Article SV

PrIMEr
Electrochemical stripping analysis

Cristina Ariño 1, Craig E. Banks2, Andrzej Bobrowski3, Robert D. Crapnell 2
,
Anastasios Economou 4 ✉, Agnieszka Królicka 3, Clara Pérez-Ràfols 1,
Dionysios Soulis4 and Joseph Wang5
Abstract | Electrochemical stripping analysis (ESA) is a trace electroanalytical technique for the
determination of metal cations, inorganic ions, organic compounds and biomolecules. It is based
on a pre-concentration step of the target analyte(s), or a compound of the target, on a suitable
working electrode. This is followed by a stripping step of the accumulated analyte using an elec-
troanalytical technique. Advantages of ESA include high sensitivity and low limits of detection,
multi-analyte capability, low cost of instrumentation and consumables, low power requirements,
potential for on-site analysis, speciation capability and scope for indirect biosensing. This Primer
covers fundamental aspects of ESA and discusses methods of pre-concentration and stripping,
instrumentation, types of working electrodes and sensors, guidelines for method optimization,
typical applications, data interpretation and interferences, and method limitations and
workarounds. Finally, the current trends and future prospects of ESA are highlighted.
Pre-concentration Electrochemical stripping analysis (ESA) is a family of electrolysed a dilute Cu2+ solution with copper depo
The process by which the electroanalytical techniques mainly applicable to the sition on a platinum electrode. He then reversed the
analyte (or its compound) quantitative determination of metal cations, inorganic polarity of the two electrodes, dissolving the copper
is deposited on the working anions, organic compounds and biomolecules. It is metal at constant current, and measured the charge
electrode.
used in fields where trace or ultra-trace quantification required to dissolve the copper deposit. The amount
is required. For example, one of the main applications of of copper was then calculated using the Faraday law15.
ESA is to monitor and speciate heavy metals in environ- However, Geoffrey Barker can be considered the inven-
mental samples1–3. Other important applications involve tor of modern stripping techniques when, in a landmark
pharmaceutical analysis, food analysis, clinical chemistry paper, he formulated the complete concept of stripping
1
Department of Chemical and forensics4–6. techniques at a mercury drop electrode16. The evolution
Engineering and Analytical The term ‘electrochemical stripping analysis’ refers of ESA and associated important advances in the field17
Chemistry, University of to a group of electroanalytical methods, where the are summarized in Fig. 1.
Barcelona, Barcelona, Spain.
analysis is performed in a two-step process7. The initial Different ESA variants have been developed, depend-
2
Faculty of Science and
pre-concentration step involves pre-concentration (accu- ing on the pre-concentration method and subsequent
Engineering, Manchester
Metropolitan University,
mulation) of the analytes or their compounds onto a suit- electrochemical quantification used. Pre-concentration
Manchester, UK. able working electrode. During the second stripping step, can be performed by various approaches, including the
3
Department of Building the analyte is quantified using an appropriate electro following7,11,12: reduction or oxidation of the analyte on a
Materials Technology, analytical technique8–12. The pre-concentration step dif- suitable working electrode; adsorption of the analyte or
Faculty of Materials Science ferentiates ESA from other electroanalytical methods its compound on a suitable working electrode; chemical
and Ceramics, AGH University
because it enriches the working electrode with the target reaction of the analyte with the working electrode mate-
of Science and Technology,
Krakow, Poland.
analyte(s) or a compound of the target(s). Therefore, the rial or the oxidized form of the working electrode; extrac-
4
Department of Chemistry,
analyte concentration on the working electrode surface tion of the analyte within the working electrode material;
National and Kapodistrian is much higher than its concentration in the original ion-exchange reaction of the analyte with an exchanger
University of Athens, Athens, sample. As the subsequent electrochemical quantifica- attached on the working electrode; and ion transfer of the
Greece. tion step monitors the accumulated analyte, high sen- analyte between two immiscible electrolytes. The most
5
Department of sitivity and low limits of detection can be achieved13,14. widely used pre-concentration methods are schematically
Nanoengineering, University Other advantages of ESA include multi-analyte capa- described in Fig. 2a and involve either electroreduction
of California San Diego,
La Jolla, CA, USA.
bility, low cost of instrumentation and consumables, or adsorption. Electroreduction occurs by electrolysis of
✉e-mail: aeconomo@ low power requirements, potential for on-site analysis, metal cations at solid, mercury or green metal — such
chem.uoa.gr speciation capability and scope for indirect biosensing. as bismuth, tin or antimony — working electrodes18,19
https://doi.org/10.1038/ ESA traces its roots back to the 1930s with (Fig. 2a(i)). The metal cations are reduced to the corre-
s43586-022-00143-5 Christian Zbinden’s experiments. Zbinden exhaustively sponding metals, forming a deposit on the solid electrode,
NAture RevIews | METHoDS PrimErS | Article citation ID: (2022) 2:62 1
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Primer
Working electrode
or an amalgam with a mercury electrode or an alloy with Electrochemical quantification is normally performed
An electrode at which one or green metal electrodes. Organic compounds or metal by voltammetry or (chrono-)potentiometry. The relevant
more analytes undergo a redox complexes can be adsorbed at different types of working stripping modes are termed stripping voltammetry and
reaction and whose response electrodes20,21 (Fig. 2a(ii)). To induce adsorption of analytes potentiometric stripping analysis (PSA), or stripping
is used as an analytical signal.
on the electrodes, metal cations are usually converted into (chrono-)potentiometry, respectively.
Convective mass transfer complexes with organic ligands possessing surface-active This Primer focuses on the instrumentation and elec-
A mechanism of mass transfer properties, whereas many organic compounds are inher- trodes used in ESA, typical applications of ESA in various
to the electrode based on the ently surface-active and adsorb spontaneously on the fields, guidelines for method optimization and method
forced movement of solution
working electrode. limitations. The Primer does not cover more specialized
caused by stirring, vibrations
or heating.
The amount of analyte, or its compound, that topics such as less common pre-concentration methods,
accumulates on the electrode determines the sensi- chemically modified electrodes with selective ligands
Voltammetry tivity of detection. Normally, pre-c oncentration is and theoretical aspects of ESA.
An electroanalytical technique performed under conditions which promote efficient
that involves scanning the
potential of the working
pre-concentration and selective attachment or binding Experimentation
electrode versus time and of the analyte to the working electrode. For example, Instrumentation
measurement of the current desirable pre-concentration conditions may involve long ESA uses simple and inexpensive instrumentation of
versus potential. deposition times, convective mass transfer of the analyte small size, low power requirements and no need for
to the working electrode surface or favourable potential maintenance. This is a distinct advantage over com-
(Chrono-)Potentiometry
An electroanalytical technique
of the working electrode. peting techniques, such as atomic spectrometry, which
that involves a redox reaction In the stripping step, the pre-concentrated analyte rely on laboratory-based instrumentation. The princi
at the working electrode and undergoes a redox reaction, which can be exploited ple of the modern three-e lectrode potentiostat —
measurement of the potential for quantification (Fig. 2b). In the case of electrolytic comprising a working electrode, a reference electrode and
versus time.
pre-concentration of metal cations, stripping involves a counter electrode — was described in 1942 (ref.22)
Stripping voltammetry oxidation of the accumulated metals back into solu- and the vast majority of ESA applications still use a simi
A two-step electrochemical tion as metal cations. For adsorbed species, stripping lar set-up23. In this configuration, the potential of the
measurement. The first step is involves reduction or oxidation of the accumulated working electrode is controlled or measured with respect
to accumulate material at an
organic compound, or reduction of the accumulated to the reference electrode and current flows exclusively
electrode, whereas the second
step is to measure the amount
metal complexes. between the working electrode and the counter electrode
of accumulated species by The method used to perform the stripping step (Fig. 3Aa). Today, ESA experiments are conducted with
voltammetry. and record the electrochemical response is criti- multipurpose instruments commercialized by differ-
cal and depends on the specific application (Fig. 2c). ent manufacturers that control the pre-concentration
conditions — time and potential — and can implement
the selected stripping technique, such as different vari-
ants of stripping voltammetry and PSA, under computer
1930 control24. These instruments can accommodate differ-
First use of term stripping analysis ent types of working, counter and reference electrodes
for determination of Cu(II)
1940
depending on the application of interest. They usually
provide additional input/output lines to trigger exter-
nal ancillary equipment, such as stirrers and pumps.
Complete protocol of stripping 1950 In addition to conventional benchtop electrochemical
techniques, invention of workstations, portable battery-powered and handheld
hanging/static mercury electrode
1960 instruments capable of conducting ESA are now avail
Theory of ESA, thin-film mercury
electrode and pulsed techniques able. This has enabled on-site or point-of-care stripping
1970
developed measurements to be performed in conjunction with
Multipurpose instruments, PSA integrated electrochemical sensors2,25. For multiplexed
developed, speciation studies and
real-life applications experiments, multi-potentiostats are available that can
1980 control either several working electrodes, which share
Computerized instruments,
adsorptive stripping analysis common reference and counter electrodes26, or many
New methods of pre-concentration, 1990 independent three-electrode cells27. Ιn many cases,
microelectrodes, screen-printed ESA experiments are conducted using instruments
electrodes fabricated in-house and controlled by proprietary soft-
2000
ware28,29. Paper-based instruments are also possible30.
Green electrode materials, ESA for FIGURE 3Ab–d illustrates schematics of a conventional
2010 biosensing and miniaturized
devices benchtop three-electrode set-up using a batch cell,
an online configuration featuring a three-electrode
2020 flow-through cell and a typical portable instrument with
an integrated three-electrode sensor.
Types of working electrodes

