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Trace metal analysis with solid-state electrodes – Part 4

Trace metal analysis with solid-state electrodes – Part 4

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.

Catch up on the series «Trace metal analysis with solid-state electrodes» here:

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.

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

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.

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.

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

For further information about the 946 Portable VA Analyzer, visit the Metrohm website!

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), see Figure 2) or with any Metrohm VA Stand using the electrode shaft (see Figure 3).

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.

To download our free informative flyer, click the button below!

This leaflet explains even more about the handling and troubleshooting of the electrode shaft for screen-printed electrodes.

Applications

Anodic stripping voltammetric determination of cadmium and lead

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).

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.

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.

For more information about this application, download our free application note:

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.

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

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

The relative standard deviation for 3 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 about this application, download our free application note:

Key features of the screen-printed electrodes

  • Mechanically robust, inexpensive, maintenance-free, miniaturized solid electrodes
  • Electrode holder fits all Metrohm VA Stands
    • 884 Professional VA, 797 VA Computrace, 663 VA Stand
  • Solution-proof electrode holder
  • Fast and easy exchange of SPEs
  • Simultaneous determination of Ni and Co, as well as Cd and Pb
  • Limit of detection in low μg/L and even high ng/L range
  • Suitable for on-site diagnostics

What’s next?

In the next part of this series on solid state electrodes, we will have a look at an ultra-sensitive and robust sensor for heavy metal detection: the glassy carbon electrode with some of its associated applications.

Post written by Dr. Jakub TymoczkoApplication Specialist VA/CVS at Metrohm International Headquarters, Herisau, Switzerland.

Oven method for sample preparation in Karl Fischer titration

Oven method for sample preparation in Karl Fischer titration

Maybe you have experienced one of the following situations in the laboratory. You need to determine the water content of a sample using Karl Fischer titration and you realize one or more of these issues:

  • The sample does not dissolve in the KF reagent. No solubilizer helps, the sample is still not dissolving, and the results are far from reproducible.
  • The sample reacts with the KF reagent. The titration does not stop, and there is no endpoint detected.
  • The sample contaminates the titration cell and the electrode(s). Even if you replace the reagent after every measurement, the obtained results are out of specification.

There is a way to solve the above-mentioned problems. Trust me—it’s fantastic!!

The solution is the oven method or gas extraction technique.

What is Karl Fischer titration? Download our free Monograph to learn more from the experts.

What is the oven method?

The oven method is a sample preparation technique used in Karl Fischer titration to analyze samples…

For more help, take a look at our frequently asked questions in Karl Fischer titration under the section «Sample Handling» here on our website:

The principle is very simple.

The sample is weighed into a headspace vial and closed with a septum cap. When placed in an oven, the water evaporates and a carrier gas (usually air or nitrogen) dried with a molecular sieve transports the released water into the titration cell, where the determination of the water content takes place. The water is separated from the sample matrix, avoiding side reactions and contamination.

The temperature of the oven is chosen according to the temperature stability of the sample. This leads to the question to which temperature the sample should be heated. What is the optimal oven temperature?

Finding the optimal oven temperature

Using a suitable oven temperature to analyze a sample is crucial to obtain the correct results. The oven temperature should be as high as possible, within reason. This guarantees a fast and complete release of the water and subsequently, short titration times. However, you should avoid choosing a temperature that is too high. Decomposition of the sample usually leads to the formation of unwanted substances that can falsify the water content. Therefore, as a rule of thumb, I recommend choosing an oven temperature 20 °C below the decomposition temperature of the sample.

But what can you do if you have no idea at which temperature your sample should be analyzed? No worries! There are several ways to find the optimal oven temperature.

One possibility is to search in the literature. The more information on temperature stability of the sample you find, the better off you will be. If you are able to find a decomposition temperature, it will help immensely to define the optimal oven temperature. Maybe you are lucky and someone else has already analyzed the same sample; then you may also find a recommended oven temperature. A good start is reading our free Application Bulletin AB-280, which lists several substances.

Are you searching for Karl Fischer titration oven applications? Look no further – the Metrohm Application Finder contains several applications you can download for free! Check them out here:

If literature research does not reveal a suitable oven temperature, you must determine it yourself. How this is done depends upon the type of instrument you are using.

