Talanta 224 (2021) 121732

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Talanta
journal homepage: www.elsevier.com/locate/talanta

Electrochemical micropipette-tip for low-cost environmental applications:

Determination of anionic surfactants through their interaction with
methylene blue
Andrea González-López, Estefanía Costa-Rama, M. Teresa Fernández-Abedul *
Departamento de Química Física y Analítica, Universidad de Oviedo, 33006, Oviedo, Spain

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

Keywords: Miniaturization is one of the main requirements in the design of portable devices that allow in-field analysis. This
Micropipette-tip electrochemical cell is especially interesting in environmental monitoring, where the time of the sample-to-result process could be
Stainless-steel electrodes decreased considerably by approaching the analytical platforms to the sampling point. We employed traditional
Electrochemical analysis
mass-produced and low-cost elements (micropipette tips and pins) in an out-of-box application to generate an
Water analysis
Sodium dodecyl sulphate
innovative and cost-effective platform for analytical purposes. We have designed simple and easy-to-use elec­
Methylene blue trochemical cells inside polypropylene micropipette tips with three stainless-steel pins acting as the working,
reference and counter electrodes of a potentiostatic system. The pin acting as working electrode was previously
coated with carbon ink, meanwhile the rest were used unmodified. In this way, electrochemical in-the-tip
measurements were done directly using low volumes (μL) of sample. The devices showed good reproduc­
ibility, with a relative standard deviation of 7% (n = 5) for five different tip-based complete electrochemical
cells. As a proof-of-concept, its utility has been probed by the determination of an anionic surfactant (sodium
dodecyl sulphate, SDS) in water through its interaction with methylene blue (MB). Two different alternatives
were presented based on the: 1) increase in the current intensity of the cathodic peak of MB due to the presence
of SDS; 2) electrochemical determination of the MB remaining in the aqueous phase after extraction of the pair
SDS-MB to an organic medium.

1. Introduction systems [7]. Batch injection analysis has also been demonstrated for
epinephrine determination using pin-based cells [8]. Their versatility
The design of miniaturized and low-cost sensing devices is an area of and low size enabled the design of arrays for performing simultaneous
enormous interest in the field of Analytical Chemistry. They are defi­ measurements using a multichannel potentiostat [6]. Similarly, other
nitely required to move (bio)chemical analysis from the bench to the mass-produced elements of common use such as staples have been
field [1]. In fact, the combination of wireless sensors with smartphones modified for utilising them as electrodes in new electrochemical
is producing platforms well suited to perform decentralized analysis [2, low-cost platforms [9].
3]. In this context, the electrochemical detection must be pointed out Among the items that are commonly present in most (bio)chemical
since it is low cost and easily miniaturized, and provide highly selective laboratories and can be employed in out-of-box applications are
and sensitive methodologies [4]. micropipette tips. They can be used for different purposes apart from
In terms of cost-effectiveness, the use of common elements for out-of- dispensing liquids, their main function. These novel applications include
box applications is clearly increasing. They are already mass-produced sample purification, as in the case of tips containing a bed of chroma­
items that can be utilized for novel applications. In 2016, Whiteside’s tography media for the detection of human chorionic gonadotropin
group introduced the use of stainless-steel pins as electrodes in combi­ (hCG) and prostate-specific antigen (PSA) in urine samples [10], or se­
nation with thread for microfluidic determination of lactate [5]. The lective extraction, with integrated molecularly-imprinted monoliths, of
modification of these metallic elements with carbon ink allowed their the toxin berberine [11] or the pesticide methomyl [12]. More recently,
use to determine glucose enzymatically, in static [6] and flow-based our research group designed an enzymatic immunoassay in which the

* Corresponding author.
E-mail address: [email protected] (M.T. Fernández-Abedul).

https://doi.org/10.1016/j.talanta.2020.121732
Received 16 July 2020; Received in revised form 26 September 2020; Accepted 1 October 2020
Available online 5 October 2020
0039-9140/© 2020 Elsevier B.V. All rights reserved.
A. González-López et al. Talanta 224 (2021) 121732