The working electrode represents the most impor-
Fig. 1 | Historical evolution of ESA. ESA, electrochemical stripping analysis; tant component of an electrochemical cell. The gen-
PSA, potentiometric stripping analysis. eral criteria for an ideal working electrode include
2 | Article citation ID: (2022) 2:62 www.nature.com/nrmp
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a b
Pre-concentration Stripping
Mn+sol Metal ion in solution
(i) Electrolysis (ii) Adsorption M dep Electrodeposited metal
M am M al M al M am M am Metal amalgamated with Hg
M dep A ads M dep – ne– ne–
– A ads
+ ne– + ne– M n+
Mn+ads
ads M al Metal alloyed with Sb, Bi or Sn
+ ne– Mn+sol Mn+sol – ne M–
n+
M n+ – ne –
+ ne–
sol sol
+ ne–
Mn+sol A sol Mn+sol B sol Hydrophobic ligand
Mn+sol
M
Enhanced Static
mass transfer solution Mn+sol Complex in solution
+
Mn+sol
Mn+ads Adsorbed complex
c
Stripping techniques A ads Adsorbed organic analyte
(i) Stripping voltammetry (ii) PSA A sol Organic analyte in solution
B sol Product in solution

+ Linear sweep Response
Constant current
+ +
E
Reduction reaction
I
+ ne–
t Reduction signal
– +
E Oxidation reaction
Response − ne–
– Oxidation signal
– –
+ Differential pulse Δt/ΔE O Oxidant
Electrode
E
– +
t Response E
+ Chemical oxidation
ΔI
–
M +O Mn+
+ Square wave –
E
M al + O Mn+
E
– M am + O Mn+
t
–
Fig. 2 | The principle of ESA. a | Methods of pre-concentration in electrochemical stripping analysis (ESA). In electrolyti-
cal methods (part i), metal cations are reduced and accumulated on the working electrode as metals. In adsorptive meth-
ods (part ii), metal cations (after conversion to surface-active complexes with organic ligands) and organic compounds are
adsorbed on the working electrode. b | Stripping mechanisms involving oxidation or reduction of the accumulated ana-
lyte. c | Stripping methods in ESA. Stripping voltammetry (part i) involves stripping of the analyte using a potential scan of
the working electrode while a voltammogram (potential versus time) is recorded. Potentiometric stripping analysis (PSA)
(part ii) involves stripping of the analyte using a constant current or a chemical agent and a potentiogram (derivative of
time versus potential) is recorded.
minimal non-faradaic (or capacitive) contributions, wide the accumulation step are not uniform and intermetal-
Potentiometric stripping
analysis polarization potential window, low cost, mechanical stabil- lic compound formation is common. As a result, their
(PSA). An electrochemical ity, ease of machining or forming into different shapes, applications in ESA are limited.
measurement where material reproducible surface morphology, low toxicity, resistance Carbon paste electrodes (CPEs) are made in-house
is accumulated at an electrode. to fouling and high electron transfer rate. Additional cri- by mixing graphite and a hydrophobic binding liquid,
The accumulated material is
then removed either by chemi-
teria for the selection, design or fabrication of a suitable such as paraffin or silicone. The accumulation on CPEs
cal reaction or electrochemi- working electrode are analyte-specific. They are mainly is often based on a synergistic adsorptive/extractive
cally at constant current associated with the desired analyte pre-concentration mechanism, in which the hydrophobic binder in the
while the electrode potential mechanism on the electrode surface, issues of sensitivity, paste serves as an extraction medium. Therefore, these
is measured.
selectivity and the preferred antifouling properties. electrodes are very useful for the determination of many
Potentiostat Solid electrodes made of various forms of carbon — less polar organic compounds by ESA32.
An instrument used to measure such as glassy carbon and boron-doped diamond — and Mercury working electrodes have traditionally been
electric current. It controls inert metals — such as platinum — are commercially used for ESA of metals and organics. Liquid mercury
the potential between working available in the form of discs or wires. Such electrodes has many favourable attributes as an electrode material.
and reference electrodes and
measures the current between
have some limitations as working electrodes31. They For example, it is available at high purity; has adsorptive
working and auxiliary require careful pretreatment, polishing, conditioning properties, which are useful in adsorptive accumulation;
electrodes. and cleaning. Additionally, deposits formed during has a high hydrogen reduction overpotential; the drop
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Aa b B
Mass transfer
Potentiostat Benchtop potentiostat
E A
V i Deposition time
Reference
Potential (V)
electrode Stripping method
Counter
electrode and conditions
Deposition potential
Working
Time (t)
electrode
Stirrer bar
Chemical environment
c d
Benchtop potentiostat Interferents Deposition
O2 pH morphology
Portable potentiostat
with integrated connector
Signal (I or ∆t/∆E)
Outlet
Electrode size
Three-electrode
Flow out disposable sensor Electrode
composition
and morphology
Potential window
Inlet
Potential (V)
Flow in
Fig. 3 | Experimental set-ups and main variables in ESA. A | Functionality of a three-electrode configuration in electro-
chemical stripping analysis (ESA), where V is a voltmeter, A is an ammeter, E is potential of the working electrode with
respect to the reference electrode and i is current that flows between the counter and working electrodes (part Aa).
Schematics of different experimental set-ups in ESA: laboratory benchtop potentiostat with a batch cell (part Ab), labora-
tory benchtop potentiostat with a flow-through cell (part Ac) and portable potentiostat equipped with a three-electrode
sensor (part Ad). B | Variables that affect the signal in ESA.
can be reproduced with high precision; a new surface These working electrodes can be fabricated by machin-
Reference electrode
An electrode with respect
is available for each measurement; and mercury forms ing bulk metal rods. Alternatively, a thin film of the green
to which the potential of the amalgams with many metals. These properties facilitate metal can be electrodeposited on a conductive support,
working electrode is measured the accumulation and stripping steps, while minimiz- such a boron-doped diamond41, glassy carbon42, carbon
in an electrochemical cell. ing the formation of intermetallic compounds. For many paste43 and various metals31, either simultaneously with
years, the hanging mercury drop electrode (HMDE) — the target metals (in situ deposition) or in a separate solu-
Counter electrode
An electrode that carries the which consists of a drop of mercury suspended at the tion (ex situ deposition). Another fabrication method is
electric current flowing through end of a capillary filled with mercury — has dominated to modify an electrode with metal precursor compounds
an electrochemical cell. Any ESA17. It is commercialized by several manufacturers — oxides or salts — that are converted into the green
electrochemical processes that under different names, such as the HMDE or the multi metal during analysis39,40.
occur on the surface of this
electrode are not of interest.
mode electrode. The mercury film electrodes, which Gold working electrodes in the form of wires, rods
consist of a thin layer of mercury deposited on a con- or gold thin films are commercially available and widely
Non-faradaic (or capacitive) ductive substrate33, can be easily prepared in the labo- used for mercury, arsenic and selenium detection by
contributions ratory and provide even lower limits of detection than ESA as there is a strong interaction of these elements
Refers to the current arising
the HMDE34,35. with a gold surface44. Gold electrodes can also be used
from an electrical double layer
charging at an electrode– A family of more environmentally friendly sensors for the monitoring of other trace metals45.
solution interface. Non-faradaic are the various amalgam electrodes, which are fabricated Screen-printed electrodes (SPEs) are fabricated by
current is not associated with by ex situ amalgamation of mercury with gold, silver squeezing the chosen conductive printing ink on an
a redox reaction. or copper36,37, as it has been shown that the amount of insulating substrate through a screen mesh template46.
Polarization potential
mercury released from these sensors is negligible38. The printing material is normally a graphite-containing
window However, the use of mercury is discouraged owing to ink; however, gold, platinum and silver SPEs can be pro-
A range of electrode potentials current and future health and environmental concerns, duced by using graphite ink loaded with these metals.
where, when compared with alongside respective legislation to address these issues38. SPE devices are becoming increasingly popular for ESA
the current from of the investi-
A major requirement for alternative electrode materials is as screen printing offers versatility in terms of electrode
gated reaction, the electric
current from the electrode a sufficiently high hydrogen reduction overpotential that design, potential for integration and miniaturization,
or electrolyte reaction is would enable efficient operation even in acidified sam- choice of materials and scope for mass production of
negligible. ples. Over the past two decades, non-toxic green metals low-cost, disposable and highly reproducible sensors47–49.
— antimony, tin and, in particular, bismuth — have been Importantly, this manufacturing approach enables the
Electron transfer rate
The rate at which electrons are
increasingly applied as working electrode materials. They construction of integrated three-electrode sensors that
exchanged between a working display an attractive performance in ESA and compare do not require external reference and counter electrodes
electrode and a redox species. favourably with that of mercury-based electrodes39,40. and can operate even with drop-sized samples. SPEs are
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Overpotential
produced by, or can be ordered to individual specifica- microwaves, magnetic fields or heating of the working
Additional potential above the tions from, many companies. However, they can also be electrode70,71. Finally, in many cases pre-concentration
equilibrium Nernst potential manufactured in-house using standard screen-printing is performed in flow-through electrochemical cells
value that is required for an equipment. under flow conditions that promote mass transport
electric current to flow through
the working electrode.
Other, more specialized laboratory-based fabrica- to the electrode surface57. For methods involving elec-
tion and microfabrication approaches can produce fully trolytic pre-concentration of metals, the deposition
Anodic stripping integrated sensing devices for ESA. These methods potential should be more negative than the reduction
voltammetry include microengineering50–53, injection moulding54 and potentials of the target metal(s). However, a very neg-
(ASV). A stripping voltammetry
3D printing55,56. In addition, different flow-through ative pre-concentration potential may cause excessive
method where electrochemical
oxidation occurs during the
cells 57,58, fluidic or microfluidic platforms 59,60 and hydrogen evolution, which could interfere with the
stripping step of material three-electrode paper-based fluidic devices61,62 have been deposition process. On the other hand, it was recently
accumulated at the working reported for ESA. shown that ultra-cathodic deposition beyond the point
electrode. Microelectrodes, with active dimensions of a few of hydrogen evolution can, under some circumstances,
Cathodic stripping
to a few tens of micrometres, or ultra-electrodes and yield substantial enhancement in sensitivity72,73. For
voltammetry nano-electrodes, with active dimensions of less than methods involving adsorptive pre-concentration, the
(CSV). A stripping voltammetry 100 nm, offer numerous advantages compared with efficiency of adsorption depends on the hydrophobicity,
method where electrochemical macro-electrodes. These advantages include enhanced molecular structure and charge of the target adsorbate,
