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«Analyze This»: 2020 in review

«Analyze This»: 2020 in review

I wanted to end 2020 by thanking all of you for making «Analyze This» – the Metrohm blog for chemists such a success! For our 60th blog post, I’d like to look back and focus on the wealth of interesting topics we have published this year. There is truly something for everyone: it doesn’t matter whether your lab focuses on titration or spectroscopic techniques, or analyzes water samples or illicit substances – we’ve got you covered! If you’re looking to answer your most burning chemical analysis questions, we have FAQs and other series full of advice from the experts. Or if you’re just in the mood to learn something new in a few minutes, there are several posts about the chemical world to discover.

We love to hear back from you as well. Leaving comments on your favorite blog posts or contacting us through social media are great ways to voice your opinion—we at Metrohm are here for you!

Finally, I wish you and your families a safe, restful holiday season. «Analyze This» will return on January 11, 2021, so subscribe if you haven’t already done so, and bookmark this page for an overview of all of our articles grouped by topic!

Stay healthy, and stay curious.

Best wishes,

Dr. Alyson Lanciki, Scientific Editor, Metrohm AG

Quickly jump directly to any section by clicking a topic:

Customer Stories

We are curious by nature, and enjoy hearing about the variety of projects where our products are being used! For some examples of interesting situations where Metrohm analytical equipment is utilized, read on.

From underwater archaeological research to orbiting Earth on the International Space Station, Metrohm is there! We assist on all types of projects, like brewing top quality beers and even growing antibiotic-free shrimp – right here in Switzerland.

Interested in being featured? Contact your local Metrohm dealer for details!

Titration

Metrohm is the global market leader in analytical instruments for titration. Who else is better then to advise you in this area? Our experts are eager to share their knowledge with you, and show this with the abundance of topics they have contributed this year to our blog.

For more in-depth information about obtaining the most accurate pH measurements, take a look at our FAQ about pH calibration or read about avoiding the most common mistakes in pH measurement. You may pick up a few tips!

Choose the best electrode for your needs and keep it in top condition with our best practices, and then learn how to standardize titrant properly. Better understand what to consider during back-titration, check out thermometric titration and its advantages and applications, or read about the most common challenges and how to overcome them when carrying out complexometric titrations

If you are interested in improving your conductivity measurements, measuring dissolved oxygen, or the determination of oxidation in edible fats and oils, check out these blog posts and download our free Application Notes and White Papers!

Finally, this article about comprehensive water analysis with a combination of titration and ion chromatography explains the many benefits for laboratories with large sample loads. The history behind the TitrIC analysis system used for these studies can be found in a separate blog post.

Karl Fischer Titration

Metrohm and Karl Fischer titration: a long history of success. Looking back on more than half a century of experience in KFT, Metrohm has shaped what coulometric and volumetric water analysis are today.

Aside from the other titration blog posts, our experts have also written a 2-part series including 20 of the most frequently asked questions for KFT arranged into three categories: instrument preparation and handling, titration troubleshooting, and the oven technique. Our article about how to properly standardize Karl Fischer titrant will take you step by step through the process to obtain correct results.

For more specific questions, read about the oven method for sample preparation, or which is the best technique to choose when measuring moisture in certain situations: Karl Fischer titration, near-infrared spectroscopy, or both?

Ion Chromatography (IC)

Ion chromatography has been a part of the Metrohm portfolio since the late 1980s. From routine IC analysis to research and development, and from stand-alone analyzers to fully automated systems, Metrohm has provided IC solutions for all situations. If you’re curious about the backstory of R&D, check out the ongoing series about the history of IC at Metrohm.

Metrohm IC user sitting at a laboratory bench.

Common questions for users are answered in blog posts about IC column tips and tricks and Metrohm inline ultrafiltration. Clear calculations showing how to increase productivity and profitability in environmental analysis with IC perfectly complement our article about comprehensive water analysis using IC and titration together for faster sample throughput.

On the topic of foods and beverages, you can find out how to determine total sulfite faster and easier than ever, measure herbicides in drinking water, or even learn how Metrohm IC is used in Switzerland to grow shrimp!

