This new series of blog posts covers a range of new sensors suitable for the determination of «heavy metals» using voltammetric methods.
The quantification of heavy metal ions plays an important role in many applications, including environmental monitoring, waste management, research studies, or even in clinical tests. Heavy metals occur naturally, but the rise of industrialization and urbanization in the past two centuries are responsible for increased levels in our environment. These dangerous elements are released and accumulate in the soil, and in ground or surface water. They enter the food chain directly from drinking water or through bioaccumulation in plants and animals. It is for this reason that pregnant women are discouraged from eating seafood, on the basis of mercury (Hg) accumulation through the food chain.
The degree of toxicity depends on the type of metal, its biological role, and most importantly, its concentration. Increased concentrations of lead, iron, cadmium, copper, arsenic, chromium, or nickel in drinking water are most often responsible for human poisoning. To highlight the toxicity of certain heavy metals in drinking water and to protect human health, guideline values or limit values for the heavy metal concentration in drinking water have been set by international organizations as the World Health Organization (WHO) or by such authorities as the U.S. Environmental Protection Agency (EPA) or the European Commission.
Several techniques have been developed for heavy metal ion analysis in the past. Commonly used techniques include atomic absorption spectrometry (AAS), inductively coupled plasma (ICP), or fluorescence spectrometry. However, these techniques require expensive equipment combined with high maintenance costs and trained personnel. Therefore, a price-effective, straightforward and sensitive method that allows detection of metal ions in water samples is highly desired.
Stripping voltammetry is the right solution for these challenges providing a simple, rapid, and cost-effective alternative for the aforementioned techniques that is also suited for untrained personnel. In addition, detection limits in the ng/L range and the possibility to determine the trace levels of heavy metals in the field make it so interesting and valuable.
The principle of stripping voltammetry
Voltammetric determination of heavy metals consists of two steps. In the first step, the analyte is preconcentrated on the surface of the working electrode as shown using the example of anodic stripping voltammetric determination of lead (Pb) in Figure 1.
Figure 1. Anodic stripping voltammetry – deposition of lead (solution stirred).
In the subsequent stripping step (Figure 2), the analyte is released. This can be achieved by oxidation or reduction depending on the method used for the determination. This step generates the analytical signal, which has to be proportional to the deposited amount of analyte.
Figure 2. Anodic stripping voltammetry – stripping of lead (solution not stirred).
Besides anodic stripping voltammetry, cathodic stripping voltammetry or adsorptive stripping voltammetry are also possible to utilize and work in a similar manner. All of these methods have something in common: every voltammetric determination is as good as the sensor used for the measurement. Therefore, in this series of posts we want to introduce our powerful sensors and demonstrate the outstanding performance with a few typical applications.
Need for new sensors
The need for heavy metal ion determinations in the field, sensor costs, and environmental issues are the main triggers for research on new sensors in voltammetry. Non-toxic and inexpensive materials are preferred for new sensors. The properties of these materials, however, can lead to some restrictions. First is the limited number of elements that can be detected on a particular electrode material (e.g., gold, carbon or bismuth). In addition, it is difficult to determine several elements simultaneously at the same mercury-free sensor. The choice of the most suitable electrode material in combination with the optimum sensor design helps to overcome these issues.
Bismuth as an alternative electrode material
In the past, there were many attempts to find less toxic electrode materials than mercury for the determination of heavy metal ions, but none have achieved exceptional electroanalytical performance. Twenty years ago (2000), an American researcher by the name of Joseph Wang reported a bismuth film electrode for the first time (Joseph Wang, 2000).
Figure 3. Bismuth crystal.
After this initial revolutionary report, bismuth-based electrodes prepared as in-situ and ex-situ films on solid-state electrodes such as carbon, have been growing in popularity. The broad electrochemical window and low toxicity of bismuth were key factors. In addition, bismuth is able to form alloys with quite a high number of heavy metals and it exhibits high hydrogen overpotential, similar to mercury. These properties are particularly interesting for stripping voltammetry. The hydrogen evolution is suppressed very efficiently with the consequence that noise-free measurements at negative potentials can be carried out. Bismuth electrodes based on bismuth films are a good option. However, film deposition is an additional step that is time-consuming.
New sensor in VA: the Bi drop electrode
With the Bi drop electrode, a novel solid-state electrode is now available for the determination of heavy metal ions in drinking water. A bismuth drop of approximately 2 mm diameter serves as the working electrode within the voltammetric measurement.