reduction occurs during the
mass transport, reduced ohmic drop, low parasitic as well as the potential, which defines the charge, of the
stripping step of material
accumulated at the working
capacitive currents and scope for miniaturization. electrode74. Therefore, the optimum pre-concentration
electrode. Several types of microelectrodes have been used in potential is often determined experimentally.
ESA63,64. Their main drawback is the low signal due to
Faradaic current their small size, which makes measurements sensitive Stripping step
An electric current that arises
from redox reactions of
to extraneous noise. This problem can be addressed by The stripping step can be implemented by various means,
electroactive species at a using arrays of interconnected microelectrodes arranged normally different variants of stripping voltammetry and
working electrode. in a geometrical pattern. This enables current amplifica- PSA. It must be noted that the pre-concentration step
tion proportional to the number of the elements in the is similar in both voltammetric and (chrono-)poten-
Voltammogram array65. Single microelectrodes or arrays can be made tiometric stripping methods. As a result, the relevant
The representation of current
versus potential.
of carbon, platinum, gold, iridium, boron-doped dia- pre-concentration parameters are the same.
mond and alloys. They are usually modified with mer- In stripping voltammetry methods, the poten-
Constant current PSA cury, bismuth and gold films, plus antifouling coatings, tial of the working electrode is scanned with respect
(Constant current potentiomet- such as agar and Nafion. Single microelectrodes can be to time in a linear fashion or using a pulsed mod-
ric stripping analysis) or con-
stant current stripping (chrono)
fabricated in-house or purchased, but the fabrication ulated waveform 19,75 (Fig. 2c(i)) . Depending on the
potentiometry . An electro- of microlectrode arrays requires access to specialized potential scan direction, the relevant techniques
chemical measurement where microengineering manufacturing facilities. are termed anodic stripping voltammetry (ASV) and
material is accumulated at an Working electrodes modified with polymers66, metal cathodic stripping voltammetry (CSV). As the potential
electrode. The accumulated
nanomaterials and micro-materials42,67–69 and metal of the working electrode reaches the redox potential of
material is then electrochemi-
cally removed at constant
oxides69 extend the sensing applicability in ESA. The an accumulated species, a redox semi-reaction occurs
current while the electrode modification step aims to enhance the detection sensi- giving rise to a faradaic current, which is recorded as a
potential is measured. tivity or selectivity and to improve the robustness of the peak-shaped response in the voltammogram. Pulsed
relevant sensors, through protection from matrix effects voltammetric waveforms — such as differential pulse
or stabilization of the sensing layer. However, these types or square wave — are preferable to a linear scan wave-
of modified sensors are not available off the shelf and form because they can discriminate against the par-
fabrication in the laboratory requires the development of asitic capacitive current resulting in lower limits of
proprietary modification methods and skilled personnel. detection75,76. The differential pulse waveform discrimi
nates well against the capacitive current but is limited
Pre-concentration variables to relatively low scan rates. By contrast, the square wave
In ESA, the sensitivity critically depends on the amount modulation combines higher scan rates with efficient
of analyte accumulated on the surface of the electrode discrimination against the capacitive current, but can
during pre-concentration. This is mainly defined by lead to low sensitivity in the case of electrochemically
the rate of mass transport to the electrode, the depo irreversible stripping reactions77. The different param
sition time and the deposition potential. Longer eters of the scanning waveform, such as scan speed, pulse
pre-concentration times enhance the sensitivity, but amplitude, pulse duration and pulse frequency, affect the
lead to an undesirable increase in analysis times. This features of the voltammogram, including peak height,
can be addressed by more efficient mass transfer of peak width and background characteristics. Usually,
the analyte to the surface of the working electrodes these parameters are optimized experimentally.
during the pre-concentration step. Normally, this is In PSA, the accumulated species is oxidized using a
achieved by forced convection, for example mechan- chemical oxidant. Alternatively, the accumulated spe-
ical stirring of the solution using a magnetic stirring cies is oxidized or reduced using a current of appropri-
bar or rotation of the electrode. However, in addition ate polarity. This variant of PSA is sometimes referred
to these conventional methods, some unconventional to as constant current PSA or constant current stripping
techniques have been developed to enhance mass trans- (chrono-)potentiometry78,79 (Fig. 2c(ii)). The potential of
fer, such as the application of vibrations, ultrasound, the working electrode is monitored with respect to time
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Potentiogram
and the differential Δt/ΔE is recorded as a peak-shaped accumulated species and, in this case, deoxygenation
A representation of the response in the potentiogram. In stripping (chrono-) is recommended by purging with an inert gas, such as
differential Δt/ΔE versus potentiometry, which exploits a chemical species such nitrogen or argon; an alternative approach involves the
potential. as dissolved O2 as an oxidizing agent, the supply of oxi- use of an electrochemical bult-in oxygen filter89.
dant to the electrode surface defines the sensitivity of For method optimization in ESA, the different
detection and should remain as constant as possible. instrumental parameters — deposition time, deposition
In constant current stripping chrono-potentiometry, potential, mass transfer conditions, stripping method and
the oxidizing or reducing current is user-defined and relevant variables — and chemical conditions — sample
determines the sensitivity of detection. pH, electrolyte type and concentration — should be
The choice of stripping technique depends on the judiciously selected to achieve optimum sensitivity and
application of interest. However, it is generally acknowl- selectivity. The majority of reported methods are based
edged that PSA with chemical oxidation of the accu- on univariate optimization, where the parameters are
mulated species is more tolerant to adsorption effects singly optimized one after the other. However, chemo-
caused by organic matter in many samples80. It is also metric optimization techniques have been reported that
suitable for low ionic strength and low conductivity involve simultaneous intentional variations of the exper-
solutions78 and unaffected by capacitive contributions. imental conditions under a predetermined protocol90–93.
Consequently, it may be preferable to stripping voltam- These optimization strategies are faster and take account
metry in the case of slow electrochemical kinetics81, but of possible interactions between the various parameters.
is more sensitive to variations in hydrodynamic condi- The main variables that determine the signal in ESA are
tions82. Only scarce data exist regarding the relative sen- schematically illustrated in Fig. 3B.
sitivity achieved with each stripping technique. A recent
study summarizing the literature on iron and copper Results
determination by PSA and stripping voltammetry con- The response in ESA is visualized as a voltammogram
cluded that no clear advantage of either technique could or potentiogram, where the presence of analytes is
be documented83. observed in the shape of peaks. Prior to quantification,
stripping peaks should be assigned to the corresponding
Sample preparation and optimization chemical species. This is particularly important in metal
Some liquid samples with a simple matrix, for exam- analysis because different oxidation states or complexed
ple tap water, can be analysed without pretreatment. forms, such as free metal and labile or inert complexes,
However, many liquid samples and most solid samples will result in peaks with different peak potential and
— including beverages, pharmaceuticals, fuels, food, and height85,94. In stripping voltammetry, peak current val-
environmental and clinical material — require sample ues are usually considered as the analytical parameter,
treatment in order to release the target analytes, con- although the use of peak area is preferable for voltammo-
vert them into quantifiable species and eliminate matrix grams with an intricate baseline or non-Gaussian peak
interferents. Sample treatment ranges from simple UV shape (Fig. 4A). If (chrono-)PSA is considered, the area
irradiation for organic matter removal to more complex under the peak-shaped response is recommended as the
procedures, such as microwave or acid digestion, dry analytical parameter95,96 (Fig. 4A).
ashing or ultrasound-assisted extractions3,4. The quality of the results of an analytical determi-
Sample processing prior to ESA must ensure that the nation is directly related to the accuracy with which
sample is well buffered at the optimal pH for analysis. In peak currents and peak areas are measured, alongside
environmental and biological samples, heavy metals are the suitability of the selected calibration method. In this
found as free hydrated cations, as complexes with organic context, the appropriate baseline subtraction method
ligands (humic and fulvic acids) and inorganic anions is of great relevance. Different algorithms for baseline
(Cl−, SO42−) or adsorbed on colloidal matter84–86. As the subtraction have been proposed97–99 and the software of
pH of the sample decreases, metals are released from modern electrochemical instruments includes integrated
their bound form as free metal cations, leading to an routines to perform this task. Figure 4B illustrates how
enhanced stripping response19,87. For many organic com- appropriate definition of the baseline affects the current
pounds, the pH determines their speciation and charge. to be measured — the same is applicable for peak areas
This, in turn, determines their adsorptive properties — using ASV as an example. It must be pointed out that
and the potential at which they are stripped. Local pH direct subtraction of a blank signal is not usually consid-
changes at the electrode surface during electrodeposi- ered owing to the difficulty of reproducing the matrix of
tion should also be considered. For instance, highly neg- the sample. Therefore, the use of analysis tools provided
ative working electrode potentials can cause a local pH by electrochemical software is the preferred way consid-
increase, which can lead to the formation of hydroxides ered for measurements. If the obtained voltammograms
or metal oxides on the surface of the working electrode. are largely affected by background current or instrumen-
Consequently, appropriate buffers are usually added to tal noise, preprocessing is recommended before peak
the sample, which additionally increase the solution integration. Preprocessing can range from derivative
conductivity. An elegant method to acidify the sample signal transformation100 and function fitting101 to digital
without the addition of chemicals has been recently pro- smoothing102. This data treatment can be directly per-
posed and is based on the in situ local electrochemical formed with the software provided by the instrument, or
production of protons using a protonator electrode88. undertaken externally using different algorithms103–107.
Finally, dissolved oxygen may cause oxidation of the However, excessive preprocessing can introduce artefacts
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A B
a b
I = 1.093 μA
Signal (current or Δt/ΔE)