Near-Infrared Spectroscopy (NIRS)

Metrohm NIRS analyzers for the lab and for process analysis enable you to perform routine analysis quickly and with confidence – without requiring sample preparation or additional reagents and yielding results in less than a minute. Combining visible (Vis) and near-infrared (NIR) spectroscopy, these analyzers are capable of performing qualitative analysis of various materials and quantitative analysis of a number of physical and chemical parameters in one run.

Our experts have written all about the benefits of NIR spectroscopy in a 4-part series, which includes an explanation of the advantages of NIRS over conventional wet chemical analysis methods, differences between NIR and IR spectroscopy, how to implement NIRS in your laboratory workflow, and examples of how pre-calibrations make implementation even quicker.

A comparison between NIRS and the Karl Fischer titration method for moisture analysis is made in a dedicated article.

A 2-part FAQ about NIRS has also been written in a collaboration between our laboratory and process analysis colleagues, covering all kinds of questions related to both worlds.

Raman Spectroscopy

This latest addition to the Metrohm family expands the Metrohm portfolio to include novel, portable instruments for materials identification and verification. We offer both Metrohm Raman as well as B&W Tek products to cover a variety of needs and requirements.

Here you can find out some of the history of Raman spectroscopy including the origin story behind Mira, the handheld Raman instrument from Metrohm Raman. For a real-world situation involving methamphetamine identification by law enforcement and first responders, read about Mira DS in action – detecting drugs safely in the field.

Mira - handheld Raman keeping you safe in hazardous situations.

Are you looking for an easier way to detect food fraud? Our article about Misa describes its detection capabilities and provides several free Application Notes for download.

Process Analytics

We cater to both: the laboratory and the production floor. The techniques and methods for laboratory analysis are also available for automated in-process analysis with the Metrohm Process Analytics brand of industrial process analyzers.

Learn about how Metrohm became pioneers in the process world—developing the world’s first online wet chemistry process analyzer, and find out how Metrohm’s modular IC expertise has been used to push the limits in the industrial process optimization.

Additionally, a 2-part FAQ has been written about near-infrared spectroscopy by both laboratory and process analysis experts, which is helpful when starting out or even if you’re an advanced user.

Finally, we offer a 3-part series about the advantages of process analytical technology (PAT) covering the topics of process automation advantages, digital networking of production plants, and error and risk minimization in process analysis.

Voltammetry (VA)

Voltammetry is an electrochemical method for the determination of trace and ultratrace concentrations of heavy metals and other electrochemically active substances. Both benchtop and portable options are available with a variety of electrodes to choose from, allowing analysis in any situation.

A 5-part series about solid-state electrodes covers a range of new sensors suitable for the determination of «heavy metals» using voltammetric methods. This series offers information and example applications for the Bi drop electrode, scTrace Gold electrode (as well as a modified version), screen-printed electrodes, and the glassy carbon rotating disc electrode.

Come underwater with Metrohm and Hublot in our blog post as they try to find the missing pieces of the ancient Antikythera Mechanism in Greece with voltammetry.

If you’d like to learn about the combination of voltammetry with ion chromatography and the expanded application capabilities, take a look at our article about combined analysis techniques.

Electrochemistry (EC)

Electrochemistry plays an important role in groundbreaking technologies such as battery research, fuel cells, and photovoltaics. Metrohm’s electrochemistry portfolio covers everything from potentiostats/galvanostats to accessories and software.

Our two subsidiaries specializing in electrochemistry, Metrohm Autolab (Utrecht, Netherlands) and Metrohm DropSens (Asturias, Spain) develop and produce a comprehensive portfolio of electrochemistry equipment.

This year, the COVID-19 pandemic has been at the top of the news, and with it came the discussion of testing – how reliable or accurate was the data? In our blog post about virus detection with screen-printed electrodes, we explain the differences between different testing methods and their drawbacks, the many benefits of electrochemical testing methods, and provide a free informative White Paper for interested laboratories involved in this research.

