Advances in Sample Preparation 8 (2023) 100097

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Advances in Sample Preparation

journal homepage: www.elsevier.com/locate/sampre

Recent elaborations in electromembrane microextraction technique for

preconcentration of chromium species: A mini-review
Waleed Alahmad a, *, Shaymaa A. Mohamed a, Ahmad Halabi b, c, *
a
Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok, Thailand
b
Department of Analytical Chemistry, Faculty of Pharmacy, Al_Shamal Private University, Idlib, Syria
c
Department of Chemistry, Faculty of Science, Idlib University, Idlib, Syria

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

Keywords: In recent years, electromembrane microextraction techniques have been used widely for the analysis of chro­
Hexavalent chromium mium species (trivalent and hexavalent chromium) in different environmental matrices. It is based on the
Trivalent chromium electrokinetic migration across a membrane under the effect of an external electrical field between two aqueous
Electromembrane extraction
phases. Trace analysis in complex matrices usually requires an effective sample preparation step to isolate,
Gel electromembrane microextraction
Green sample preparation
extract, and enrich the target analytes. Due to its distinctive qualities, including a high degree of enrichment
Environmental analysis factors, clean-up, and conformity with green chemistry principles, electromembrane microextraction techniques
are among the methods for extracting chromium that have gained much attention in recent years. These tech­
niques could be classified into two groups; electromembrane extraction (EME) which is based on using hydro­
phobic compounds (e.g., a few microliters of organic solvents) to separate the two aqueous solutions (donor and
acceptor solutions), and gel electromembrane microextraction (G-EME) which is based on using a membrane
made of biopolymers. In this review, the most recent advancements in EME and G-EME technologies for the
extraction of chromium species in environmental samples in the last five years were summarized. Furthermore,
the performance of the systems is evaluated in terms of their precision and accuracy, detection limits, and merits
and drawbacks. Finally, future perspectives on these techniques were discussed.

1. Introduction
In the environment, chromium exists primarily in two oxidation
states: trivalent and hexavalent. The biological and toxicological prop­
erties of each oxidation state differ significantly. Cr(III) plays an essen­
tial role in maintaining the normal metabolic process of fatty acids,
cholesterol, and glucose in mammals. Moreover, it is widely used as a
dietary supplement [1,2]. In contrast, due to its numerous uses, Cr(VI) is
a highly hazardous and carcinogenic element that frequently appears as
a contaminant in food, soil, and water [3]. The World Health Organi­
zation has established the maximum contaminant level of hexavalent
chromium in drinking water at 0.05 mg L− 1 [4]. Analyzing these various
forms of trace substances can be quite challenging. That is why sample
preparation is necessary to reduce any interference from the matrices
and to concentrate the specific analytes of interest.
The impossibility of direct analysis of the complex sample matrices
using analytical instruments led to finding solutions for this obstacle,
represented in the sample treatment/preparation step. Pre-analytical
treatment offers the benefit of reducing matrix effects and enhancing
the concentration of the target analytes, thus enabling modern analyt­
ical instruments to achieve improved sensitivity [5–7]. Significant ef­
forts have been put into establishing various sample preparation
methods over the past few decades. Electromembrane-based extraction
methods, among them, provide innovative alternatives to conventional
sample processing since the membranes are reliable and simple to set up,
need little organic solvent, and offer clean-up capacity and high
enrichment factors for intricate matrixes [8–10]. These techniques could
be classified into two main groups; electromembrane microextraction
which is based on using hydrophobic compounds (e.g., a few microliters
of organic solvents) to separate the two aqueous solutions, and gel
electromembrane microextraction which is based on using membrane
made of biopolymers.
There have been several excellent reviews published in the past
decade on methods for removing and preconcentrating chromium spe­
cies prior to analysis [11–14]. To the best of our knowledge, no review
has addressed the advancement of electromembrane-based

* Corresponding authors.
E-mail addresses: waleed.al@chula.ac.th, waleed.alahmad.cu@gmail.com (W. Alahmad), ahmadghbc@gmail.com (A. Halabi).