Some instruments offer you the possibility to run a so-called temperature gradient or temperature ramp. The sample is heated at a constant rate (e.g., 0.5 °C or 2 °C per minute) in a defined temperature range (e.g., 50 to 250 °C). At the same time, the released water is determined. In the end, the software will display a curve, showing you the released water as a function of the temperature. The following graph shows an example of such a temperature gradient curve.

The blue line corresponds to the determined water content, whereas the orange line indicates the drift value. An increasing drift signals the release of water, but it can also be a sign for decomposition, especially if the drift no longer decreases to a low level. In this graph, the drift peak at 50 °C corresponds to the blank value and free water. Between 120 and 200 °C, the drift value increases again, meaning the sample releases water. Then the drift decreases and remains low and stable up to 250 °C. There are no signs of decomposition up to 250 °C. As we do not know what would happen at temperatures above 250 °C, the optimal oven temperature for this sample is 230 °C (250 °C – 20 °C = 230 °C).

In case the instrument you use does not offer the option to run a temperature gradient, you can manually increase the temperature and measure the sample at different temperatures. In an Excel spreadsheet, you can display the curve (released water against temperature). If there is a temperature range where you see reproducible water contents, then you have found the optimal oven temperature.

Here is an example of a sample which started to decompose at temperatures above 106 °C (left sample vial) and thus is turning brown. An optimal temperature would therefore be 85 °C.

Sample analysis with a KF oven – step by step

After you have found the optimal oven temperature, water content determination in the sample can begin.

  • First, I recommend to run a system preparation. This means running a determination, but with an empty sample vial. During this preparation step, all tubes in the system are purged with dried carrier gas, and any traces of water are removed.
  • Next, you need to determine the blank value. The sample vials and the caps contain some residual moisture. With the blank determination, the amount of water contained in an empty sample vial is determined. The mean value of e.g. 3 blank value determinations is then subtracted from the water content obtained for the samples.
  • Finally, you can analyze the samples.

Please keep in mind that the same parameters for the system preparation, the blank value determination, and the sample determination must be used. This is of importance if you want to measure a check standard before and/or after the sample analysis or sample series. If the optimal oven temperature for the standard is different from the one for the sample, I recommend that you determine a blank value for the standard as well.

Checking an oven system

There are special, solid water standards available to check the performance of an oven system. These water standards are perfect to inspect the complete oven system and to ensure that the evaporated water reaches the titration cell and is determined there. Such standards include a certificate stating the water content.

Using the certified value, you can calculate the recovery when determining the water content of the standard with the oven. If the recovery value is between 97–103%, everything is fine. However, if the recovery is outside this range, the oven system should be checked for leaks or water deposits. It might be that only the molecular sieve needs to be exchanged. Possibly, the reagent is exhausted and needs to be replaced.

There are other reasons which explain recovery values which are too high or too low. The reason must be found, as incorrect recovery values also mean that the determined sample water content is wrong. Have a look at our free Application Bulletin 280 for detailed information on troubleshooting an oven system.

Summary

The oven method is a simple and convenient way to analyze difficult samples. Side reactions are reduced to a minimum. The titration cell and the reagent are not contaminated with sample. In case you have to analyze a large series of samples, automation of the oven method is possible. Have a look at the available instruments for the oven method on our website!

Want to learn more

about Karl Fischer titration

Watch our free webinars here!

Post written by Michael Margreth, Sr. Product Specialist Titration (Karl Fischer Titration) at Metrohm International Headquarters, Herisau, Switzerland.

Frequently asked questions in near-infrared spectroscopy analysis – Part 1

Frequently asked questions in near-infrared spectroscopy analysis – Part 1

Whether you are new to the technique, a seasoned veteran, or merely just curious about near-infrared spectroscopy (NIRS), Metrohm is here to help you to learn all about how to perform the best analysis possible with your instruments.

In this series, we will cover several frequently asked questions regarding both our laboratory NIRS instruments as well as our line of Process Analysis NIRS products.

1. What is the difference between IR spectroscopy and NIR spectroscopy?

IR (infrared) and NIR (near-infrared) spectroscopy utilize different spectral ranges of light. Light in the NIR range is higher in energy than IR light (Figure 1), which affects the interaction with the molecules in a sample.

Electromagnetic Spectrum
Figure 1. The electromagnetic spectrum.