inner surface of a micropipette tip was turned into a capture zone for area and electrical conductivity, low background currents and a wide
anti-tissue transglutaminase (IgA) [13], antigen of interest for the potential window [19,20]. The bottom of the tip has a diameter that
diagnosis of the celiac disease. allows the introduction of the pin covered with a thick film of carbon,
Moving further in this direction, in this work we have added a new with the head of the pin acting as stopper. Following this new design, the
functionality to this common and affordable consumable material, easily electrochemical cell can be fabricated in an extremely fast and repro­
found in laboratories. With this aim, we have integrated a very simple ducible way employing inexpensive materials.
pin-based electrochemical cell inside a micropipette tip. Already in Thus, we present here a modified micropipette tip that acts as elec­
1991, a micropipette tip was used as a platform for the fabrication of trochemical cell, very useful for in-field analysis. The combination of
carbon fiber ultramicroelectrodes [14]. Following this idea of using the common (stainless-steel pins) and lab (micropipette tips) materials
tip as container, miniaturized electrochemical devices were designed described here draw us to the idea of a simple “everywhere” electro­
using micropipette tips combined with e.g., graphite composite [15] or analysis that could be performed by non-qualified personal. The porta­
epoxy resin [16]. In these examples, the micropipette tip acted as the bility of the system makes it useful for environmental analysis, e.g. on-
body of the working electrode, that had to be immersed in the sample site analysis of water and wastewater. Then, we decided to evaluate
solution for performing measurements, as happens with e.g., a poly­ this new electrochemical lab-on-a-tip device for assessing the quality of
meric cylinder that encloses carbon paste or a pencil lead. The other two water in terms of the presence of anionic surfactants. They mainly come
electrodes (reference and counter electrodes) had to be introduced in the from household aqueous discharge, industrial laundering and other
solution as well, which could be done: i) independently, as different cleansing operations. Surfactants are considered emerging contami­
elements, or ii) integrated in the outer part or the tip. Apart from these nants. They have negative effects on water quality since they tend to
approaches, the tips were used, after sealing the bottom, as low-cost and congregate providing properties such as foaming, emulsification and
low-volume electrochemical cells. Following this, three small-size elec­ particle suspension. Moreover, surfactants can pass through wastewater
trodes with a pencil graphite working electrode were introduced in a treatment plants and reach environmental and even drinking water.
tip-based cell [17]. However, in all these cases the tip was modified and These compounds produce harmful effects in aquatic flora and fauna,
could not be used in combination with a micropipette for performing its and also in human health [21]. Therefore, the concentration of surfac­
original function: aspirating and dispensing solutions. There is a unique tant in water is an important parameter for assessing water quality. In
report on the use of a micropipette-tip as container of a complete elec­ the United States, ionic surfactants (mostly anionic) are about two thirds
trochemical cell retaining its function [18]. In that case, the sample was of the total surfactants used [22]. The standard analytical method
aspirated and analyzed thanks to the introduction of three wire elec­ highlights anionic surfactants, such as sodium dodecyl sulphate (SDS),
trodes (with gold-based working and reference electrodes) and a cotton as the most common substances present in water and it is based in their
wool filter (for medium storage and sample purification) inside the tip, methylene blue (MB) activity. Anionic surfactants interact with MB, a
in a new lab-on-a-tip approach for decentralized electroanalysis of Cu2+ cationic dye, forming an ionic pair. This complex is transferred from the
in water. aqueous solution into an immiscible organic solvent upon equilibration.
In this work, we propose the use of a simpler and cheaper device that The blue color intensity obtained in the organic phase is measured
employs stainless-steel pins as electrodes and integrates them in the spectrophotometrically and is proportional to the concentration of
micropipette tip, which becomes now multifunctional. A pin modified anionic surfactants. This interaction has also been applied inversely to
with carbon ink is used as working electrode, and two unmodified pins adsorb MB (dye discharged to the environment from textiles, dyeing and
are used as reference and counter electrodes. One important advantage printing industries) on SDS-modified zeolites [23]. We have applied a
is that the modification of pins with carbon ink allows their use in many modification of this standard analytical method in which a reduction in
applications. Carbon materials, such as carbon paste/ink and graphite, the sample volume and, henceforth, in the use of reagents, is achieved
are widely used in electrochemistry because of their advantageous [24].
properties: carbon is cheap and chemically inert, and shows high surface Moreover, instead of using a colorimetric assay, we have taken

Fig. 1. Schematic representation of the: A) different parts of the pin and their functions, B) modification of the stainless-steel pins used as working electrodes, C)
electrochemical cell fabricated using a 100–1000 μL micropipette tip.