https://doi.org/10.1016/j.sampre.2023.100097
Received 24 August 2023; Received in revised form 1 October 2023; Accepted 10 October 2023
Available online 11 October 2023
2772-5820/© 2023 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
W. Alahmad et al.
microextraction methods for chromium species. We present here a re­
view of recent advances in electromembrane-based microextraction
techniques for extracting and preconcentrating Cr species, from an
analytical perspective. There is also a focus on the benefits and draw­
backs of these strategies.
2. Classification of electromembrane-based extraction
techniques
2.1. Electromembrane extraction (EME)
EME was designed for selective extraction and preconcentration of
polar and charged analytes, whereas the driving force is the electrical
potential applied across a thin liquid membrane of organic solvent (few
microliters) held inside the pores of a polymeric membrane (supported
liquid membrane or SLM) or a plug of organic solvent is wedged between
two plugs of aqueous phases inside a transparent capillary tubing (free
liquid membrane or FLM). SLM/FLM is used to separate the sample from
a clean acceptor solution. EME may be regarded as a green extraction
method since it uses extremely small amounts of organic solvent
[15–17]. As voltage-assisted partitioning explains extraction selectivity,
the properties of the SLM solvent as well as the magnitude and polarity
of the electric field also play a role. In addition, a voltage applied to an
SLM can accelerate the mass transfer of charged or ionizable analytes
over the SLM and into the acceptor solution using an electrokinetic
migration mechanism [18]. EME has been performed in various tech­
nical formats, for example, hollow fiber [19], on-chip [20], and 96-well
[21]. In recent years, several attempts have been made to replace the
organic-based SLM with a green membrane to comply with the green
chemistry criterion. For example, deep eutectic solvents (DESs) as a
liquid membrane have been investigated in EME applications as green
and sustainable media [22]. However, EME with DESs as SLM for the
extraction of chromium species has not been reported yet. Another
example is gel electromembrane extraction based on biopolymer mem­
brane compositions which has been used for the extraction of both Cr
(VI) and Cr(III).
2.2. Gel electromembrane microextraction (G-EME)
In order to adhere to the green chemistry principles, a newly
improved form of EME called G-EME has been created to replace
petroleum-based SLM/FLM with a biopolymer aqueous membrane,
which has brought several benefits over conventional electromembrane
extractions. Biopolymer aqueous membranes used include tragacanth,
agar, agarose, and chitosan. These materials have to be able to dissolve
in water or another green solvent and form a solid phase either at room
temperature or below zero temperature (− 4 ◦ C). The most common two
materials used in G-EME to form the membranes are agar and agarose.
These materials are not soluble in water at room temperatures, therefore
Fig. 1. Schematic illustration of the (A) EME and (B) G-EME setup and apparatus. [taken from [22] with permission from Elsevier].
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Advances in Sample Preparation 8 (2023) 100097
heating of these solutions is required in the fabrication step. They are
prepared at different concentrations resulting in different porosity. For
example, agarose gel membranes with concentrations of 2 %, 3 %, and 4
% (w/v) had pore sizes of about 370 nm, 290 nm, and 240 nm,
respectively, which means that the higher concentration (% w/v) had a
lower pore size [23]. Moreover, the pH of these membranes can be
adjusted through the preparation step resulting in better results and
feasibility compared to EME whereas the pH of SLM could not be
tunned.
G-EME is a highly intriguing strategy for future green analytical
chemistry because it is entirely solvent-free [24]. The setup and
extraction technique are comparable to EME, where the electrical po­
tential applied across the gel membrane acts as the driving force. Fig. 1
shows the difference in setup between EME and G-EME [22]. For the
past ten years, G-EME has been widely employed in several sectors for
the extraction and preconcentration of various types of analytes [23,25,
26].
3. EME & G-EME applied towards the determination of
chromium species
3.1. Cr(VI) detection
The conventional setup of EME consisted of a porous polypropylene
hollow fiber membrane impregnated with organic solvents (1-octanol or
2-nitrophenyl octyl ether (2-NPOE) in most cases) [16] or polymer in­
clusion membrane [27]. The acceptor solution is filled into the lumen of
this fiber and sealed at the end. A platinum electrode is usually inserted
in the lumen and placed in a vial containing a sample solution (donor
solution). To complete the circuit in the setup, another platinum elec­
trode is placed in the donor solution. The driving forces come from the
power supply operating at different voltages and a constant current.
After the extraction, the acceptor is withdrawn from the lumen and
brought further for quantitative analysis [16]. Other than the electro­
kinetic migration method, the organic solvent may occasionally be
combined with an ionic carrier to improve the extraction efficiency [27].
Instead of using an ionic carrier, Tahmasebi et al. modified the
polypropylene hollow fiber membrane with polyaniline (PANI) polymer
via electrochemical polymerization of aniline in an acidified medium
[28]. It is important to note that 1-octanol and acetonitrile were added
to the polymerization process for improved aniline diffusion and poly­
merization in the hollow fiber pores. The results revealed that increasing
the effective surface area of the PANI nanostructure enhanced the sep­
aration performance by increasing the possibility of PANI interacting
with Cr(VI) via an anion exchange mechanism. Under optimized
extraction conditions, the linear range was between 0.02 and 2 µg L− 1
while the enrichment factor (EF) was equal to 106, which is considered
superb. The LOD level was attained at 0.006 µg L− 1 which showed the
advantage of this modification over the conventional approach using the
W. Alahmad et al. Advances in Sample Preparation 8 (2023) 100097