This energy difference has both advantages and disadvantages, and the selection of the ideal technology depends very much on the application. The higher energy NIR light is absorbed less than IR light by most organic materials, broadening the resulting bands and making it difficult to assign them to specific functional groups without mathematical processing.

However, this same feature makes it possible to perform analysis without sample preparation, as there is no need to prepare very thin layers of analyte or use ATR (attenuated total reflection). Additionally, NIRS can quantify the water content in samples up to 15%.

Want to learn more about how to perform faster quality control at lower operating costs by using NIRS in your lab? Download our free white paper here: Boost Efficiency in the QC laboratory: How NIRS helps reduce costs up to 90%.

The weaker absorption of NIR light leads to using long pathlengths for liquid measurements, which is particularly helpful in industrial process environments. Speaking of such process applications, with NIR spectroscopy, you can use long fiber optic cables to connect the analyzer to the measuring probe, allowing remote measurements throughout the process due to low absorbance of the NIR light by the fiber (Figure 2).

Electromagnetic Spectrum
Figure 2. Illustration of the long-distance measurement possibility of a NIRS process analyzer with the use of low-dispersion fiber optic cables. Many sampling options are available for completely automated analysis, allowing users to gather real-time data for immediate process adjustments.

For more information, read our previous blog post outlining the differences between infrared and near-infrared spectroscopy.

2. NIR spectroscopy is a «secondary technology». What does this mean?

To create prediction models in NIR spectroscopy, the NIR spectra are correlated with parameters of interest, e.g., the water content in a sample. These models are then used during routine quality control to analyze samples.

Values from a reference (primary) method need to be correlated with the NIR spectrum to create prediction models (Figure 3). Since NIR spectroscopy results depend on the availability of such reference values during prediction model development, NIR spectroscopy is therefore considered a secondary technology.

Electromagnetic Spectrum
Figure 3. Correlation plot of moisture content in samples measured by NIRS compared to the same samples measured with a primary laboratory method.

For more information about how Karl Fischer titration and NIR spectroscopy work in perfect synergy, download our brochure: Water Content Analysis – Karl Fischer titration and Near-Infrared Spectroscopy in perfect synergy.

Read our previous blog posts to learn more about NIRS as a secondary technique.

3. What is a prediction model, and how often do I need to create/update it?

In NIR spectroscopy, prediction models interpret a sample’s NIR spectrum to determine the values of key quality parameters such as water content, density, or total acid number, just to name a few. Prediction models are created by combining sample NIR spectra with reference values from reference methods, such as Karl Fischer titration for water content (Figure 3).

A prediction model, which consists of sufficient representative spectra and reference values, is typically created once and will only need an update if samples begin to vary (for example after a change of production process equipment or parameter, raw material supplier, etc.).

Want to know more about prediction models for NIRS? Read our blog post about the creation and validation of prediction models here.

4. How many samples are required to develop a prediction model?

The number of samples needed for a good prediction model depends on the complexity of the sample matrix and the molecular absorptivity of the key parameter.

For an «easy» matrix, e.g., a halogenated solvent with its water concentration as the measurement parameter, a sample set of 1020 spectra covering the complete concentration range of interest may be sufficient. For applications that are more complex, we recommend using at least 40–60 spectra in order  to build a reliable prediction model.

Find out more about NIRS pre-calibrations built on prediction models and how they can save time and effort in the lab.

5. Which norms describe the use of NIR in regulated and non-regulated industries?

Norms describing how to implement a near-infrared spectroscopy system in a validated environment include USP <856> and USP <1856>. A general norm for non-regulated environments regarding how to create prediction models and basic requirements for near-infrared spectroscopy systems are described in ASTM E1655. Method validation and instrument validation are guided by ASTM D6122 and ASTM D6299, respectively.

Figure 4. Different steps for the successful development of quantitative methods according to international standards.

For specific measurements, e.g. RON and MON analysis in fuels, standards such as ASTM D2699 and ASTM D2700 should be followed.

For further information, download our free Application Note: Quality Control of Gasoline – Rapid determination of RON, MON, AKI, aromatic content, and density with NIRS.