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A. González-López et al. Talanta 224 (2021) 121732

advantage of the electrochemical activity of MB and its growing interest of the tip (0.59 and 1 mm, respectively) and to ease the handling of the
in biosensing (e.g. as indicator of DNA hybridization processes through device, the micropipette was placed vertically, with the head of the pin
its interaction with the double strand [25]). Then, we have adapted the acting as WE contacting a conductive copper adhesive tape piece (3
modified standard method to detect electrochemically MB, directly in “Core, ½” (W) x 54 ft (L), Electron Microscopy Sciences) manually cut (5
the micropipette tip, as a way of determining SDS, a MBAS (methylene × 25 mm) and located over the bench. Crocodile clamps were employed
blue active substance) frequently found in wastewaters. Then, when a for connecting the copper tape (and then the WE) and the other two pins
constant concentration of MB is added to the sample, its residual con­ acting as electrodes to the potentiostat (Fig. 1C). The device was clam­
centration in the aqueous phase, after interaction with MBAS and ped to a stand with a rod (as can be seen in Figure S1).
further extraction to an organic media, is indicative of the initial MBAS
concentration in the sample. 2.3. Electrochemical measurements
Additionally, and considering the influence of surfactants on carbon
electrodes, which can improve electrochemical processes [26–28], a All measurements were done using a μAUTOLAB TYPE III (Metrohm)
simplified electrochemical method for the determination of SDS without potentiostat. A volume of 360 μL of the working solution was aspirated
following the extraction protocol previously indicated, was also devel­ into the tip to record cyclic (CV) or linear sweep (LSV) voltammograms,
oped. In this way, an increase in the electrochemical signal of MB (fixed between +0.5 and − 0.6 V. For both techniques, a scan rate of 0.1 V s− 1
concentration), seen for increasing SDS concentrations, is the basis for and a step potential of 0.002 V were used.
its determination. Then, in this work, we report two simple alternatives
for SDS determination in water samples using an innovative and 2.4. Determination of SDS (MB active substance) after extraction of the
low-cost multifunctional electrochemical platform. ion pair formed with MB

2. Material and methods A modification of the standard method used for the determination of
anionic surfactants as Methylene Blue Active Substances (MBAS)
2.1. Chemicals and materials already described [24] was here employed. In this work, 1 mL of the
sample (i.e. SDS solution in ultrapure water for optimizations, or in tap
Through all this work, 100–1000 μL polypropylene micropipette tips water for real sample analysis) was mixed with 1 mL of a MB stock so­
were used (Labbox Labware). For the assembly of the system and to lution (25 μg mL− 1 in 0.5 M HCl) and 1 mL of chloroform (CHCl3). After
facilitate micropipette handling, a foot stand with a three-point gripper shaking for 30 s, the phase separation took place. Usually is the absor­
fastening tong was employed. As electrodes, 26 × 0.59 mm stainless- bance of the organic phase containing the ion pair that is measured at
steel pins (Metalurgica Folch) were selected. Carbon paste (Gwent 652 nm. But in this case, electrochemical measurements were performed
Group Ref. C10903P14) and N,N-dimethylformamide (DMF, Merck) in the aqueous phase located over the chloroform layer, by aspirating it
were employed for the preparation of the carbon ink, used in the into the tip and recording a LSV as indicated in the previous section.
working electrode. Acidic solutions of different concentrations of
methylene blue (MB, Sigma Aldrich) were prepared in 0.5 M HCl (hy­ 2.5. Determination of SDS without extraction
drochloric acid 37% from Merck). Working sodium dodecyl sulphate