Our electrochemistry instruments have also gone to the International Space Station as part of a research project to more efficiently recycle water on board spacecraft for long-term missions.

The History of…

Stories inspire people, illuminating the origins of theories, concepts, and technologies that we may have become to take for granted. Metrohm aims to inspire chemists—young and old—to be the best and never stop learning. Here, you can find our blog posts that tell the stories behind the scenes, including the Metrohm founder Bertold Suhner.

Bertold Suhner, founder of Metrohm.

For more history behind the research and development behind Metrohm products, take a look at our series about the history of IC at Metrohm, or read about how Mira became mobile. If you are more interested in process analysis, then check out the story about the world’s first process analyzer, built by Metrohm Process Analytics.

Need something lighter? Then the 4-part history of chemistry series may be just what you’re looking for.

Specialty Topics

Some articles do not fit neatly into the same groups as the rest, but are nonetheless filled with informative content! Here you can find an overview of Metrohm’s free webinars, grouped by measurement technique.

If you work in a regulated industry such as pharmaceutical manufacturing or food and beverage production, don’t miss our introduction to Analytical Instrument Qualification and what it can mean for consumer safety!

Industry-focused

Finally, if you are more interested in reading articles related to the industry you work in, here are some compilations of our blog posts in various areas including pharmaceutical, illicit substances, food and beverages, and of course water analysis. More applications and information can be found on our website.

Food and beverages
All of these products can be measured for total sulfite content.

Oxidation stability is an estimate of how quickly a fat or oil will become rancid. It is a standard parameter of quality control in the production of oils and fats in the food industry or for the incoming goods inspection in processing facilities. To learn more about how to determine if your edible oils are rancid, read our blog post.

Determining total sulfite in foods and beverages has never been faster or easier than with our IC method. Read on about how to perform this notoriously frustrating analysis and get more details in our free LC/GC The Column article available for download within.

Measuring the true sodium content in foodstuff directly and inexpensively is possible using thermometric titration, which is discussed in more detail here. To find out the best way to determine moisture content in foods, our experts have written a blog post about the differences between Karl Fischer titration and near-infrared spectroscopy methods.

To determine if foods, beverages, spices, and more are adulterated, you no longer have to wait for the lab. With Misa, it is possible to measure a variety of illicit substances in complex matrices within minutes, even on the go.

All of these products can be measured for total sulfite content.

Making high quality products is a subject we are passionate about. This article discusses improving beer brewing practices and focuses on the tailor-made system built for Feldschlösschen, Switzerland’s largest brewer.

Pharmaceutical / healthcare

Like the food sector, pharmaceutical manufacturing is a very tightly regulated industry. Consumer health is on the line if quality drops.

Ensuring that the analytical instruments used in the production processes are professionally qualified is a must, especially when auditors come knocking. Find out more about this step in our blog post about Analytical Instrument Qualification (AIQ).

Moisture content in the excipients, active ingredients, and in the final product is imperative to measure. This can be accomplished with different analytical methods, which we compare and contrast for you here.

The topic of virus detection has been on the minds of everyone this year. In this blog post, we discuss virus detection based on screen-printed electrodes, which are a more cost-effective and customizable option compared to other conventional techniques.

Water analysis

Water is our business. From trace analysis up to high concentration determinations, Metrohm has you covered with a variety of analytical measurement techniques and methods developed by the experts.

Learn how to increase productivity and profitability in environmental analysis laboratories with IC with a real life example and cost calculations, or read about how one of our customers in Switzerland uses automated Metrohm IC to monitor the water quality in shrimp breeding pools.

If heavy metal analysis is what you are interested in, then you may find our 5-part series about trace analysis with solid-state electrodes very handy.

Unwanted substances may find their way into our water supply through agricultural practices. Find out an easier way to determine herbicides in drinking water here!

Water is arguably one of the most important ingredients in the brewing process. Determination of major anions and cations along with other parameters such as alkalinity are described in our blog post celebrating International Beer Day.