6. How can NIRS be implemented in a production process?

Chemical analysis in process streams is not always a simple task. The chemical and physical properties such as viscosity and flammability of the sample streams can interfere in the analysis measurements. Some industrial processes are quite delicate—even the slightest changes to the process parameters can lead to significant variability in the properties of final products. Therefore, it is essential to measure the properties of the stream continuously and adjust the processing parameters via rapid feedback to assure a consistent and high quality product.

Figure 5. Example of the integration of inline NIRS analysis in a fluid bed dryer of a production plant.

Curious about this type of application? Download it for free from the Metrohm website!

The use of fiber optic probes in NIRS systems has opened up new perspectives for process monitoring. A suitable NIR probe connected to the spectrometer via optical fiber allows direct online and inline monitoring without interference in the process. Currently, a wide variety of NIR optical probes are available, from transmission pair probes and immersion probes to reflectance and transflectance probes, suitable for contact and non-contact measurements. This diversity allows NIR spectroscopy to be applied to almost any kind of sample composition, including melts, solutions, emulsions, and solid powders.

Selecting the right probe, or sample interface, to use with a NIR process analyzer is crucial to successful process implementation for inline or online process monitoring. Depending upon whether the sample is in a liquid, solid or gaseous state, transflectance or transmission probes are used to measure the sample, and specific fitting attachments are used to connect the probes to the reactor, tank, or pipe. With more than 45 years of experience, Metrohm Process Analytics can design the best solutions for your process. 

Visit our website to find a selection of free Application Notes to download related to NIRS measurements in industrial processes.

7. How can product quality be optimized with process NIRS?

Regular control of key process parameters is essential to comply with certain product and process specifications, and results in attaining optimal product quality and consistency in any industry. NIRS analyzers can provide data every 30 seconds for near real-time monitoring of production processes.

Figure 6. The Metrohm Process Analytics NIRS XDS Process Analyzer, shown here with multiplexer option allowing up to 9 measuring channels. Here, both microbundle (yellow) and single fiber (blue) optical cables are connected, with both a reflectance probe and transmission pair configured.

Using NIRS process analyzers is not only preferable for 24/7 monitoring of the manufacturing process, it is also extremely beneficial for inspecting the quality of raw materials and reagents. By providing data in «real-time» to the industrial control system (e.g., DCS or PLC), any process can be automated based on the NIRS data. As a result, downtimes are reduced, unforeseen situations are avoided, and costly company assets are safeguarded.

Furthermore, the included software on Metrohm Process Analytics NIRS instruments has a built-in chemometric package which allows qualification of a product even while it is still being produced. A report is then generated which can be directly used by the QC manager. Therefore, the product quality consistency is improved leading to potential added revenues.

Do you want to learn more about improving product quality with online or inline NIRS analysis? Take a look at our brochure!

In the next part of this FAQ, we will cover even more of your burning questions regarding NIRS for lab and process measurements. Don’t forget to subscribe to the blog so you don’t miss out on future posts!

Want to learn more about NIR spectroscopy and potential applications? Have a look at our free and comprehensive application booklet about NIR spectroscopy.

Download our Monograph

A guide to near-infrared spectroscopic analysis of industrial manufacturing processes

Post written by Dr. Nicolas Rühl (Product Manager Spectroscopy at Metrohm International Headquarters, Herisau, Switzerland) and Dr. Alexandre Olive (Product Manager Process Spectroscopy at Metrohm Applikon, Schiedam, The Netherlands).

Exposing secrets of ancient Greek civilization through chemistry

Exposing secrets of ancient Greek civilization through chemistry

This week, learn the story of how analytical instrumentation from Metrohm helps underwater archaeology locate hidden treasures beneath the seafloor.

 

Antikythera Mechanism: a machine lost to time

One of the most fascinating items ever salvaged from an ancient shipwreck is the so-called «Antikythera Mechanism». More than 2000 years old, this magnificent piece of mechanical engineering forced the scientific community to rewrite the history of science as it became clear that its unknown maker must have possessed knowledge and skills that were believed to simply not exist in the 1st century BC.

Figure 1. Digital reconstruction of the Antikythera Mechanism.

The Antikythera Mechanism was a complex and highly precise lunar and solar calendar that could also predict solar and lunar eclipses as well as the future dates of the Panhellenic Games. The complexity and precision of this machine inspired not only scientists but also Hublot, the Swiss brand famous for their luxury watches. Not only did Hublot recreate the Antikythera Mechanism in a wristwatch but they also started their own underwater archaeology program. This project of Hublot is fascinating—and we from Metrohm are part of it on every dive.