(SDS, Sigma Aldrich) solutions for optimization studies were prepared in In this case, the procedure does not involve any extraction with
ultrapure water. Also, chloroform (Sigma-Aldrich) was used for the chloroform. SDS influences the electrochemical signal of MB, and this
analysis of anionic surfactants. Millipore Direct-Q(R) 3 UV was used to was used to determine its concentration. Here, 360 μL of a solution
obtain purified water. containing SDS (in different concentrations) and a fixed concentration of
MB (25 μg mL− 1) were aspirated to record the LSV as commented before.
2.2. Electrochemical “in-the-tip” cell design The reduction current of MB changed according to the concentration of
SDS in solution. This allowed to obtain a calibration plot for different
We used stainless-steel pins as electrodes. The use of this kind of pins SDS concentrations.
as electrodes was reported previously [6,7], including the stability of a
stainless-steel pin acting as reference electrode by comparison with a 3. Results and discussion
saturated calomel electrode (a variation not higher than 3 mV over 30
min was observed). The various parts of the pins were used for different 3.1. Electrochemical design and characterization of the platform
purposes, all of them schematized in Fig. 1A. First of all, the
stainless-steel pins used as working electrodes (WE) were modified with The design of the electrochemical cell is based on the use of very
carbon ink. Carbon paste was diluted with N, N-dimethylformamide cheap and available elements: pins and tips. Micropipette tips are very
(50% w/w of carbon paste in DMF) to generate the carbon ink for the versatile in regard to the size (volume) and materials. In this case we
modification. The mixture was vortexed for a few seconds and then chose commercial polypropylene tips of 100–1000 μL volume, but a
sonicated (37 kHz of frequency and 320 W of power) for 1 h. different polymer could be employed (even modified) and pins could be
Stainless-steel pins were mass modified adhering them, by their head, to inserted in tips of lower/higher volume to adjust the volume of the
a piece of double-sided tape. Then, the stems were painted thrice with electrochemical cell according to the requirements of the application.
the carbon ink using a brush (Fig. 1B). Between the two first coatings, Pins are introduced unmodified in the upper part of the tip (RE and CE)
the pins were introduced in the oven at 70 ◦ C for 15 min. After the last but, depending on the volume, this height could be varied to ensure
one, they were left for 1 h at 70 ◦ C. there is always ionic contact between the three electrodes. Even being
Once the WEs were ready, two bare stainless-steel pins (one acting as very simple, the different parts of the pin can be used for different
reference electrode, RE, and the other one as counter electrode, CE) purposes. Hence: i) the sharp end allows to drill the polymeric tip ma­
were inserted in the micropipette tip at a distance of 28 and 30 mm from terial to insert horizontally the RE and CE. In this way, there is no need
the bottom, respectively. To favor this, the micropipette tip was previ­ to make holes in the tip wall to introduce wires and, in turn, the addition
ously introduced in the oven at 70 ◦ C for 2 min. After this, a volume of of glue is not required. This simplifies the procedure and saves time since
sample was aspirated, and the micropipette tip was sealed at the bottom glue curing is not needed. Moreover, as a positive pressure has to be
by introducing a pin covered with carbon ink (the WE). The final design applied, the holes made are fully closed after insertion of the pins and
of the tip-based cell is schematized in Fig. 1C. the pressure required to aspirate solutions with the micropipette is
As the diameter of the pin stem is approximately half that of the end maintained. ii) The stem is used directly as electrode (as for thread