1.2 I = 0.967 µA
4
Linear curve 1.0
3 Polynomial curve I = 0.639 μA
SA 0.8 I = 0.594 μA
I (μA)
I (μA)
AA
SB 2 0.6
0.4
AB 1
0.2
0 0.0
EA EB –1.2 –1.0 –0.8 –0.6 –0.4 –1.2 –1.0 –0.8 –0.6 –0.4
Potential Potential (V) Potential (V)
EA Qualitative SA AA Quantitative
EB information SB AB information
D External calibration
a

C
Signal
0.20
0.15
Potential sample Concentration
C
I (μA)
0.10 Standard additions

b

0.05
80 100 120 140 160 180 200
Signal
Potential (V)
Raw data
Appropriately corrected data
Overcorrected data
Potential –C
sample Added concentration
Fig. 4 | Signal processing and quantification in ESA. A | Qualitative and quantitative interpretation of the analytical sig-
nal in electrochemical stripping analysis (ESA). B | Baseline definition in ESA using two common settings in electrochemi-
cal software (linear and polynomial curve) (part Ba) and voltammetric data after baseline subtraction (part Bb). The lower
peak heights are obtained with linear curve fitting due to the intrinsic shape of the baseline. C | Effect of smoothing in sig-
nal preprocessing. Under-corrected data still display noise whereas overcorrected data lead to wider and lower voltam-
metric peaks. D | Quantitation approaches using external calibration (part Da) and standard additions (part Db) (dotted
trace represents sample response).
in data analysis. For example, the effect of overcorrection in adding small volumes of a concentrated standard solu-
stripping signals is demonstrated in Fig. 4C. tion of the analyte(s) directly into the sample, as illus-
Quantitative information is obtained by using an trated in Fig. 4Db. Additionally, internal standards can
appropriate calibration method. Establishing a correct correct for signal variability in consecutive measure-
calibration procedure is essential to prevent systematic ments. This is achieved by using the ratio of the target
errors and matrix effects. Depending on the applica- compound signal to the internal standard signal as
tion, calibration can be carried out using univariate or the analytical parameter117–119. In external calibration
multivariate methods with standard solutions108–112. The methods, the linear calibration curve should bracket
principle of univariate calibration with a calibration the expected analyte concentration in the sample and
curve prepared using external standards is illustrated in include at least 5, and preferably more, calibration points
Fig. 4Da and is based on the establishment of a relation- to improve the precision. In the case of standard addi-
ship between the signal and the concentration of an indi- tions, the signals due to the native analyte and after the
vidual analyte. By contrast, in multivariate calibration standard additions should be within the linear range of
methods, whole sets of voltammograms are mathemati- the method120.
cally treated to deduce the concentration of one or more The vast majority of commercial electrochemical
Matrix effects
analytes113. In cases where matrix effects are significant, workstations are offered bundled with proprietary user
Effects of the matrix of the
sample on the analytical the calibration method must be able to correct for the interfaces, including control, data collection, signal
response. presence of matrix interference. To this end, although processing, data evaluation and display. This has the
calibration with matrix-matched standard solutions can be advantage of significantly reducing the processing time
Matrix-matched standard used114, the method of standard additions or modified required for routine analysis.
solutions
Standard solutions prepared
standard additions is preferable because it is simpler, Method validation includes the derivation of
in a matrix similar to the matrix faster and does not require matrix-matched standard key parameters — linearity, limits of detection and
of the sample. solutions115,116. The standard additions method involves quantification, precision, accuracy and ruggedness —
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1 2
H He
ASV CSV
3 4 5 6 7 8 9 10
AdSV CAdSV
Li Be B C N O F Ne
*
11 12 13 14 15 16 17 18
Na Mg Co-deposition with copper Al Si P S Cl Ar
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
58 59 60 61 62 63 64 65 66 67 68 69 70 71
*CN, SCN
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
90 91 92 93 94 95 96 97 98 99 100 101 102 103