 The device was retrieved from an ancient shipwreck (70 BC) found off the coast of the Greek island of Antikythera in 1901. Since then, researchers have tried to get to the bottom of its mysteries. Dated to approximately 100 BC, the Antikythera Mechanism was a shockingly complex piece of machinery, the likes of which were not seen elsewhere for at least another millennium.

One of the challenges faced by underwater archeology is the fact that the cargo and debris of ancient shipwrecks is often randomly scattered across vast areas on the seafloor and also often covered by sediments. Because only fragments of the mechanism have been found and recovered, retrieving the missing pieces of the Antikythera Mechanism would be a scientific sensation.

Figure 2. Location where the Antikythera Mechanism was found in 1901 at a shipwreck in Greece.

As divers can only operate for very limited time spans at depths below 50 meters, drones are needed to investigate larger areas on the seafloor at such depths. Hublot’s engineers have built drones for this purpose, known as «Bubblots», and have equipped them with miniaturized voltammetric measuring stands from Metrohm.

«With a metal detector, all you get is «beep-beep-beep», which means there is metal around. However, in a bronze statue, there is copper, there is tin, and you have to detect the oxides of them, the exact kind of material you are facing. We have decided for Metrohm, because you are the most competent for the measuring technology we need in our drones.»

Mathias Buttet

R&D Director, Hublot

The Bubblots are utilized to perform real-time analyses of the seawater for unusual concentrations of dissolved metal salts typically associated with corroding bronze artefacts. Thus, the systematic and highly selective investigation of larger areas of seafloor for historical bronze artefacts becomes feasible.

Figure 3. Hublot’s underwater drones, known as «Bubblots», and the voltammetric measuring stand from Metrohm.

Voltammetry to the rescue

Due to its selectivity regarding different metals and their oxidation states, voltammetry is ideally suited for such investigations, as it is also very fast and robust technique. In the case of Hublot’s drones, results are obtained in a few seconds and this information can be immediately processed.

«We use this Metrohm instrument for voltammetric measurements. We take a water sample and do a live measurement of the aspirated water. The voltammetric measurement takes only a few seconds. This is enough to give us an idea of the different metals present in the solution. This allows us to do highly selective measurements very fast to cover different regions of the archaeological site.»

Sébastien Recalcati

Materials Engineer, Hublot

For a selection of free Metrohm Application Notes related to voltammetric measurements in seawater, visit our website!

Figure 4. The 910 PSTAT mini from Metrohm used in the study.
Figure 5. One of Metrohm’s disposable screen printed electrodes (SPEs) utilized in Hublot’s drone analysis of the seafloor.

Giving the Antikythera Mechanism a second life

The maker of this mechanism was far ahead of his time. He must have had skills and possessed scientific knowledge that are mind-boggling even today. The watchmakers from Hublot were inspired by this to a very special project: they rebuilt the Antikythera Mechanism in a wristwatch.

«The original Antikythera Mechanism has the size of a shoe box. Reducing the size of the mechanism and putting it into a wrist watch was not so easy. Because the Antikythera Mechanism was not a clock, it was a machine with a driving crank to show the position of the moon and the sun in relation to the stars at any given date. The absolute dream is to find the missing parts of the machine. But the debris is hidden below the seafloor, covered by sediments, one meter, sometimes two meters.»

Mathias Buttet

R&D Director, Hublot

Figure 6. The Antikythera Mechanism miniaturized and captured in a Hublot wristwatch.

We are glad to support Hublot’s archaeological mission with our analytical instruments and our expertise in chemical analysis. Metrohm wishes the Hublot team all the best.

Visit our website to learn more

about this fascinating project and to discover more related applications from Metrohm

Post written by Dr. Alyson Lanciki, Scientific Editor at Metrohm International Headquarters, Herisau, Switzerland.

History of Metrohm IC – Part 3

History of Metrohm IC – Part 3

Part 3 of this series on the history of ion chromatography development at Metrohm focuses on the near past, from the mid 2000s until a few years ago. Here, sequential suppression was introduced, making analysis even more sensitive with the removal of baseline disturbances from the chromatogram. In the rest of this blog post, I cover the 4th and 5th instrument generations, presenting professional, flexible, intelligent ion chromatography from Metrohm to the world.