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A. González-López et al. Talanta 224 (2021) 121732

process protons are involved, with oxidation favoured at acid pH. Then,
hydrochloric acid was chosen as electrolyte for the study. A volume of
360 μL of a 25 μg mL− 1 MB solution in 0.5 M HCl was aspirated and a CV
was recorded. As can be seen in Fig. 2A, a reversible redox process can be
observed with anodic and cathodic peak potentials at − 0.02 and − 0.08
V, respectively.
The intensity of the cathodic peak current was chosen as analytical
signal. The precision between different pin-based WEs and different tip-
based cells was studied recording LSVs in a 25 μg mL− 1 MB solution in
0.5 M HCl. When LSVs were performed using five different carbon ink
pins-based WEs (washing with electrolyte between measurements) and
maintaining the same micropipette tip and the same RE and CE, a
relative standard deviation (RSD) of 5% for the cathodic peak current
was obtained. The RSD obtained when the whole tip-based cell was
changed (n = 5) was 7% for the cathodic peak current. These values
demonstrated the adequate precision of the developed electrochemical
device.

3.2. Effect of SDS in the redox process of MB

As a proof-of-concept, we proved the suitability of this new low-cost

electrochemical cell to perform simple and sensitive determinations of
molecules of interest. As it was reported in previous works, submicellar
concentrations of surfactants (cationic or anionic) produced an increase
in the intensity of the oxidation and reduction peak currents as well as in
the reversibility of the electrochemical processes of aromatic species
[30–33]. In those cases, the surfactant is introduced as a modifier of the
carbon paste electrode (previously immersed in a surfactant solution
[30,31,33]), or by further addition of the surfactant to the measurement
solution [32] (approach followed in this work). Thus, the effect of SDS
on the electrochemical behavior of MB was studied recording LSVs with
the micropipette tip-based cell in presence and absence of SDS (Fig. 2B).
The concentration of SDS (20 μg mL− 1, i.e. 7.0⋅10− 5 M) was below the
critical micellar concentration (2.4 mg mL− 1 in water [34]). MB was in
slight excess compared to SDS (25 μg mL− 1, 7.8⋅10− 5 M). As expected, a
notorious increase in the cathodic peak current (from − 17.84 to − 29.83
μA) was observed when SDS was present in the measurement medium.
Taking advantage of this, calibration curves performed by varying the
concentration of MB between 0.5 and 30 μg mL− 1 in both cases (Fig. 2C),
showed a sensitivity two-fold higher when this concentration of SDS was
present in the medium. Slopes of − 1.71 (R2 = 0.996) and − 0.84 μA (μg
mL− 1)− 1 (R2 = 0.996) were obtained with and without SDS respectively.
In Fig. 2C, it can also be observed that a wider linear range was achieved
when SDS was added to the solution. This improvement is likely due to
Fig. 2. A) CV recorded in a 25 μg mL− 1 MB solution in 0.5 M HCl (scan rate 0.1 the formation of the ion pair between the MB and the surfactant, that is
V s− 1, step potential 0.002 V) using the micropipette tip-cell. B) Cathodic stabilized at the electrode surface (as in the case of SDS and catechol­
processes recorded by LSV in a 25 μg mL− 1 MB solution without SDS and with amines [30] or cationic surfactants with flufenamic acid [33] or nitro­
20 μg mL− 1 of SDS (scan rate 0.1 V s− 1, step potential 0.002 V) using the phenol [32]).
micropipette tip-cell. B) Calibration curve of MB without SDS and with 20 μg
mL− 1 of SDS. Error bars indicate the standard deviation of three replicates. 3.3. Determination of SDS using MB as indicator by both approaches:
with and without extraction
microfluidics [5]; in other previous works the electrode was the pinhead
[6–8]), either modified with carbon ink (WE) or unmodified (RE and High concentrations of surfactants could have important environ­
CE). In the last case, the part of the stem that is out of the tip can be used mental consequences and their determination becomes relevant in water
to connect the pins to the potentiostat using crocodile clips. iii) The head samples suspected of their presence. Based on previous results and
of the pin that is introduced vertically (WE) closes the tip at the bottom. taking advantage of the effect of SDS in the cathodic peak of MB, a
With this design, the connection is easily made by contacting the calibration curve for SDS was performed adding different SDS concen­
pinhead with copper tape that is adhered on a flat substrate. The area of trations to a solution containing the same MB concentration (25 μg
the WE could be changed by varying the length of the pin. In our case, mL− 1) (approach I in Fig. 3A). As Fig. 3B shows, the intensity of the
we used 26-mm long stainless-steel pins. With a diameter of 0.59 mm, an cathodic peak current of MB (25 μg mL− 1) increases with SDS concen­
approximated geometric area of 48.2 mm2 was estimated (only the tration, following the equation IMB (μA) = − 0.26 CSDS (μg⋅mL− 1) – 9.56,
lateral area of the cylinder). with a R2 of 0.994. The limit of detection (LOD) and the limit of quan­
After the three electrodes were ready inside the micropipette tip, the tification (LOQ) were calculated as 3sb/m and 10sb/m respectively,
new electrochemical platform was characterized. For this purpose, the where m is the slope of the calibration plot, and sb is the standard de­
electrochemical behavior of methylene blue (MB) was studied. To be viation of the intercept. LOD and LOQ values thus obtained were 1.3 μg
oxidized, MB has to be first reduced to the leuco form [29]. In this redox mL− 1 (4.5⋅10− 6 M) and 4.3 μg mL− 1 (1.5⋅10− 5 M) respectively.

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A. González-López et al. Talanta 224 (2021) 121732

Fig. 3. A) Scheme of both approaches (with and without extraction) for SDS determination using MB as indicator. B) Calibration curve of SDS employing the
electrochemical measurements of MB obtained without extraction. C) Picture of microcentrifuge tubes with different SDS concentrations (0, 2.5, 5, 10, 20 and 30 μg.
mL-1) after phase separation using the modified standard method for the analysis of MBAS. D) Calibration curve for SDS employing the electrochemical mea­
surements of MB that remained that in the aqueous phase after performing the modified standard method for the analysis of MBAS. Error bars correspond to the
standard deviation of 3 measurements.