All of these products can be measured for total sulfite content.
Illicit / harmful substances

When you are unsure if your expensive spices are real or just a colored powder, if your dairy products have been adulterated with melamine, or fruits and vegetables were sprayed with illegal pesticides, it’s time to test for food fraud. Read our blog post about simple, fast determination of illicit substances in foods and beverages for more information.

Detection of drugs, explosives, and other illegal substances can be performed safely by law enforcement officers and first responders without the need for a lab or chemicals with Mira DS. Here you can read about a real life training to identify a methamphetamine laboratory.

Drinking water regulations are put in place by authorities out of concern for our health. Herbicides are important to measure in our drinking water as they have been found to be carcinogenic in many instances.

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

Trace metal analysis with solid-state electrodes – Part 5

Trace metal analysis with solid-state electrodes – Part 5

In the last part of our series of articles about trace metal analysis using solid-state electrodes, we will have a look at the glassy carbon rotating disc electrode (GC RDE) and its application possibilities.

Did you read the other parts in this series? Find them here!

The Glassy Carbon Rotating Disc Electrode

A rotating disc electrode (RDE) consists of two parts: the electrode tip which is made available in different materials, and a driving axle. The electrode tip is simply screwed onto the axle (Figure 1) to assemble the complete working electrode.

Figure 1. The two parts which make up the RDE. Left: driving axle for RDE. Right: glassy carbon electrode tip, with shaft made of glass.

Glassy carbon (GC) has a long history as solid electrode material for trace metal analysis. In general, GC is carbon with an amorphous structure which is similar to glass or ceramics, but different from graphite or diamond which both have a crystalline structure.

Aside from properties including a high temperature stability and a hardness similar to quartz, glassy carbon is very chemically inert and has a low electrical resistance, making it a versatile electrode material.

In the Metrohm GC electrode tip (Figure 1), the glassy carbon rod is fused within a glass shaft—another inert material. This design creates an electrode tip that is inert against most chemicals and solvents and guarantees measurements with excellent reproducibility due to the seamless intersection between the electrode material and glass shaft.

Modification with a metal film

For trace metal applications, the GC electrode is modified with a metal film, usually mercury or bismuth. The film is plated ex-situ from an acid plating solution which contains about 20 mg/L Hg2+ or Bi3+. Such a solution can easily be prepared from commercially available metal standard solutions and can be used for the plating of several films.

Once the film is deposited on the glassy carbon electrode, multiple determinations can be carried out with the same film. When the performance deteriorates, the exhausted film is simply wiped off and a fresh film is plated. Since only the renewable film is affected by aging processes, the GC electrode itself can be used for a very long time.

Applications using glassy carbon electrodes exhibit excellent reproducibility and stability in combination with very low detection limits.

Figure 2. Glassy carbon rotating disc electrode in a 884 Professional VA instrument from Metrohm.

Applications

Cadmium and lead determinations

The risk of cadmium and lead poisoning from drinking water and the significance of the determination of these two elements has already been discussed in previous posts in this series. To monitor the guideline values of 3 µg/L for cadmium and 10 µg/L for lead, recommended by the WHO (World Health Organization), a detection limit of β(Cd) = 0.3 µg/L and β(Pb) = 1 µg/L would be sufficient.

With the glassy carbon electrode the determination is far more sensitive, featuring a ten-fold improvement on the limit of detection of β(Cd) = 0.02 µg/L and β(Pb) = 0.05 µg/L with a deposition time of 30 s. This limit can be lowered even more with an increased deposition time.

For this extremely sensitive determination, a mercury film is plated on the glassy carbon electrode. The determination of cadmium and lead is carried out by anodic stripping voltammetry (ASV).

To learn more about this application, please check our website.

Free Application Note download: AN-V-225 Cadmium and lead in drinking water – Simultaneous determination on a mercury film modified glassy carbon electrode.

The very low detection limit makes this application especially interesting when it is not only required to monitor limit values but to actually detect concentrations in the ppt (parts per trillion, ng/L) range, e.g. in environmental analysis such as for seawater research.