Have you read the other parts in this series? If not, find them here to understand the history of IC development at Metrohm over the past few decades.

«An IC system so smart that it can make logical decisions on its own? For example, diluting samples automatically, if the concentration of your target analyte is too high and results would fall outside the calibrated range?»

Dr. Markus Läubli, R&D Ion Chromatography, Metrohm AG

«This is exactly what the 850 Professional IC and MagIC Net™ software can do. In fact, our Professional IC system takes care of the liquid handling & sample preparation with hardly any work required from the user!»

Dr. Andrea Wille, Manager Competence Center Ion Chromatography, Metrohm AG

2005: Sequential suppression is introduced

Sequential suppression was introduced in 2005 to overcome issues that arise from using chemical suppression alone.

In chemical suppression (using the packed bed Metrohm Suppressor Module, MSM), the dissociated carbonic acid from carbon dioxide attributes a background conductivity of approximately 15 µS/cm. This yields in relatively large water dips as well as system peaks (from carbonate). Depending on the carbonate concentration, the system peak may interefere with other peaks of interest in the chromatogram.

Furthermore, the pH in a peak changes due to the increasing concentration of H+, as e.g. chloride is eluted as HCl. This pH change induces a decreasing baseline as the hydrogen carbonate—carbonic acid equilibrium is pushed towards development of carbonic acid. The effect is schematically illustrated in Figure 1.

Here, the calculated baseline is marked with the straight red line, but the real baseline shows small negative deviations under the analyte peaks. This negative peak area is not taken into account for the quantification of the respective analyte. This and other effects result in a deviation from the linearity of the calibration curve. In most cases it is therefore recommended to apply a quadratic curve fit.

Figure 1. Chromatogram with chemical suppression. The blue area is not taken in to account in the quantification. Negative peaks: real baseline due to pH change.

Download our free poster: Sequential suppression for conductivity detection in ion chromatography. The poster describes how different suppressors (MSM and MCS) work and mentions possible applications. 

Sequential suppression for anions

The term «sequential suppression» represents the combination of chemical suppression and CO2 suppression. The Metrohm CO2 Suppressor (MCS) removes CO2 from the eluent (mobile phase) after chemical suppression, but before detection. This shifts the equilibrium from hydrogen carbonate towards dissolved CO2. Applying sequential suppression therefore reduces the background conductivity to < 1 µS/cm, corresponding to ultrapure water itself.

As an effect of sequential suppression, the water dip as well as the system peak (carbonate peak) is reduced dramatically. The former allows easier integration of the early eluting peaks (Fig. 2), e.g. fluoride. The latter reduces the interference and disturbance of peaks of interest. Using the MCS in combination with the MSM, there are no negative baseline peaks present in the chromatogram, and the linearity is improved. Nevertheless, it is still recommended to apply a quadratic curve fit when calibrating a concentration range of one or more orders of magnitude.

Figure 2. Overlay of a chromatogram of standard anions with chemical suppression (MSM alone, blue) and a chromatogram of the same standard, but while applying sequential suppression (MSM + MCS, red). The water dip (1, injection peak) and the system peak (2, carbonate peak) are no longer present with sequential suppression.

Here you can find a selection of free application notes for download using sequential suppression for both anions and cations.

4th generation: Intelligent ion chromatography – 2007

The fourth generation of Metrohm ion chromatography was introduced in 2007, bringing with it a higher level of detection data handling and finally adding intelligence to the IC instruments.

After the introduction of the 850 Professional IC series in 2007, the respective compact versions (881 Compact IC pro and 882 Compact IC plus) were launched in 2009 (Figure 3), offering IC systems for all kinds of laboratories and sample throughput needs. The 883 Basic IC plus followed shortly after this as well in 2009 (Fig. 3).

Figure 3. New additions to the Metrohm IC family (left to right): The 850 Professional IC, 881 Compact IC pro, 882 Compact IC plus, and 883 Basic IC plus.

Aside from general improvements on the hardware modules, the conductivity detector was switched from analog to digital. The previous iteration consisted of a stand-alone detector block and an electronic unit, which was able to cover the full signal range of conductivity for IC. However, it was required to select a dedicated measuring range and an optimal full-scale (e.g., 20 µS/V) for the best signal quality.