same detection method (0.01 µg L− 1 [29]). However, it is worth
mentioning here that using EME with spectrophotometric detection
gave a higher LOD (4.1 µg L− 1 [16]). Thus, the detection instrument
plays a key role as well.
In fact, a variety of anions can be doped into PANI, including HClO4,
H2SO4, and HCl, acting as an anion exchanger in the electro­
polymerization technique. Analytes can then be used to replace these
doping anions.
On-chip EME is another format of electromembrane extraction and it
is totally different in configuration from the conventional one. Two
polymethylmethacrylate plates were used as substrates for the chip
device. Every part of the device was carved with a pattern of spiral
microfluidic channels having a specific width and depth. One of these
channels acts as an acceptor solution and another one as a donor
(sample) solution. The electrodes in On-chip EME are added in different
ways compared to the conventional EME. Herein, the full length of the
channels was covered with electrodes that were bent and embedded.
Finally, a porous polypropylene sheet membrane impregnated with

Fig. 2. (A) On-chip EME for extraction and detection of Cr(VI): a) the equipment used in the EME chip device, b) the digital visuals of the sorbent following the
absorption of the substance act as a medium for the RGB analysis, allowing for the examination of various concentration levels (taken from [30] with permission from
the Royal Society of Chemistry). (B) Schematic of EME-µ-EME procedure for the selective extraction of Cr(VI) from food samples (taken from [32] with permission
from Elsevier). (C) a) The schematic of the extraction system in gel-EME, b) the components and steps involved in the spectrometric detection of the colored gel.
(taken from [33] with permission from Elsevier).

