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  • Primer
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Electrochemical stripping analysis

Nature Reviews Methods Primers volume 2, Article number: 62 (2022) Cite this article

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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 electroanalytical 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.

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Fig. 1: Historical evolution of ESA.
Fig. 2: The principle of ESA.
Fig. 3: Experimental set-ups and main variables in ESA.
Fig. 4: Signal processing and quantification in ESA.
Fig. 5: List of elements that can be determined by ESA.
Fig. 6: Application examples of ESA.
Fig. 7: Examples of limitations in ESA.

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Author information

Authors and Affiliations

  1. Department of Chemical Engineering and Analytical Chemistry, University of Barcelona, Barcelona, Spain

    Cristina Ariño & Clara Pérez-Ràfols

  2. Faculty of Science and Engineering, Manchester Metropolitan University, Manchester, UK

    Craig E. Banks & Robert D. Crapnell

  3. Department of Building Materials Technology, Faculty of Materials Science and Ceramics, AGH University of Science and Technology, Krakow, Poland

    Andrzej Bobrowski & Agnieszka Królicka

  4. Department of Chemistry, National and Kapodistrian University of Athens, Athens, Greece

    Anastasios Economou & Dionysios Soulis

  5. Department of Nanoengineering, University of California San Diego, La Jolla, CA, USA

    Joseph Wang

Authors
  1. Cristina Ariño
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  2. Craig E. Banks
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  3. Andrzej Bobrowski
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  4. Robert D. Crapnell
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  5. Anastasios Economou
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  6. Agnieszka Królicka
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  7. Clara Pérez-Ràfols
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  8. Dionysios Soulis
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  9. Joseph Wang
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Contributions

Introduction (A.E. and D.S.); Experimentation (C.E.B. and R.D.C.); Results (C.A. and C.P.-R.); Applications (A.B. and A.K.); Reproducibility and data deposition (C.A. and C.P.-R.); Limitations and optimizations (A.E. and D.S.); Outlook (J.W.); overview of the Primer (A.E., C.A., C.E.B., A.B., R.D.C., A.K., C.P.-R., D.S. and J.W.).

Corresponding author

Correspondence to Anastasios Economou.

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Nature Reviews Methods Primers thanks Damien Arrigan, Jiri Barek, Dawei Pan and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Glossary

Pre-concentration

The process by which the analyte (or its compound) is deposited on the working electrode.

Working electrode

An electrode at which one or more analytes undergo a redox reaction and whose response is used as an analytical signal.

Convective mass transfer

A mechanism of mass transfer to the electrode based on the forced movement of solution caused by stirring, vibrations or heating.

Voltammetry

An electroanalytical technique that involves scanning the potential of the working electrode versus time and measurement of the current versus potential.

(Chrono-)Potentiometry

An electroanalytical technique that involves a redox reaction at the working electrode and measurement of the potential versus time.

Stripping voltammetry

A two-step electrochemical measurement. The first step is to accumulate material at an electrode, whereas the second step is to measure the amount of accumulated species by voltammetry.

Potentiometric stripping analysis

(PSA). An electrochemical measurement where material is accumulated at an electrode. The accumulated material is then removed either by chemical reaction or electrochemically at constant current while the electrode potential is measured.

Potentiostat

An instrument used to measure electric current. It controls the potential between working and reference electrodes and measures the current between working and auxiliary electrodes.

Reference electrode

An electrode with respect to which the potential of the working electrode is measured in an electrochemical cell.

Counter electrode

An electrode that carries the electric current flowing through an electrochemical cell. Any electrochemical processes that occur on the surface of this electrode are not of interest.

Non-faradaic (or capacitive) contributions

Refers to the current arising from an electrical double layer charging at an electrode–solution interface. Non-faradaic current is not associated with a redox reaction.

Polarization potential window

A range of electrode potentials where, when compared with the current from of the investigated reaction, the electric current from the electrode or electrolyte reaction is negligible.

Electron transfer rate

The rate at which electrons are exchanged between a working electrode and a redox species.

Overpotential

Additional potential above the equilibrium Nernst potential value that is required for an electric current to flow through the working electrode.

Anodic stripping voltammetry

(ASV). A stripping voltammetry method where electrochemical oxidation occurs during the stripping step of material accumulated at the working electrode.

Cathodic stripping voltammetry

(CSV). A stripping voltammetry method where electrochemical reduction occurs during the stripping step of material accumulated at the working electrode.

Faradaic current

An electric current that arises from redox reactions of electroactive species at a working electrode.

Voltammogram

The representation of current versus potential.

Constant current PSA

(Constant current potentiometric stripping analysis) or constant current stripping (chrono)potentiometry . An electrochemical measurement where material is accumulated at an electrode. The accumulated material is then electrochemically removed at constant current while the electrode potential is measured.

Potentiogram

A representation of the differential Δt/ΔE versus potential.

Matrix effects

Effects of the matrix of the sample on the analytical response.

Matrix-matched standard solutions

Standard solutions prepared in a matrix similar to the matrix of the sample.

Adsorptive stripping voltammetry

(AdSV). A stripping voltammetry method where pre-concentration is achieved by adsorption of the analyte or its compound.

Underpotential deposition

A phenomenon of electrodeposition of a species (typically reduction of a metal cation to a solid metal) at a potential less negative than the equilibrium (Nernst) potential for the reduction of this metal (the equilibrium potential for the reduction of a metal is the potential at which the metal will deposit onto itself).

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Ariño, C., Banks, C.E., Bobrowski, A. et al. Electrochemical stripping analysis. Nat Rev Methods Primers 2, 62 (2022). https://doi.org/10.1038/s43586-022-00143-5

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