In this series of articles featuring various solid state electrodes, we have introduced the new Bi drop electrode and the scTRACE Gold electrode and their potential in the determination of heavy metals in drinking water. In Part 4, we introduce the next type of sensors available for heavy metal analysis: the screen-printed electrode (SPE) together with two applications for the simultaneous determination of cadmium and lead as well as nickel and cobalt.

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Figure 1. Screen-printed electrode (SPE) from Metrohm DropSens.

Screen-printed electrodes (SPEs)

Screen printing microfabrication technology is well established for the manufacture of thick film electrochemical sensors. This technology enables the mass production of reproducible and mechanically robust solid electrodes. The possibility of mass production has great impact on the price and makes the SPEs inexpensive and convenient for the determination of heavy metals.

Printing technology allows production of a maintenance-free reference electrode, making the preparation of the analytical system for the analysis of heavy metals faster and more straightforward. Here, you do not need to refill the reference electrode or clean the sensor after a finished determination. The integration of three electrodes (working, reference, and auxiliary – see Figure 1) on a single platform, with the simultaneous miniaturization of their size and the corresponding device, both supports and facilitates transportation of the equipment to the sampling point and the determination of heavy metals on-site.

The simplest and the fastest way to modify the properties of these screen-printed electrodes for heavy metal detection is to deposit (in situ or ex situ) a metal film (either bismuth or mercury) electrochemically on the working electrode. This approach allows flexible use of single sensor type (e.g., carbon) SPEs for a wide range of applications.
 

If you're curious about other uses for SPEs, read our other blog article:

Virus detection using screen-printed electrodes

Mercury film modified SPEs

The mercury film on the carbon working electrode consists of a very thin layer of mercury adsorbed onto the electrode surface. The mechanisms of accumulation and the stripping are the same as those which occur at a conventional mercury drop electrode.

Bismuth film modified SPEs

Because bismuth is not toxic, there are two environmental friendly methods for the preparation of the bismuth film: in situ plating and ex situ plating. With ex situ plating, a bismuth film is prepared in a separate solution before the first determination. Then the modified electrode is rinsed with ultrapure water and can be further used for the analysis.

 

Screen-printed electrodes can only be used for a limited number of measurements and have to be replaced at regular intervals. The lifetime and the frequency of replacement depend on the type of electrode and the application.

Currently, screen printed electrodes allow the on-site, simultaneous determination of cadmium and lead. Therefore, below I will present a method for the cadmium and lead determination using the ex situ modification of the Metrohm DropSens 11L carbon screen printed electrodes with a mercury film.

In addition to the cadmium and lead determination, a method using an ex situ bismuth film for nickel and cobalt will be introduced. Both measurements (cadmium and lead, as well as nickel and cobalt) can be carried out with the 946 Portable VA Analyzer (version for screen printed electrodes (SPE), Figure 2) or with any Metrohm VA Stand using the electrode shaft (Figure 3).

 

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Figure 2. 946 Portable VA Analyzer (SPE version).

For further information about the 946 Portable VA Analyzer, click the link below.

946 Portable VA Analyzer

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Figure 3. Electrode shaft for screen-printed electrodes (SPE).

With the electrode shaft, you can now use screen-printed electrodes in any Metrohm VA Stand. Whether you are performing voltammetric trace analysis or you want to explore new application fields with your own modified sensor, the electrode shaft allows simple use of SPEs.
 

Learn more about the electrode shaft for SPEs in our free flyer.

Flyer: Electrode shaft for screen-printed electrodes – Screen-printed electrodes for VA Analysis

 

Applications

Anodic stripping voltammetric determination of cadmium and lead

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Figure 4. Example for determination of cadmium and lead in tap water spiked with β(Cd) = 2 µg/L and β(Pb) = 2 µg/L.

Cadmium and lead are toxic elements, and their concentration in drinking water has to be monitored. The provisional guideline values in the World Health Organization’s «Guidelines for Drinking-water Quality» are set to a maximum concentration of 3 µg/L for cadmium and 10 µg/L for lead. The Metrohm DropSens 11L carbon screen printed electrode modified with an ex situ mercury film allows the simultaneous determination of cadmium and lead in drinking water samples (Figure 4).

Using the 946 Portable VA Analyzer with a 90 s deposition time, a limit of detection (LOD) of 0.3 µg/L for both elements can be achieved. This is more than sufficient to monitor the provisional WHO guideline values.

The relative standard deviation for 5 measurements in a check standard solution with β(Cd) = 2 µg/L and β(Pb) = 2 µg/L is 14% and 12%, and the recovery rate is 88% and 82% for cadmium and lead, respectively.

Adsorptive stripping voltammetric determination of nickel and cobalt

Nickel and cobalt can be released either directly, or via the wastewater–river pathway, into drinking water systems. In the EU, the legislation specifies 20 µg/L as the limit value for the nickel concentration in drinking water.

The simultaneous and straightforward determination of nickel and cobalt is based on adsorptive stripping voltammetry (AdSV) using dimethylglyoxime (DMG) as a complexing agent. Prior to the first determination, the Metrohm DropSens 11L carbon SPE has to be modified with an ex situ bismuth film. The unique properties of the non-toxic Bi film combined with AdSV results in an excellent performance in terms of sensitivity. When using the 946 Portable VA Analyzer the limit of detection for 30 s deposition time is approximately 0.4 µg/L for nickel and 0.2 µg/L for cobalt, and can be lowered further by increasing the deposition time.
 

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Figure 5. Example determination of nickel and cobalt in tap water with the modified Metrohm DropSens 11L carbon SPE.

The disposable sensor does not need maintenance such as mechanical polishing or mechanical cleaning. This method is best suited for manual systems.

The relative standard deviation for three subsequent measurements in a check standard solution (β(Ni) = 2 µg/L β(Co) = 2 µg/L) is 7% and 8% respectively, and the recovery rate is 100% for nickel and 94% for cobalt.
 

For more information, download our free Application Note.

Ni and Co in drinking water – Simultaneous determination in low µg/L range on SPEs modified with a Bi film

Key features

of the screen-printed electrodes:

  1. Mechanically robust, inexpensive, maintenance-free, miniaturized solid electrodes
  2. Electrode holder fits all Metrohm VA Stands (884 Professional VA, 797 VA Computrace, 663 VA Stand)
  3. Solution-proof electrode holder
  4. Fast and easy exchange of SPEs
  5. Simultaneous determination of Ni and Co, as well as Cd and Pb
  6. Limit of detection in low μg/L and even high ng/L range
  7. Limit of detection in low μg/L and even high ng/L range

Other installments in this series

This blog article was dedicated to the topic of screen-printed electrodes (SPEs) and how they can be used for for the determination of heavy metal ions in drinking water and the environment. Other installments are dedicated to trace metal analysis with these solid-state electrodes:

Author
Tymoczko

Dr. Jakub Tymoczko

Application Specialist VA/CVS
Metrohm International Headquarters, Herisau, Switzerland

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