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Fig. 5 | List of elements that can be determined by ESA. AdSV, adsorptive stripping voltammetry; ASV, anodic stripping
voltammetry; CAdSV, catalytic adsorptive stripping voltammetry; CSV, cathodic stripping voltammetry; ESA, electrochemical
stripping analysis.
calculated in the manner recommended by regulatory the sample analysed, the type and concentration of the
authorities121–123. supporting electrolyte, and the instrumental parameters.
Instrumental variables include the type of working elec-
Applications trode, the analyte pre-concentration time and potential
ESA has long been considered a powerful tool for and the stripping step mode.
the determination of trace metals, organics and The lowest detection limits achieved by the most
metal–organic compounds in a wide range of sam- popular ESA techniques range from 10−10 to 10−11 mol l–1
ples11–13,79,124–126. Its advantages include low limits of (ref.40). Typical applications include the determination of
detection, good selectivity and the capacity to simulta- metals and organic compounds in various samples. For
neously detect several elements. Despite the fact that a example, samples may be environmental, such as natural
direct comparison between ESA and competing trace water, sediments, soil, fly ashes, minerals and airborne
metal analysis techniques is application-dependent, the particulate matter. Alternatively, they could be indus-
applicability, precision and sensitivity of ESA are con- trial, from industrial fluids and waste, metals, alloys,
sidered comparable with those of modern atomic spec- gasoline, oils, ceramics and pigments. Other applications
trometry and mass spectrometry approaches, but at a deal with biological, biochemical and clinical material
small fraction of their cost127–131. However, ESA outper- originating from plants, hormones, nucleic acids, organs,
forms these approaches for on-site and online monitor- body fluids and tissues. Additional sample types include
ing applications owing to portable instrumentation and food-related material, for example foodstuff, wines and
availability of disposable sensors. For instance, low-cost juices, pharmaceuticals in both formulations and antibi-
portable ASV analysers have been found to match the otics or samples in forensics, for instance drugs in body
performance of advanced spectroscopic approaches for fluids, gun powder residues and explosives.
the determination of lead in water and blood132,133. ESA
is also the preferred approach for analysis of samples Trace metals and metalloids
containing high concentrations of inorganic salts, such ASV has been widely used for the simultaneous meas-
as seawater, and redox or chemical speciation studies of urement of heavy metal content — in particular cop-
some metal ions and their complexes. In addition, ESA, per, lead, cadmium and zinc — in water samples and
unlike atomic spectrometry methodologies, is applicable other media, including blood and body fluids. The
to many organic compounds and biomolecules. The sen- range of metals that can be quantified by different ESA
sitivity, selectivity, linear range and limit of detection of techniques is presented in Fig. 5. For example, the lead
ESA techniques in routine applications are dependent on concentration in blood can be determined on-site using
numerous parameters. These include the composition of commercially available portable ASV-based analysers134.
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Adsorptive stripping
This enables a lead exposure assessment of children135, including animal tissues, fruit and vegetables, dairy
voltammetry lead miners and smelters133 and wild animals136,137. New products, sugar, beverages and juices4. A prerequisite
(AdSV). A stripping ASV procedures continue to be developed and applied for this is the preliminary removal of the sample matrix,
voltammetry method where for determination of copper, lead, cadmium or zinc using which can complicate quantification of heavy metals
pre-concentration is achieved
new sensors, configurations and procedures19,39,40,57,138–140. and metalloids at trace and ultra-trace concentrations.
by adsorption of the analyte or
its compound. ASV has also been exploited for the quantification of Careful decomposition of the sample is necessary to
other metals forming alloys, notably for the detection eliminate organic matter. This ensures quantitative
of mercury or arsenic, using gold working electrodes141,142. retention of the analytes and coverts them into a form
Alongside ASV, researchers have developed methods suitable for ESA quantification. Other fields where ESA
involving adsorptive pre-concentration, for example is invaluable are forensic analysis, for example for gun-
adsorptive stripping voltammetry (AdSV) and PSA with shot residue detection161, fuel quality control162, battery
adsorptive pre-concentration, for the detection of metal research and energy applications163 and pharmaceu-
cations that form complexes with certain ligands143. Such ticals6. Notably, multi-element methods can quantify
adsorptive accumulation of metal complexes expands the several target metals at the same working electrode in
scope of ESA towards important metals — such as iron, a single run45,164, or at devices with spatially separated
nickel, cobalt, uranium, vanadium and molybdenum working electrodes with each electrode dedicated to a
— that cannot be readily pre-concentrated by electro single target metal165. An example of multi-element ASV
lysis. These procedures have mostly been applied to analysis in a single run is illustrated in Fig. 6a, which
the analysis of sea and inland water samples for trace shows the voltammogram in a sample containing zinc,
elements that are toxic or essential for aquatic organ- cadmium, indium, lead and bismuth.
isms141,144–146. To increase the sensitivity of adsorptive ESA methods may be applied for the speciation of
procedures it is possible to exploit efficient adsorptive trace metals, including labile and inert fractions of met-
accumulation of the electroactive species, combined als, redox species and covalently bound species. The
with catalytic reactions. During these processes, ana- considerable potential of ESA methods in speciation
lytes induce cyclic or non-cyclic catalytic reactions in studies has been documented in numerous reviews that
the vicinity of the working electrode surface147–151. The present various procedures exploiting conventional and
dual amplification induced by such adsorptive-catalytic modern approaches to metal speciation by means of
methods enables the sensitivity to be enhanced by one ESA79,94,141,166–170. ASV allows differentiation of electro-
or two orders of magnitude. This allows inorganic ion chemically inert and labile fractions of metal in water
detection, for example of molybdenum, cobalt and plat- media. The latter include free and reversible complexed
inum, at concentrations as low as 10−12–10−13 mol l–1. The metal ions capable of reduction and accumulation at the
proper selection of ligand and catalytic agent plays a sig- electrode surface166,167. This is achieved via the proper
nificant role in achieving extremely high sensitivity in selection of solution pH, supporting electrolyte and
catalytic adsorptive stripping methods. deposition potential and, if necessary, the addition of a
Water samples are analysed in the laboratory or complexing ligand. An interesting example of mercury
on-site using automated flow systems57,141,152–154. These speciation by means of ASV with a gold film electrode
automatic analysers have been used to couple ESA with is the quantification of methylmercury in the presence
continuous flow analysis, flow injection analysis and of inorganic mercury171. The addition of a diethylenetri-
sequential injection analysis57,140. Various flow cells with aminepentaacetic acid (DTPA) complexing ligand to a
miniaturized electrodes obtained by thin-film deposi- solution containing both species results in transforma-
tion on chips and photolithography, along with portable tion of Hg+ to the electrochemically inactive Hg–DTPA
instrumentation, can be used in stripping flow systems. complex. This occurs at the potential where methyl-
This facilitates on-site procedures, reduces the time of mercury undergoes reduction to the metallic state and
analysis, facilitates sample handling and eliminates oxy- enables selective determination of CH3Hg+.
gen interference57,140. The application of submersible AdSV and PSA with adsorptive pre-concentration
voltammetric probes has also been reported for in situ uses the competition of substances naturally present in
monitoring of metal pollutants in water and to evalu- water samples and the added ligand during complex for-
ate their depth profiles154–156. Additionally, protocols mation with metal ions. This occurs in the time between
have been developed for remote monitoring of mercury ligand addition and the adsorption equilibrium141. By
traces157 or nickel and uranium152,158 in seawater and titrating the sample with the selected metal and mon-
inland water. itoring the concentration of labile metal, it is possible
ESA can also be applied to monitor industrial pro- to calculate the complexing capacity or the amount of
cesses. This is particularly useful for procedures involv- metal bound by the dissolved organic material172.
ing highly concentrated media in the zinc industry (Case ASV and AdSV are highly suitable for investigating
study 1), metal plating, batteries and energy storage redox speciation of metals in environmental media.
technologies or in the electrolysis of brine. For example, This is because either one species is electrochemically
traces of elements such as cobalt, nickel, iron, manga- inactive within the applied potential range or one of the
nese, titanium, molybdenum and chromium were deter- investigated oxidation states of a given metal selectively
mined offline and online in brine using AdSV or catalytic forms an electrochemically inactive complex. ESA tech-
adsorptive stripping voltammetry (CAdSV)159,160. niques have been successfully used to detect couples
Different ESA methods have been applied to deter- such as Cr(VI)/Cr(III), Fe(III)/Fe(II), Tl(III/I), V(V/IV),
mine metals and metalloids in various food samples, Mn(IV/II), U(VI/V), As(V/III), Se(VI/IV), Sn(IV/II)
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a Cd Fig. 6 | Application examples of ESA. a | Example of

