8.12212 2212.44 2212.22
5 8.12488 8.12378 3317.68 3317.26 5 8.12192 8.12198 1643.30 1643.22
6 8.13448 8.13480 6745.14 6744.02 6 8.12282 8.12294 3561.12 3560.74
7 8.12774 8.12788 3565.68 3565.18 7 8.12140 8.12146 2066.20 2066.10
8 8.12906 8.12924 3330.98 3330.46 8 8.12730 8.12736 1836.48 1836.34
9 8.12562 8.12576 3321.48 3320.92 9 8.12202 8.12210 1495.78 1495.68

juice). In order to achieve this goal, low-concentrated aqueous so-
lutions of twelve different food additives, their nine mixtures and
six dissolved natural juices (pure and with additions of two
exemplary articial preservatives) were analyzed using the IS
technique. The interpretation of the obtained impedance spectra
was made in terms of the equivalent electrical circuit approach.
The EEC which was proven to be appropriate for the analysis of
the spectra of the investigated samples consisted of a capacitor
connected in parallel with a series of a resistor and a constant phase
element. It was characterized by four parameters, namely C, R, Q
and n, the last two of which are specic for the CPE. It turned out
that due to small absolute values and signicant errors of C and Q
they are not useful in characterizing the properties of the investi-
gated materials. On the other hand, the parameter R corresponding
to one of the elements of the tted EEC may be used for the dif-
ferentiation among the analyzed compounds on the same grounds
 A. Nakonieczna et al. / Food Control 66 (2016) 116e129 127

1 , versus their conductivity, k, for (a) EEC and (b) EEC . The numbers
Fig. 12. The average of the resistance reciprocals of the investigated solutions of concentration 0.05 mM, Rav 1 2
indicate the particular mixture. CoD is the coefcient of determination of a linear t.

1 , versus their conductivity, k, for (a) EEC and (b) EEC . The numbers
Fig. 13. The average of the resistance reciprocals of the investigated solutions of concentration 0.1 mM, Rav 1 2
indicate the particular mixture. CoD is the coefcient of determination of a linear t.

Fig. 14. Parameters of EEC1 for the investigated dissolved juices and their samples with sodium citrate and ascorbic acid. (For interpretation of the references to color in this gure
legend, the reader is referred to the web version of this article.)
128 A. Nakonieczna et al. / Food Control 66 (2016) 116e129
Fig. 15. The EEC1 resistance reciprocals of the investigated dissolved juices and their samples with sodium citrate and ascorbic acid, R
1, versus their conductivity, k. CoD is the
coefcient of determination of a linear t. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)
as the conductivity of their aqueous solutions. The CPE parameter n
may also be used for differentiation, because its value is strongly
dependent on the ionic composition of the solutions.
The results of the paper indicated that impedance spectroscopy
is a promising technique for food quality and safety control in the
context of the articial additives content. The outcomes of the
conducted research are an auspicious start to development of a
technique of analyzing food products due to two reasons. First, the
presented method provides an opportunity to select a pair of pa-
rameters (R and n, assuming EEC1) which allows the discrimination
among various chemical compounds present in a liquid sample.
Second, the aforementioned role of the parameters also applies to
complex systems (multi-compound mixtures and enriched juices
studied in the current paper). Building a model for the exact
discrimination among various substances on the background of
different liquid food products would require further systematic
research which takes more types of chemical compounds and foods
into account. The results obtained for the investigated solutions of
widespread food additives and juices would serve as a basis for
future quality tests of more complex liquid materials of natural
origin. It should be emphasized that the only limitation of the
employed technique is the conductivity of the investigated sam-
ples. Apart from investigating liquid samples, which were the ob-
jects of the current study, it also offers a possibility of measuring
solid food specimens by designing a sensor with a construction that
is adjusted to examining solid materials.
Acknowledgments
The research was supported by the National Center for Research
and Development (NCBR) grant no. PBS1/A9/12/2012.
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