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organic solvent is used to separate both acceptor and donor solutions.
Zarghampour et al. took advantage of this format by exploring the
determination of Cr(VI) in tap water and wastewater samples [30].
Herein, the polypropylene membrane was impregnated with 2-nitro­
phenyl octyl ether containing 15 % di-(2-ethylhexyl) phosphate.
The interesting point about this work is that the Cr(VI) was reacted
and complexed with diphenylcarbazide (DPC) prior to the EME step. Cr
(VI) reacts with DPC in an acidic solution, therefore, the effect of acidity
of the aqueous solution on the formation of metal-chelate and extraction
efficiency was studied in 0–20 mmol L− 1 sulfuric acid. The best effi­
ciency was obtained in the sample solution containing 10 mmol L− 1 of
H2SO4. Through the EME extraction, the sample solution (which
included the Cr(VI)-DPC) as well as the acceptor solution (500 µL of 100
mM HCl) were injected into the designated channels using a syringe
pump and a micro-syringe, respectively. Due to the ease with which the
analyte can be released from the SLM into the acceptor solution, the
extraction efficiency of EME is improved by raising the HCl content in
the acceptor phase (AP) of alkaline analytes.
In order to increase the sensitivity, the colored complexes in the
acceptor solution were preconcentrated onto 2 mg of strong cation ex­
change (SCX) sorbent in a silicon tube. The detection part was conducted
using a smartphone instead of using sophisticated and expensive in­
struments. The token photos of the colored solid phase (Fig. 2a) were
analyzed in RGB analysis and the reported LOD was equal to 10 µg L− 1.
Even though this LOD is high compared to other methods, it is still
enough to show the toxicity of water samples. However, the complexity
of the microfluidic system’s design made it difficult for the extraction
and detection systems to be integrated. In addition, a significant volume
of organic solvent was still employed compared to conventional EME.
Micro-EME (µ-EME) with free liquid membrane (FLM) design was
reported for the first time by Nojavan et al. for the determination of Cr
(VI) in plating, textile, and paint manufacturing wastewaters [31]. An
utterly different setup from the previous work above we can see in
µ-EME. In detail, a micro-hematocrit capillary tube (ID 1.15 mm, length
75 mm, and volume 75 µL) was filled with donor phase (DP) (60 µL),
1-octanol containing 5 % Aliquat® 336 (as the liquid membrane) (1 µL),
and AP (6 µL), successively. The extraction unit is horizontally posi­
tioned and the negative and positive electrodes were placed in the DP
and AP, respectively. It is worth mentioning here that the whole µ-EME
system was kept without stirring (fully stagnant). Using electrothermal
atomic absorption spectrometry (ETAAS) as a detection technique, the
reported LOD was 0.06 µg L− 1. However, the recoveries were lower, and
RSDs were higher than other EME reports as shown in Table 1.
The same research group combined the conventional EME with
µ-EME (Fig. 2B) for the selective extraction and detection of Cr(VI) from
food samples (milk powder, basil, and fish samples) utilizing ETAAS as a
detection technique [32]. The SLM in the conventional EME was a
polypropylene hollow fiber membrane impregnated with 2.5 % (w/v)
Aliquat® 336 in 1-octanol and the AP (40.0 µL of aqueous solution
(pH=9.0) contains ClO−4 (0.1 M)) was filled in the lumen of this mem­
brane. For combining the EME and µ-EME, the authors used the acceptor
solution of step-1 (EME) as a donor solution in a µ-EME after adjusting
the pH from 9.0 to 2.0. To set up µ-EME, the capillary glass tube was
filled sequentially with 50.0 µL donor solution (pH=2.0), 1.0 µL 5.0 %
(w/v) Aliquat® 336 in 1-octanol (as the FLM), and 10.0 µL aqueous
acceptor solution (pH=9.0) contains ClO−4 (0.5 M) as a counter ion. As a
point of clarification, in carrier-mediated transport across the membrane
for the release of the analyte into the acceptor solution, a counter ion
must be present for it to be displaced by the analyte. Under the opti­
mized conditions, a low detection limit (0.003 µg L− 1) with a very high
preconcentration factor (584) were valuable outcomes of this method
compared with traditional procedures. However, high RSD% values (˂
11.9) and low relative recoveries (64 %) were reported as shown in
Table 1.
In order to reduce the number of steps in the extraction and detection
of Cr(VI), Sahragard et al. introduced a one-step colorimetric G-EME
sensing platform for the simultaneous extraction and quantification of
Cr(VI) [33]. Herein, colorimetric reagents containing DPC (1 % (w/v))
and nitric acid (0.5 mM) were mixed with the agarose gel (2 % (w/v)) in
the gel fabrication step. The Cr(VI) ion migrated, via electromigration,
from the solution in the sample and underwent a chemical reaction with
the previously added reagents within the gel, resulting in the formation
of a violet hue. It is worth mentioning here that there is no AP in this
system and the gel membrane, thus, the anode electrode was fixed in the
gel membrane which is held inside the vial (Fig. 2C, a). Following
extraction, the colored gel-containing vial was placed within a

Table 1
Highlights the electromembrane-based extraction technique designed for Cr(VI) extraction and detection.
Analytes & (Samples) Extraction/Detection SLM/Acceptor phase Enrichment Linear LOD RSD Recovery Ref.
technique factor range (µg % (%)
(µg L− 1) L− 1)