Nickel and cobalt measurements

Another application with very low detection limits using the GC electrode is the determination of nickel and cobalt. This electrode allows the detection of concentrations down to β(Ni) = 0.05 µg/L and β(Co) = 0.03 µg/L. For this application, the electrode is modified with a bismuth film. The determination of nickel and cobalt is carried out by adsorptive stripping voltammetry (AdSV) using the complexing agent DMG (dimethylglyoxime).

Figure 3. Determination of β(Ni) = 0.34 µg/L and β(Co) < LOD in tap water (30 s deposition time) using the GC RDE.

For decades, this method was successfully executed with the mercury drop electrode. The use of a bismuth film on a glassy carbon electrode offers a non-toxic alternative with a similar sensitivity as the established method. Besides the high sensitivity, this application also shows excellent repeatability.

20 consecutive determinations of β(Ni) = 0.5 µg/L and β(Co) = 0.5 µg/L, carried out on the same bismuth film, showed an average recovery of 105% for nickel, with a relative standard deviation (RSD) of 2.0%. The recovery for cobalt was 112% with a RSD of 3.3%. This makes this method a viable tool in environmental analysis when natural background concentrations, which are often in the ppt (ng/L) range, should be investigated.

For further details about this application, please refer to Application Note AN-V-224: Nickel and cobalt in drinking water – Simultaneous determination in low ng/L range on the GC RDE modified with a bismuth film.

Chromium(VI) monitoring

Legal limits for chromium are relatively high. For example, the guideline value of the World Health Organization (WHO) is 50 µg/L for drinking water. These values usually refer to the total chromium concentration, but there are significant differences in toxicity between Cr(III) and Cr(VI). Even miniscule doses of Cr(VI) are toxic as well as carcinogenic.

Since the beginning of this century, there have been ongoing discussions in the scientific community about whether an additional limit value only for Cr(VI) is required, and what this value should be.

Measuring techniques are needed which allow the determination of Cr(VI) in the ng/L range. Using the glassy carbon electrode modified with a mercury film it is possible to detect Cr(VI) concentrations down to 0.05 µg/L. Cr(VI) is determined by adsorptive stripping voltammetry (AdSV) with DTPA (diethylenetriaminepentaacetic acid) as complexing agent. The recovery of a concentration of β(Cr(VI)) = 0.1 µg/L is 111% with a relative standard deviation of 4.4% (triplicate determination).

If you are interested to learn more, download our free Application Note V-277: Chromium(VI) in drinking water – Ultra-sensitive determination on the mercury film modified glassy carbon electrode (DTPA method).

All the above-mentioned applications can be carried out manually with a 884 Professional VA system (Figure 4), but it is also possible to run small sample series with an automated setup.

Figure 4. 884 Professional VA with two 800 Dosinos for automatic addition of electrolyte and standard solution.

Summary

This was the last post in our five-part series on heavy metal analysis with solid state electrodes. If this or one of the previous posts sparked your interest in one of the applications, do not hesitate to contact your local Metrohm representative.

For a complete overview of the different applications that can be performed with the SSEs exhibited in this series, check out the table below. Click on each application note or bulletin for a free download! 

Overview: Applications with Metrohm SSEs
Element Electrode Application Document Lab Portable
Ag GC RDE Application Bulletin 207

As scTRACE Gold Application Note V-210
Application Note V-211

Bi scTRACE Gold Application Note V-218

Cd, Pb GC RDE (Hg film) Application Note V-225

Cd, Pb SPE (Hg film) Application Note V-231

Cd, Pb Bi drop Application Note V-221

Cr(VI) GC RDE (Hg film) Application Note V-227

Cr(VI) scTRACE Gold (Hg film) Application Note V-230

Cu scTRACE Gold Application Note V-213

Fe scTRACE Gold Application Note V-216

Fe Bi drop Application Note V-222

Hg scTRACE Gold Application Note V-212

Ni, Co scTRACE Gold (Bi film) Application Note V-217

Ni, Co GC RDE (Bi film) Application Note V-224

Ni, Co SPE (Bi film) Application Note V-232

Ni, Co Bi drop Application Note V-223

Pb scTRACE Gold (Ag film) Application Note V-214

Sb(III) scTRACE Gold Application Note V-229

Se(IV) scTRACE Gold Application Note V-233

Te(IV) scTRACE Gold Application Note V-234

Tl scTRACE Gold (Ag film) Application Note V-228

Zn scTRACE Gold Application Note V-215

Post written by Barbara ZumbrägelProduct Manager VA/CVS at Metrohm International Headquarters, Herisau, Switzerland.