–0.84 V multi-element anodic stripping voltammetry (ASV) analysis
in a single run in a sample containing Zn(II), Cd(II), In(III),
In
Pb(II) and Bi(III). b | Adsorptive stripping voltammetry
–0.72 V
(AdSV) of caffeine at a bare screen-printed electrode (SPE)
and SPEs modified with Nafion and Nafion + graphene.
c | Principle of affinity biosensing using metal-based nano
Current
Pb
–0.56 V particles as labels and electrochemical stripping analysis
(ESA). AuNP, gold nanoparticle; BSA, bovine serum albu-
–1.14 V min; QD, quantum dot. Part b reprinted from ref.204,
CC BY 4.0 (https://creativecommons.org/licenses/by/4.0/).
Zn –0.16 V
Case study 1. One spectacular example of how ESA can
Bi
be applied for on-site monitoring of an industrial pro-
cess is the determination of trace metal contaminants in a
zinc plant electrolyte during purification181. The concen-
–1.4 –1.2 –1.0 –0.8 –0.6 –0.4 –0.2 0.0 0.2
trated zinc sulfate solution used to produce electrolytic
E (V)
b zinc is obtained by leaching zinc ores with sulfuric acid
and contains some impurities. The contaminant concen-
tration needs to be reduced to an acceptable level before
the electrolyte is placed in the electrolytic tanks. If this
is not done, the electrolyte will reduce the current effi-
ciency of the electrolytic process and, subsequently, dam-
age the metallic zinc end product. Atomic spectrometry
Current
techniques are not viable for monitoring the purification