Cr(VI) (Tap, drinking, and EME/UV–Vis 2-NPOE /Acetic acid 0.5 M 80 10–60 4.1 ˂ 3.0 95–125 [16]
mineral waters) 15–80 6.2
10–80
7.0
Cr(VI) (Spring and sea EME/ET-AAS 1 octanol/NaOH (pH = 13) 106 0.02–2 0.0006 ˂ 80–105 [28]
waters) 12.3
Cr(VI) (Tap and waste EME(Chip)/ 15 % (v/v) DEHP in NPOE/HCl 100 mM *NR 30–1000 10 ˂ 8.5 96–102 [30]
waters) Colorimetry (RGB)
Cr(VI) (Industrial waste µ-EME/ET-AAS 5 % Aliquat®336 in octanol/NaClO4 0.5 M 9.1 0.5–14 0.06 12.3 74–85 [31]
waters)
Cr(VI) (milk powder, basil, EME-µ-EME /ET-AAS 2.5 % Aliquat®336 in octanol/NaClO4 0.1 M @ 584 0.01–5 0.003 ˂ 64–110 [32]
and fish samples) 5 % Aliquat®336 in octanol/NaClO4 0.5 M 11.9
Cr(III) and Cr(VI) (Tap, EME/Colorimetry 1-octanol/Acetic acid 0.7 M 245–271 3–30 1.0 ˂ 7.0 84–107 [19]
drinking, and mineral (RGB) and and
waters) 3–70 0.7
Cr(III) and Cr(VI) (Tap, DG-EME/ Agarose gel/DI water 40 and 47 10–200 3.0 ˂ 9.8 84–103 [36]
drinking, and mineral Colorimetry (pH = 2&3) and and
waters) (RGB) 7–200 2.0
Cr(III) and Cr(VI) & (Tap, DG-EME/ Agarose+5 %dextrin/DI water (pH = 3) 52 and 45 1.5–200 0.5 ˂ 7.2 89–104 [37]
drinking, mineral, and Colorimetry and and
wastewaters) (RGB) 2–200 0.7
Cr(III) and Cr(VI) & ( IT-G-EME Agarose gel/DI water 42 and 36 20–250 7.0 ˂ 8.8 92–108 [38]
Drinking and mineral /Colorimetry (RGB) (pH = 4&5)
waters)

*NR: Not Reported.

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handmade holder, exposed to LED light, and its absorbance was
measured with a portable spectrometer. The reported LOD was equal to
5 µg L− 1 while the relative recovery values were between 96 % and 110
%, with RSDs of ≤4 %. The overall analysis time could be reduced, while
enhancing the relative standard deviation and sensitivity, by minimizing
the number of steps involved in the process. This improvement was
observed in comparison to the EME, on-chip EME, and G-EME systems.
An interesting study was conducted by Çalık et al. on the kinetic
transport of Cr(VI) in EME [34].
Celgard 2500 membrane (with polypropylene structure) was used in

Fig. 3. (A) Two different setups of EME. (a) DEME for Cr speciation. (b) SEME for determination of Cr(VI)/Cr(III), [taken from [19] with permission from Elsevier];
(B) Schematic illustration of the dual gel electromembrane extraction setup for the simultaneous extraction of Cr(VI) and Cr(III), [taken from [36] with permission
from Springer. (C) Schematic illustration of the proposed IT-G-EME setup, [taken from [38] with permission from Elsevier].