A second approach for SDS determination (approach II in Fig. 3A) lower the concentration of the remaining MB in aqueous phase and, in
was developed modifying the standard method to detect anionic sur­ turn, the analytical signal. Thus, this intensity correlated linearly with
factants [23]. This is based on the spectrophotometric measurement the concentration of SDS following the equation IMB (μA) = 0.37 CSDS
performed in the organic phase, which contains the ion pair SDS-MB. In (μg⋅mL− 1) – 13.78 with a R2 of 0.997. A LOD of 1.2 μg mL− 1 (4.2⋅10− 6
this work we have only considered SDS since is the anionic surfactant M) and a LOQ of 3.7 μg mL− 1 (1.3⋅10− 5 M) were obtained using the
usually present at higher concentration [22], but all the anionic sur­ above formula. Therefore, similar LODs were obtained for both meth­
factants that form ion pairs with MB (MBAS) could be determined odologies, although the measurement after the extraction provides a
jointly. After following the modified method explained in the experi­ slightly higher sensitivity (almost one and a half times).
mental section, an aqueous and an organic phase were obtained after
extraction with chloroform and phase separation. The organic phase 3.4. Application to tap water samples analysis
contains the ionic pair MB-SDS and in the aqueous phase remains the
excess of MB that has not reacted. Thus, the aqueous phase was aspirated In order to evaluate the accuracy of this new tip-based electro­
inside the micropipette tip-cell for performing the electrochemical chemical device, both methods (with and without previous extraction)
measurement. As the ion pair has been extracted, the analytical signal were probed with spiked water samples. Related to the possible in­
(intensity of the peak current of the cathodic process of MB) will be terferences in real samples, two main cases could be considered. On the
indirectly proportional to the concentration of anionic surfactants (SDS) one hand, any compound that could be reduced at the potential of MB or
in the sample. lower could be considered as interferent. However, reduction processes
For this study, different concentrations of SDS were tested using a in organic molecules are not as common as the oxidation ones, and the
fixed concentration of MB (25 μg mL− 1). Each SDS solution (in ultrapure potential of reduction is not extremely negative. Moreover, instead of a
water) was mixed for 30 s with 1 mL of MB solution and 1 mL of chlo­ chronoamperogram, a linear sweep or cyclic voltammogram is recorded,
roform as explained in the Section 2.4. After phase separation, the layer that could be more informative about the processes present. On the other
at the top was aspirated into the micropipette-tip-cell and the micropi­ hand, any anionic compound that could interact with cationic methy­
pette was clamped to the stand to proceed with the measurements. lene blue could decrease its content in solution and behave as interferent
As can be seen in Fig. 3C, as SDS concentration increases, aqueous when extraction is performed. This is the reason why the standard
and organic phases (top and bottom) become lighter and darker method on which we are based for SDS determination is reported as
respectively, due to the interaction of MB with SDS and further extrac­ method for MBAS determination, in order to consider all the com­
tion with chloroform. In Fig. 3D, a calibration plot with the measure­ pounds. Similarly, when no extraction is carried out, other surfactants
ments performed in the aqueous phase after phase separation for six could increase the signal of MB. However, SDS is one of the main MBAS
different concentrations of SDS is shown, where IMB is the intensity of and the most common anionic surfactant. In case important in­
the MB cathodic peak current obtained from a LSV recorded from +0.5 V terferences are suspected, a thorough study should be performed
to − 0.6 V. As can be observed, the higher the SDS concentration, the previously.

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A. González-López et al. Talanta 224 (2021) 121732

Table 1 Declaration of competing interest

Results of the recovery test in tap water samples for both methods for SDS
determination (mean value ± standard deviation for three replicates). The authors declare that they have no known competing financial
[SDS] added [SDS] found Recovery interests or personal relationships that could have appeared to influence
(μg⋅mL− 1) (μg⋅ mL− 1) the work reported in this paper.
Sample With 8 7±1 93%
1 extraction Acknowledgment
Without 8 8±1 98%
extraction
Sample With 17 19 ± 1 111% Andrea González-López thanks the Consejería de Educación y Cul­
2 extraction tura del Gobierno del Principado de Asturias for the award of her
Without 17 17 ± 1 98% “Severo Ochoa” grant (BP17-36).
extraction

Appendix A. Supplementary data

Tap water from a municipality (Lugones, Siero) located in the center
of the Principality of Asturias, Spain, was spiked with two different SDS Supplementary data to this article can be found online at https://doi.
concentrations (8 and 17 μg mL− 1). Samples were analyzed by both org/10.1016/j.talanta.2020.121732.
methodologies and the results obtained are reported in Table 1. Using
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