The new IC Conductivity Detector for 850 Professional IC instruments consisted of only the «detector block» itself. The complete electronics were now integrated within the thermostated detector block. Besides the digital data acquisition capability, this significantly improves the signal stability which yields in an extremely low noise level. The digital detector could now handle the full conductivity range without the need for any range or full-scale settings.

MagIC Net, the new fully in-house developed software for both hardware control and data handling, brought many enhanced features and capabilities to the world of Professional IC (Figure 4). Here, «Intelligent IC» was born. Intelligent IC stands for the automatic recognition of most of the hardware components, e.g., the high pressure pump, the separation column, etc. This information is stored in every determination, allowing users full system traceability for each analysis.

Figure 4. MagIC Net software for the full hardware control and data handling of Metrohm IC instruments.

MagIC Net also brought forth many special control functions enabling sophisticated Inline Sample Preparation and automatic calibration techniques. Logical decisions are available, allowing analysts to perform logical dilutions for example. Here, the logical decision-making software decides whether an analysis is a standard, a QC standard, or a sample. After the chromatographic run, the results can be tested for concentrations out of the calibration range. When such outliers are found, MagIC Net calculates new dilution factors and automatically re-runs the samples with the new values. At the end, perfect results are available for all analytes without manual redilution and re-injection.

5th generation: Modular flexibility arrives – 2013

The fifth generation of Metrohm ion chromatography arrived with an upgrade to the Professional IC system allowing even more application capabilities. The 940 Professional IC Vario and the 930 Compact IC Flex were introduced in 2013 (Figure 5).

Figure 5. The Metrohm 940 Professional IC Vario (left) and the 930 Compact IC Flex (right), developed with flexibility in mind.

These instruments were followed in quick succession by the 942 Extension Modules Vario as well as the stand-alone 945 Professional Detector with conductivity and/or amperometric detection options to further broaden application suitability.

The 941 Eluent Production Module, also introduced in 2013, enabled the continuous preparation of all types of eluents via dilution of concentrated mobile phase constituents. Commercial as well as homemade concentrates may be applied. Therefore, the eluent production is not reduced to standard or costly eluents.

Figure 6. Ultimate modularity for the laboratory – mix and match modules: the Metrohm 940 Professional IC Vario TWO/ChS set up for AnCat analysis, containing 2 IC Conductivity Detectors, sitting atop two 942 Extension Modules Vario LQH and a 941 Eluent Production Module.

Intelligent IC: Not only limited to the laboratory

After the introduction of the new MagIC Net software for IC analysis, an updated version of the Metrohm IC process analyzer from Metrohm Process Analytics was also developed and launched. In 2016, the Process IC ONE and Process IC TWO were introduced, only differing in the amount of measurement channels and detectors (Figure 7). These process analyzers were built using the 940 Professional IC Vario series with the same functionality for the laboratory, in a rugged housing suitable for harsh industrial conditions.

The use of various MISP techniques (Metrohm Inline Sample Preparation) such as Inline Ultrafiltration and Inline Dilution, along with nine configurable wet part modules for further sample conditioning, integrated eluent production, and the possibility to connect one system to up to 20 process points for time-saving sequential analysis at multiple areas inside of a plant further expanded the application capabilities beyond what any lab instrument could offer. The use of liquid level sensors and integrated alarms for leakages and out-of-specification data results in maximum analyzer uptime due to reduced maintenance intervals.

Figure 7. The Metrohm Process IC TWO configured for AnCat analysis, with optional PURELAB® flex 5/6 from ELGA®, a pressureless inline ultrapure water feed.

Are you interested in ion chromatography applications for industrial process analysis and optimization? Did you know that you can also monitor the air quality indoors as well as in the environment with these products? Check out our selection of FREE Process Application Notes (PANs) for IC:

What’s next?

After the mid 2010s, more focus was given to the development of hyphenated techniques to support IC as part of a comprehensive analytical solution for more difficult sample matrices and analytes. In the next installment, I will discuss TitrIC, VoltIC, Combustion IC (CIC), and more, as well as what is on the horizon for the process analysis world. Stay tuned, and don’t forget to subscribe to the blog!

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Post written by Dr. Markus Läubli, Manager Marketing Support IC at Metrohm International Headquarters, Herisau, Switzerland.