5
W. Alahmad et al.
this study due to its ease of use and economic properties. The effect of
the type of carrier and its concentration and the solvent type was
investigated. The kinetic data represented by the rate constant (k), the
flux value (J), the permeability coefficient (P), and the recovery factor
(RF%) were calculated from the following equations:
ln(C / C0 ) = − kt (1)
P = (V / A)xK (2)
J = PxC (3)
RF = ((C0 − C) / C0 )x100% (4)
C is the concentration of Cr(VI) in the sample phase at t time, the
initial concentration in the sample phase is the initial concentration; t is
the transport time; V is the sample volume, and A is the surface area of
the membrane.
Four different types of organic solvents, namely kerosene, 2-NPOE,
dichloromethane, and chloroform, were tested. The kinetic data
showed that the highest values for k, P, J, and the RF% were observed
when using 2-NPOE as SLM. Moreover, Aliquat® 336 showed superior
carrying ions properties over bis(2-ethylhexyl) phthalate (2-DEHP) ac­
cording to the kinetic data. In addition, the mass transportation rises as
the carrier concentration increases, without reaching a level of viscosity
that would impede transportation in the membrane phase. The k and P
values had increased as the concentration of Aliquat® 336 increased.
However, the amount of Cr(VI) that may be transported through the
SLM is constrained by the high carrier concentration in the membrane
phase. The findings of this study indicate that the carrier concentration
plays a significant role in facilitating the transport of metal cations in the
EME process.
3.2. Speciation of Cr(III) and Cr(VI)
In aqueous media, the distribution of Cr(III) and Cr(VI) species is
largely dependent on pH, oxidizing and reducing compounds, and redox
potential. In light of these factors and because Cr(III) and Cr(VI) have
distinct levels of toxicity and bioavailability, it is crucial to assess the
concentrations of each chromium species.
Alahmad et al. applied the conventional EME for the detection of Cr
species onto the µPAD for the first time [19]. The detection chemistry
was based on the reaction between Cr(VI) and DPC to form a purple
color. In their work, two different approaches were used for Cr specia­
tion (Fig. 3A). Single EME (SEME) was used for the Cr(VI) detection in
the first approach. It was necessary to convert all types of Cr species to Cr
(VI) using cerium (IV) in order to achieve the total Cr, as in previous
studies, in order to detect Cr(III). Then, Cr(III) was obtained by sub­
traction of Cr(VI) from the total Cr. The reported dynamic range was
3–70 µg L− 1 for Cr(VI) and 3–30 µg L− 1 for Cr(III). In the second
approach, anionic Cr(VI) and cationic Cr(III) ions were extracted
simultaneously using a dual EME (DEME). As opposed to the previous
approach, this one involved the oxidation of Cr(III) to Cr(VI) by Ce(IV)
after extraction and before colorimetric detection on the PAD. In terms
of linearity, this DEME exhibited a range of 3–70 µg L− 1 for Cr(VI) and
50–150 µg L− 1 for Cr(III). The findings indicated that both methods
yielded a comparable LOD of 0.7 µg L− 1 for detecting Cr(VI). However,
SEME demonstrated a superior LOD for Cr(III) compared to DEME, with
a difference of 1.0 µg L− 1 versus 5.5 µg L− 1, respectively. In comparison
to another work with the same detection chemistry and using the same
platform but without using the EME step, the LOD for that work was 180
µg L− 1 (Cr(VI)) [35] which is almost 257 times higher than the work
using the EME step. Herein, it is shown the importance of using EME for
high-sensitivity detection.
Tabani et al. developed, for the first time, dual gel-EME (DG-EME)
for the simultaneous extraction of Cr(VI) and Cr(III) [36]. To fabricate
the gel membranes, the agarose powder was dissolved in Milli-Q water
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Advances in Sample Preparation 8 (2023) 100097
and heated in a microwave. A specific quantity of the heated solution
was swiftly moved to a 0.5-mL Eppendorf tube using a micropipette and
placed in a refrigerator at 4 ◦ C for a duration of 60 min. Using cathodic
and anodic electrodes, two Eppendorf tubes containing gel with pH 5.0
and pH 4.0 were used for the extraction of Cr(III) and Cr(VI), respec­
tively, as shown in Fig. 3B. The detection chemistry was the same as in
previous work [19]. The LODs obtained by DG-EME (LOD of 2.0 µg L− 1
for Cr(III) and 3.0 µg L− 1 for Cr(VI)) were somewhat higher than those
obtained by EME. It is possible that this could be explained by a dilution
effect of APs due to electroendosmosis (EEO), resulting in a decrease in
sensitivity.
To solve the problem raised by EEO, the same group modified the
agarose gel membrane with 5 % (w/v) dextrin [37], resulting in a
lowering of the EEO and better LODs (0.5 and 0.7 µg L− 1 for Cr(III) and
Cr(VI), respectively,).
Inspired by the µ-EME extraction system, Varanusupakul et al.
developed an in-tube gel electro-membrane microextraction (IT-G-EME)
miniaturized extraction system for the simultaneous extraction of Cr(III)
and Cr(VI) [38]. The arrangement included narrow tubes made of
polymers, which served as the container for the liquid AP. Additionally,
a small agarose gel membrane, measuring 2.5 mm, was positioned at the
starting point of the tubes. A circular-shaped vial (1.5 mL, pH 5.5)
containing chromium species as DP was connected between the two
previous tubes. Later on, the open end of each tube was filled with 30 µL
of aqueous AP (pHs were adjusted at 5.0 and 4.0 for anodic and cathodic
APs, respectively). At the end of extraction, each aqueous AP was
separately withdrawn by micropipette for quantitative analysis using
the same chemistry described in the previous work [19]. Even though
the LOD reported in this work is high (7.0 µg L− 1) compared to other
methods, it is sufficient to indicate if the samples are contaminated or
not. Also, a wide linear range between 20 and 250 µg L− 1 was obtained
by this method. The key properties of these extraction techniques
employed for the identification of Cr species are shown in Table 1.
Summarizing the advantages and drawbacks of the EME and G-EME
methods is a difficult task.
Selecting the device, configuration, and extraction method will
depend mostly on the objectives and the goals of the work as well as the
matrices. To compare the most effective application for each system, we
can strive to emphasize the benefits and potential drawbacks of each
setup. Table 2 shows the pros and cons of these systems for the extrac­
tion of Cr species. All these systems showed the ability to extract Cr(VI)
and Cr(III) efficiently after tuning the extraction parameters. EME suf­
fers from using organic solvents and the need for additives to improve
extraction efficiency. On the other hand, G-EME is a green extraction
technique and does not require the addition of additives to the mem­
brane compositions. In addition, G-EME is less selective than EME, and
EEO can occur during the extraction process.
4. Conclusion and future perspectives
The latest developed electromembrane microextraction approaches
and systems for chromium species in the last five years have been
reviewed. The analytical advantages of these systems, the membrane
arrangements, and the detection strategies for the preconcentration and
identification of Cr species have been emphasized.
EME has been widely used for Cr detection due to its excellent
extraction efficiency and the adjustable sample volume at milliliter
level. µ-EME has been introduced to reduce the usage of organic solvents
and to eliminate the need for stabilization of liquid membranes in
porous supporting materials (hollow fiber). Kinetically, the addition of
carriers such as Aliquat® 336 to the SLM/FLM enhanced the mass
transportation and resulted in better sensitivity.
To comply with the green chemistry principles, G-EME has been
developed where the petroleum-based SLM was replaced by a green
membrane. This technique showed high selectivity and extraction effi­
ciency as well. However, It has suffered from the EEO effect that could
W. Alahmad et al. Advances in Sample Preparation 8 (2023) 100097