process. By contrast, solutions containing high concen-
trations of zinc with high ionic strength are ideal media
for analytical investigation with ESA. To control the puri-
SPE
fication processes, Bond’s team elaborated several origi-
SPE–Nafion nal online procedures with a HMDE working electrode.
SPE–Nafion–graphene These procedures can be used to perform simultaneous
ASV quantification of cadmium, lead, antimony and cop-
1.8 1.6 1.4 1.2 1 0.8 0.6 per. They can also be used for simultaneous detection
E (V) of nickel and cobalt via AdSV with dimethyldioxime,
c or for extremely sensitive and selective AdSV determi-
nation of cobalt in the presence of α-benzildioxime as
a ligand and nitrite as a catalytic agent182,183. The last of
–
AuCI4 Anodic stripping
HCI voltammetry these procedures has an additional advantage, as it does
not require the matrix exchange procedure. When ASV
is combined with AdSV with chloroanilic acid as a ligand,
Cd Pb it is possible to detect total antimony and perform a spe-
ciation study of Sb(V) and Sb(III). Other elements are
determined offline, for example germanium using AdSV
Anodic stripping
Cd2+ Pb2+ voltammetry with pyrocatechol violet and total arsenic by means
HNO3
of CSV. Specially designed on-stream voltammetric
analysers allow automation of numerous stages of deter-
mination, data acquisition and the transfer of data to a
central computer, all of which enable increased control
of the process. The interference caused by the extremely
high excess of zinc is eliminated using a bottom-drain
Capture BSA Target Reporting AuNP PbS CdS Electrode flow-through cell that facilitates matrix exchange.
biomolecules biomolecules biomolecules QD QD
Case study 2. The CAdSV method with DTPA and
and Sb(V/III). AdSV and CAdSV methods have found nitrate is among the most useful techniques, as it ena-
wide applications for chromium speciation in various bles the differentiation of Cr(VI), non-reactive and reac-
environmental samples145,150. tive Cr(III) in solution. The procedure is based on the
The past two decades of research have seen the appli- formation of a Cr(III)–DTPA complex, which adsorbs
cation of not just mercury electrodes but also environ- on the electrode surface and then reduces to the Cr(II)
mentally friendly sensors such as silver amalgam173–175 and complex. This is immediately reoxidized in the presence
various types of bismuth film electrodes176–180. A CAdSV of nitrate, regenerating the complex with Cr(III). These
procedure to monitor chromium traces using a submers- reduction/oxidation processes repeat multiple times in a
ible electrochemical probe and dialysis membrane that catalytic cycle150,184,185. The combined adsorptive/catalytic
prevents electrode fouling has also been described156. effects enhance the sensitivity and decrease the limit of
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quantification for chromium down to concentrations and the instrumental and chemical conditions are para-
of approximately 10−11 mol l–1. The CAdSV signal is also mount for maximizing the amount of adsorbate on the
dependent on the chemical forms of the Cr(III) spe- working electrode surface. An example is illustrated in
cies that form complexes with DTPA186–190. Complexes Fig. 6b for the determination of caffeine by AdSV, which
formed by non-labile Cr(III) ions with organic ligands demonstrates the drastic signal enhancement afforded
found in natural waters are voltammetrically inactive by modifying a SPE with Nafion and graphene204.
in the presence of DTPA and nitrate ions. Hydrated
Cr(III) ions originally present in the solution form Case study 3. An example of an organic substance deter-
stable complexes with DTPA. After about 30–40 min mined via ESA is thiomersal, an organometallic com-
at ambient temperature, slow structural changes make pound with preservative and antimicrobial properties
these complexes unresponsive to CAdSV. This pro- that is used in topical medications, cosmetics and vac-
cess becomes increasingly rapid if the temperature is cines. The R1-S-Hg-R2 group of thiomersal can pro-
increased to around 40 °C, or when certain aminopo- duce signals specific to both reduction and oxidation.
lycarboxylic acids such as nitrilotriacetic acid (NTA), The reduction-specific response can be recorded at the
ethylenediaminetetraacetic acid (EDTA) or diamino- HMDE or renewable Ag(Hg) film electrode and is well
cyclohexanetetraacetic acid (DCTA) are added to the developed and highly sensitive205,206. The oxidation-
sample191. Instantaneous Cr(III) ions, which appear at specific signals of thiomersal observed at positive poten-
the surface of the working electrode upon reduction of tials can be recorded with carbon electrodes, such as the
Cr(VI) to Cr(III), form complexes with DTPA. These CPE and the CPE modified by addition of La2O3. La2O3
complexes adsorb to the electrode surface and are cat- facilitates charge transfer and improves sensitivity to the
alytically active in the presence of nitrate ions, provid- oxidation of thiomersal. The La2O3/CPE electrode ena-
ing an enhanced CAdSV response. These differences in bled thiomersal to be quantified in vaccines and pharma-
behaviour of the Cr(VI) and Cr(III) species enabled the ceutical dose samples207. In addition, a carbon SPE coated
design of speciation studies. Total chromium may be with chitosan can also be used to determine thiomersal208.
quantified with the same CAdSV procedure after oxi-
dation of the Cr(III) species to Cr(VI) via UV irradia- Biosensing
tion of the samples. Numerous CAdSV procedures using Over the past decade, ESA has found wide applicability
DTPA and nitrate have been applied for the speciation in the bioaffinity sensing of proteins, cells and DNA209–211.
of chromium in various materials. After combining the One of the most common biosensing methods is the sand-
CAdSV method with tangential ultrafiltration of river wich approach illustrated in Fig. 6c. First, a capture bio-
water samples, it was possible to evaluate the distribution molecule with affinity to the target is immobilized on the
of Cr(VI) and Cr(III) in the solution and the isolated working electrode surface. Then, the modified electrode is
colloidal fraction. From this, the total chromium in the put in contact with the sample and the target is selectively
particulate could be derived190. attached to the capture biomolecule. A reported probe
with affinity to the target biomolecule, labelled with metal
Organic compounds — silver, copper or gold — nanoparticles or metal-based
Trace levels of many organic compounds with electroac- quantum dots — usually nanocrystals composed of CdS
tive groups can also be detected by means of ESA192–194. or PbS — is introduced and selectively binds with the tar-
The accumulation of target organic compounds can pro- get, forming a sandwich structure. Finally, the metal labels
ceed according to different protocols20,21. These rely on are dissolved and converted into the respective cations,
electrolytic pre-concentration, including formation of which are quantified by ESA. As each biomolecular probe
insoluble compounds with the electrode material, and can accommodate a large number of quantifiable labels,
non-electrolytic pre-concentration, which may involve very low limits of detection (in the range of femtomoles
adsorption at open-circuit potential, adsorption at an per litre) can be achieved. Additionally, multiplexed
applied potential, extraction-based accumulation, ion detection of several target biomolecules is possible using
pair formation and ion exchange. different metal-based nano-labels with different stripping
Most analytical protocols for determining organic peak potentials212.
compounds involve adsorptive accumulation of the
analyte. Such analytes include the active ingredients Reproducibility and data deposition
of various pharmaceuticals, organometallic com- Reproducibility aspects are related to analyte losses or
pounds, pesticides and herbicides, food colourants, contamination213, control of the instrumental parame-
explosives and emerging contaminants, for example ters, the fabrication process itself and chemical issues,
acrylamide195, carcinogens194 and cannabis196. ESA is such as the formation of intermetallic compounds or the
typically conducted in aqueous solutions5,21, but can fouling of electrode surface. From an analytical point of
also be performed in non-aqueous media such as ace- view, repeatability and reproducibility are considered
tonitrile with tetrabutylammonium salts for the deter- as the within-run precision and between-run precision
mination of explosive materials, for example TNT197. of a method, respectively. Both are related with ran-
Macromolecules, such as proteins and nucleic acids, dom errors and are expressed as a percentage relative
can also accumulate on the electrode surface and are standard deviation214. For ESA measurements, repeat-
determined via PSA and CSV198,199. Organic compounds ability refers to repetitive measurements using a single
can also be determined using a vast array of working device, whereas reproducibility refers to measurements
electrodes32,63,200–203. The selection of working electrode performed with different devices215,216.
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Control of instrumental parameters related to both overcome by the use of ion-transfer stripping voltam-
the pre-concentration/deposition step and stripping metry between two immiscible electrolytes (aqueous
step is fundamental to obtain reproducible results217,218. and organic), which is applicable to the detection of
In the former, control of deposition time and potential many ionic species that do not possess redox proper-
should be accompanied by accurate control of the mass ties (for example, oligopeptides, neurotransmitters,
transport. This is because hydrodynamics determines the vitamins and polysaccharides)63. The target analyte is
pre-concentration efficiency. On the other hand, factors transferred from the aqueous to the organic phase and
that affect the stripping step should be carefully con- is accumulated close to the interface by modulating the
trolled, such as the magnitude of the oxidizing current or potential difference between the two immiscible phases.
the concentration of oxidant in stripping potentiometry78. During the stripping step, the analyte is transferred back
The replacement of simple bare electrodes — for exam- from the organic phase to the aqueous phase by scan-
ple mercury, platinum or carbon — by modified electrodes ning the potential while the current resulting from the
also introduces additional sources of uncertainty. Fouling transfer of the ionic analyte is measured.
is the accumulation of unwanted material on the electrode
surface. It is caused by adsorption of molecules from the Sample contamination
sample solution or products of the electroanalytical pro- As ESA is a trace analytical technique, the accuracy of
cess. They inhibit the direct electron transfer process and the results is strongly dependent on the degree of sam-
affect both the repeatability and durability of an electrode. ple contamination19,221,222. Contamination may stem from
To minimize this problem, different strategies have been impurities in reagents or containers, and from the ambi-
effectively applied. Among them, the inclusion of a clean- ent environment during sampling or sample treatment.
ing or conditioning step prior to the measurement can The principles of Good Laboratory Practice should
be useful if products of the electroanalytical reaction are be observed during handling and storage of samples.
retained on the electrode. Another strategy considers the Laboratory conditions should be carefully controlled to
inclusion of a protective layer or permselective barrier on avoid contamination by dust and airborne particulates.
the electrode to prevent the fouling agent reaching the Reagents and water of the highest possible purity should
electrode219. Then, reproducibility in between electrodes be used. Many samples, such as seawater, contain suffi-
will be affected by the manufacturing process. The more cient conductivity to allow analysis without the addition
modification steps introduced into the device, the greater of a supporting electrolyte, whereas use of microelec-
the variability. This issue can be partially addressed by trodes alleviates the need for a supporting electrolyte in
using electrodes manufactured by inherently precise many samples223. The use of closed flow systems min-
high-throughput approaches, such as screen-printing and imizes the risk of contamination from environmental
microengineering methods. sources57. To avoid metal leaching from and adsorption
The sample matrix also affects reproducibility. It on laboratory containers, polyethylene, rather than glass,
influences the background current, whereas the sample vessels and cells should be used and cleaned thoroughly
might contain species that interact with the electrode or with acid.
affect the analyte response. The pH and concentration of
the complexing agent in adsorptive pre-concentration Electrode conditioning and regeneration
of trace metals should be carefully controlled. The tar- The condition of the electrode surface is very important
get metals may form intermetallic compounds with in ESA. In this respect, use of the HMDE or the single-use
co-deposited metals or with the electrode material — type of electrode, such as screen-printed sensors224, is
usually mercury or bismuth — causing a decrease, shift advantageous as a new, clean surface is available for each
or distortion of the signals19. Some authors point out that stripping cycle. For solid reusable electrodes, remains of
PSA minimizes these problems owing to the nature of accumulated species or redox species deposits generated
the stripping step, in which the evolution of a potential during the stripping step can alter the electrode response
is considered78. or contribute to carry-over phenomena. Therefore, some