The electrode works without the need for polishing or film deposition—only electrochemical activation is required. This significantly shortens the entire analysis time. Once activated, series of heavy metal determinations with high repeatability in the low μg/L and even ng/L range are possible.
The Bi drop electrode allows for mercury-free monitoring of the limit values of the heavy metals cadmium, lead, nickel, cobalt, and iron in drinking water. Since the electrode does not require mechanical treatment, it is especially suitable for online applications. Another advantage of the Bi drop electrode is fact that cadmium and lead as well as nickel and cobalt can be determined simultaneously.
The sensor is cost-efficient, stable, extremely sensitive, and is able to deliver more reproducible results than other previously examined bismuth-based electrodes. To demonstrate the broad possibilities and flexibility of the Bi drop electrode, examples for anodic stripping voltammetry, adsorptive stripping voltammetry, and direct voltammetric determination will be presented and discussed.
Anodic stripping voltammetric determination of cadmium and lead
To reduce the toxic effects of cadmium on the kidneys, skeleton, and respiratory system, as well as the neurotoxic effects of lead, 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.
Figure 5. Example for determination of cadmium and lead in tap water spiked with β(Cd) = 2 µg/L and β(Pb) = 2 µg/L.
A completely mercury‑free sensor, the Bi drop electrode allows the simultaneous determination of cadmium and lead in drinking water without any additional film plating step. With a 60 s deposition time, a limit of detection (LOD) of 0.1 µg/L for cadmium and 0.5 µg/L for lead can be achieved. This outstanding sensitivity is more than sufficient to monitor the provisional WHO guideline values.
Not only is the sensitivity impressive, but also the reproducibility and accuracy. The relative standard deviation for 10 measurements in a check standard solution (β(Cd) = 1 µg/L and β(Pb) = 5 µg/L) is 5% and 3%, and the recovery rate is 90% and 100% for cadmium and lead, respectively.
Direct determination of iron
The presence of iron in drinking water can lead to an unpleasant, harsh metallic taste or reddish-brown stains. In addition, «iron bacteria» which can grow in waters containing iron as low as 100 µg/L, create a reddish-brown slime that can clog plumbing and cause an offensive odor. Over a longer period, the formation of insoluble iron deposits is problematic in many industrial and agricultural applications, such as water supply, system cooling, or field irrigation. To avoid these problems, the U.S. Environmental Protection Agency (EPA) defines the Secondary Maximum Contaminant Level (SMCL) for water treatment and processing plants as 300 µg/L iron in drinking water.
The voltammetric determination of the iron triethanolamine complex on the non-toxic Bi drop electrode does not require enrichment. The system uses catalytic signal enhancement, allowing both the detection at very low levels with a limit of detection of 5 µg/L and measurements in a wide range of concentrations up to 500 µg/L.
This method is best suited for automated systems or process analyzers, allowing fully automatic determination of iron in a large sample series and providing stable results. The relative standard deviation for 10 measurements in a check standard solution (β(Fe) = 50 µg/L) is 3% and the recovery rate is 111%.
Adsorptive stripping voltammetric determination of nickel and cobalt
The main sources of nickel pollution are from electroplating processes, metallurgical operations, or leaching from pipes and fittings. Catalysts used in the petroleum and chemical industries are major application fields for cobalt. In both cases, the metal is either released directly, or via the wastewater–river pathway into the drinking water system. Therefore 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). The unique properties of the non-toxic Bi drop electrode combined with AdSV results in an excellent performance in terms of sensitivity. The limit of detection for 30 s deposition time is approximately 0.2 µg/L for nickel and 0.1 µg/L for cobalt, and can be lowered further by increasing the deposition time.
Figure 7. Determination of nickel and cobalt in tap water spiked with β(Ni) = 0.5 µg/L and β(Co) = 0.5 µg/L.
This method is best suited for automated systems or process analyzers, allowing fully automatic determination of these metals in large sample series and providing stable and accurate results. The relative standard deviation for 10 subsequent measurements in a check standard solution (β(Ni) = 1 µg/L β(Co) = 1 µg/L) is 4% and 5% and the recovery rate is 106% for nickel and 88% for cobalt.
Key features of the Bi drop electrode
- Non-toxic, completely mercury-free alternative for trace metal determination
- Simultaneous determination of Ni and Co, as well as Cd and Pb
- Limit of detection in low μg/L and even ng/L range
- Suitable for automated and online systems
Post written by Dr. Jakub Tymoczko, Application Specialist VA/CVS at Metrohm International Headquarters, Herisau, Switzerland.