Table 2 Finally, we expect that the knowledge gained from the present study
Advantages and disadvantages of different types of reported membrane-based will spur scientists to create more microextraction platforms based on
microextraction systems for the determination of Cr(III) and Cr(VI) ions. new electromembrane technologies for a variety of sample types.
Extraction Advantages Disadvantages
system Declaration of Competing Interest
a
EME Extensive cleanup. Organic solvents are still
High enrichment factors. needed. The authors declare that they have no known competing financial
Remarkable efficiency. An ion-pairing reagent or interests or personal relationships that could have appeared to influence
Facile automation. carrier is required.
the work reported in this paper.
Acceptable selectivity. Rely entirely on the power
polymeric membrane. supply.
Electrolysis of water. Data availability
Large sample volume.
The effect of Data will be made available on request.
Electroendosmosis is NOT
obvious.
b
µ-EME Only a few microliters of organic Organic solvents are still
solvent are used. needed. Acknowledgment
Acceptable selectivity. An ion-pairing reagent or
Requirement for small sample carrier is required.
This project was supported by the Al_Shamal Private University,
quantities (~ 70 µL). Rely entirely on the power
A miniaturized extraction setup. supply. Idlib, Syria, and by the Department of Chemistry, Faculty of Science,
Electrolysis of water. Chulalongkorn University, Thailand. The authors would like to thank
low enrichment factor. Prof. Dr. Mohamed Nedal Khateeb for his continuous support, inspira­
The DP cannot be stirred. tion, and leadership.
The effect of
Electroendosmosis is NOT
obvious. References
c
G-EME It is completely green chemistry The effect of
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