In some cases, where the aim is to minimize uncon- form of conditioning or cleaning after the stripping step
trolled variability, the use of internal standard calibra- is necessary to return the electrode to its initial condition.
tion procedures could be recommended instead of more Cleaning can be either mechanical or electrochemical225.
common and extended external calibration plots or Mechanical cleaning involves polishing the electrode
standard addition calibration methods220. with an abrasive material. This approach is not practical
for field sensors that are intended to be left in an envi-
Limitations and optimizations ronment for a long time period. Renewable in situ elec-
Range of species detectable by ESA trodes have been developed. One example is the silver
A prerequisite for detection of an analyte by ESA is the liquid amalgam film electrode. This is based on cyclic
ability of the analyte itself, or a compound of the ana- renovation of the electrode surface, achieved prior to
lyte, to pre-concentrate on a suitable working electrode. each measurement by coating a silver wire with a fresh
This requirement narrows the range of analytes that can liquid amalgam film226. A second example is the bismuth
be detected by ESA with respect to other voltammetric bulk electrode. This electrode has a sensor body partly
techniques as there are many organic and inorganic spe- filled with the internal electrolyte solution. Before each
cies that do not lend themselves to deposition. Another measurement, the electrode is cleaned and activated227.
general limitation is that the target, or its compound, Electrochemical cleaning, which involves cycling the
must be electrochemically active. This limitation can be potential or holding the potential at a judiciously selected
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a Pb b Chemometrical separation
Pb+Cu Chemical separation Pb
Pb Original data
Cd
In
Current
Current
Cd Pb
In
Cu Pb
Pb–Cu
Pb Cd
In
–1.4 –1.2 –1 –0.8 –0.6 –0.4 –0.2 0 0.2 0.4 –1.1 –0.9 –0.7 –0.5 –0.3 –0.1
E (V) E (V)
Fig. 7 | Examples of limitations in ESA. a | Formation of an intermetallic lead-copper compound in anodic stripping
voltammetry (ASV) at a carbon electrode and its effect on the respective voltammogram. b | Separation of the overlapping
cadmium and indium peaks in ASV using chemical separation (shift of the cadmium peak upon change of the supporting
electrolyte) and chemometric separation (curve fitting using the Peakfit option in OriginLab). ESA, electrochemical
stripping analysis.
predetermined value for a defined period of time, can be This forms a more stable gallium–copper intermetallic,
used to condition the electrode surface225,228. thereby releasing zinc. This method of adding a third
element can be successfully used to minimize several
Formation of intermetallic compounds other intermetallic interferences233. Finally, the applica-
In many samples, several metal cations are likely to be tion of neural networks234,235 and support vector regres-
present in a wide concentration range. Intermetallic sion methods236 have been reported to address the effect
compounds can form as a result of alloying with the of intermetallic compounds.
electrode or with other metals present in the solution
during the deposition process. Compared with when the Overlapping stripping peaks
metal is deposited alone, intermetallics can exhibit com- Overlapping stripping peaks can result from two or more
pletely different stripping behaviour. A typical example metals depositing independently, not as an intermetal-
is the formation of an intermetallic copper–zinc com- lic compounds but by stripping at similar potentials, for
pound. This results in suppression of the zinc peak, and example cadmium and thallium, cadmium and indium
appearance of the copper–zinc intermetallic stripping or copper and bismuth. This makes quantification diffi-
peak, which is in close proximity to the copper strip cult. The degree of overlap depends on many factors, such
ping peak. As the intermetallic and copper peaks severely as the electrode material, the solution matrix, the relative
overlap, the effect is a virtual enhancement of the cop- concentrations of the metals and the deposition potential.
per peak229. Various methodologies have been applied Prior to ESA analysis, interfering metals can be removed
to prevent the formation of intermetallics. To this end, by using a pretreatment processes, such as ion-exchange
the selection of a suitable working electrode is critical. resins237,238. Some approaches used to improve resolu-
On solid electrodes, intermetallic compounds are more tion between adjacent peaks include a suitable working
severe than on mercury or bismuth electrodes because electrode222, control of the chemistry239 and application
the different metals are more likely to interact with each of different chemometric approaches, for example curve
other. In addition, at solid electrodes, electrodeposited fitting240, fast Hartley transform deconvolution241, multi-
metals often give rise to more than one peak due to the component analysis242, independent component analy-
formation of deposits with different stripping potentials, sis243 and neural networks244,245. Figure 7b illustrates the
known as underpotential deposition. This phenomenon separation of overlapped indium and cadmium peaks
complicates the analytical signal interpretation31,230. by using a chemical approach (changing the supporting
Figure 7a illustrates a case study where a copper–lead electrolyte) and a chemometric approach of peak fitting.
intermetallic compound is formed, resulting in drastic
changes of the lead peak and the appearance of a spu- Surface-active compounds
rious peak arising from the copper–lead stripping. In Organic matter in many environmental and biological
the case of mercury and bismuth electrodes where the samples — such as proteins, fats, cells and surfactants
Underpotential deposition target metals are dissolved to form amalgams and alloys, — can block or foul the surface of the electrode246,247. In
A phenomenon of electrodepo- respectively, interactions between the pre-concentrated most cases, a gradual decrease, or even complete sup-
sition of a species (typically
metals and intermetallics are less likely to form. Careful pression, of the stripping signal results from electrode
reduction of a metal cation to a
solid metal) at a potential less choice of the supporting electrolyte231, deposition poten- fouling by organic materials. The effects of organic
negative than the equilibrium tial and time can be used to address the effect of inter- matter are particularly critical in methods involving
(Nernst) potential for the metallic compounds232. Another approach is preferential adsorptive accumulation owing to competition with
reduction of this metal (the formation of an alternative intermetallic compound. For the analyte for sites on the electrode surface. Different
equilibrium potential for
the reduction of a metal is the
example, the formation of the copper–zinc intermetal- schemes have been developed to alleviate matrix effects
potential at which the metal lic compound, which complicates the determination of due to surface-active compounds. These include the use
will deposit onto itself). Zn(II), can be prevented by adding Ga(II) to the sample. of sample decomposition with acids4, addition of fumed
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silica that preferentially adsorbs these compounds248, capabilities provide continuous remote monitoring
use of permselective coatings such as Nafion249,250, pre- of water resources for detecting sudden metal dis-
treatment of the sample with exchange resins251 and UV charges156,257–259. Remarkably, ESA has been used widely for
irradiation to destroy organic matter145. in situ field operations since the mid-1970s, particularly
during oceanographic shipboard missions260.
Outlook Another area attracting increasing attention is min-
Ninety years have passed since Zbinden reported the use iaturized and microfluidic devices. Microfluidic systems
of stripping analysis for detecting metal ions in 1931, can process small sample quantities in channels from
demonstrating the new concept for determination of tens to hundreds of micrometres in size. Microfluidic
copper15. Over the past six decades there has been tre- devices can incorporate important experimental steps
mendous progress in the fundamental and practical into a single device. These steps include sample prepa-
aspects of ESA, including new stripping principles and ration, separation, reaction and detection. Consequently,
electrode materials. During the 1980s, introduction of use of microfluidic devices can reduce transport, pro-
alternative, non-electrolytic, adsorptive accumulation cessing and labour expenses. This makes them an
schemes expanded the scope of ESA towards additional ideal choice for chemical assays in developing coun-
trace metals, as well as organic compounds of biologi- tries or resource-limited environments. By contrast,
cal and environmental significance. These advances paper-based analytical devices enable fluidic manipula-
greatly increased the range and power of ESA, allowing tion of samples and reagents within hydrophilic channels
trace measurements to be performed rapidly, reliably delimited by hydrophobic barriers on paper substrates.
and inexpensively. Gradually, ESA is moving away from Paper-based analytical devices provide a convenient way
traditional centralized laboratory-based measurements to perform ESA for point-of care or on-site applications
to decentralized field and home testing, with diverse in a cost-effective manner. They achieve this by taking
applications ranging from continuous remote sensing to advantage of the many favourable attributes of paper as
single-use measurements. Bulky instruments and electro- a platform: low cost, wide availability, flexibility, cap-
chemical cells based on toxic mercury drop electrodes are illary action, biodegradability and low weight. Several
being replaced with handheld analysers and disposable microfluidic devices and electrochemical paper-based
printed strip electrodes252. Significant developments in analytical devices have been reported for ESA of metals
electrochemical sensing approaches, along with advances and metalloids in various samples165,261–263.
in microelectronic technology, have led to the introduc- Current ESA assays offer the unique ability to detect
tion of remote and wearable ESA platforms. Over the up to four or five trace metals simultaneously, down to
next decade, these sensors, connected to smartphones in remarkably low (sub-nanomolar and sub-picomolar)
a wireless mode, are expected to accelerate the realiza- detection limits using compact, low-powered, inexpen-
tion of decentralized environmental and clinical testing sive instrumentation. Despite such impressive capabil-
of toxic metals and organic compounds of biological ities and tremendous progress, the widespread use and
significance. Such future use of ESA sensors is expected commercial activity of ESA are hindered by its limited
to bring new opportunities for the monitoring of water scope for big-scale, multiplexed analysis and the differ-
quality, for example home-based drinking water testing ent sample pretreatments required to address matrix
kits for toxic heavy metals such as lead and cadmium. effects. Continued multidisciplinary efforts between
These rapid changes are facilitated by the develop- electrochemists, analytical chemists, electrical engineers,
ment of wearable electrochemical sensors. Already, biologists, material scientists, statisticians, biologists and
such developments have brought a major paradigm medical practitioners are expected to address existing
shift in electroanalytical chemistry253. On-body ESA gaps towards the next generation of smaller, faster and
systems are expected to offer continuous monitoring of better ESA systems. These collaborative efforts will result
trace metals in sweat, tears, interstitial fluids and saliva. in new advanced electrode materials and innovative ESA
Proof-of-principle demonstration of such capabilities approaches (capable of measuring rapidly over a dozen
include a non-invasive epidermal sensor to monitor trace elements in ultrasmall microlitre samples), and
zinc in sweat254 and an electrochemical sensor screen powerful new analytical capabilities that will accelerate
printed on underwater garments to monitor copper in new and novel applications in new frontiers (for exam-
seawater255. These applications require the use of flexi- ple, under the skin and within our cells). A growing use
ble electrodes on textiles and accessories integrated with of ESA is expected for investigation of metal nanopar-
conformal electronic circuitry and displays. Forensic ticles and their application as electrochemical labels for
applications, for example assays of gunshot residues, diverse bioaffinity assays264. Such progress and vision
will rely on stretchable gloves for swipe-and-detect will allow ESA to retain its place as one of the most
measurements of antimony or lead256. powerful tools for trace analysis.
Networks of in situ submersible ESA sensor arrays,
remote probes and autonomous boats with ESA Published online xx xx xxxx
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Electrochemical stripping analysis

NAture RevIews | METHoDS PrimErS | Article citation ID: (2022) 2:62 1

Types of working electrodes

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(i) Stripping voltammetry (ii) PSA A sol Organic analyte in solution

B sol Product in solution

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Signal (current or Δt/ΔE)

Signal (current or Δt/ΔE)

0.10 Standard additions

Signal (current or Δt/ΔE)

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90 91 92 93 94 95 96 97 98 99 100 101 102 103

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a Cd Fig. 6 | Application examples of ESA. a | Example of

techniques are not viable for monitoring the purification

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