Comprehensive water analysis: combining titration, IC, and direct measurement in one setup

Comprehensive water analysis: combining titration, IC, and direct measurement in one setup

If you perform water analyses on a regular basis, then you know that analyzing different parameters for drinking water can be quite time-consuming, expensive, and it requires significant manual labor. In this article, I’d like to show you an example of wider possibilities in automated sample analysis when it comes to combining different analytical techniques, especially for our drinking water.

Water is the source and basis of all life. It is essential for metabolism and is our most important foodstuff.

As a solvent and transporting agent it carries not only the vital minerals and nutrients, but also, increasingly, harmful pollutants, which accumulate in aquatic or terrestrial organisms.

Within the context of quality control and risk assessment, there is a need in the water laboratory for cost-effective and fast instruments and methods that can deal with the ever more complex spectrum of harmful substances, the increasing throughput of samples, and the decreasing detection limits.

Comprehensive analysis of ionic components in liquid samples such as water involves four analytical techniques:

  • Direct measurement
  • Titration
  • Ion chromatography
  • Voltammetry

Each of these techniques has its own particular strengths. However, applying them one after the other on discrete systems in the laboratory is a rather complex task that takes up significant time.

Back in 1998, Metrohm accepted the challenge of combining different analytical techniques in a single fully automated system, and the first TitrIC system was introduced.

What is TitrIC?

The TitrIC system from Metrohm combines direct measurement, titration, and ion chromatography in a fully automated system.

Direct measurements include temperature, conductivity, and pH. The acid capacity (m and p values) is determined titrimetrically. Major anions and cations are quantified by ion chromatography. Calcium and magnesium, which are used to calculate total hardness, can be determined by titration or ion chromatography.

The results are displayed in a common table, and a shared report is given out at the end of the analysis. All methods in TitrIC utilize the same liquid handling units and a common sample changer.

For more detailed information about the newest TitrIC system, which is available in two predefined packages (TitrIC flex I and TitrIC flex II), take a look at our informative brochure:

Efficient: Titrations and ion chromatography are performed simultaneously with the TitrIC flex system.

Figure 1. Flowchart of TitrIC flex II automated analysis and data acquisition.

How does TitrIC work?

Each water sample analysis is performed fully automated at the push of a button—fill up a sample beaker with the sample, place it on the sample rack, and start the measurement. The liquid handling units transfer the required sample volume (per measurement technique) for reproducible results. TitrIC carries out all the work, and analyzes up to 175 samples in a row without any manual intervention required, no matter what time the measurement series has begun. The high degree of automation reduces costs and increases both productivity and the precision of the analysis.

Figure 2. The Metrohm TitrIC flex II system with OMNIS Sample Robot S and Dis-Cover functionality.

To learn more about how to perform comprehensive water analysis with TitrIC flex II, download our free application note AN-S-387:

Would you like to know more about why automation should be preferred over manual titration? Check out our previous blog post on this topic:

Calculations with TitrIC

With the TitrIC system, not only are sample analyses simplified, but the result calculations are performed automatically. This saves time and most importantly, avoids sources of human error due to erroneously noting the measurement data or performing incorrect calculations.

Selection of calculations which can be automatically performed with TitrIC: 

  • Molar concentrations of all cations
  • Molar concentrations of all anions
  • Ionic balance
  • Total water hardness (Ca & Mg)
  • … and more

Ionic balances provide clarity

The calculation of the ion balance helps to determine the accuracy of your water analysis. The calculations are based on the principle of electro-neutrality, which requires that the sum in eq/L or meq/L of the positive ions (cations) must equal the sum of negative ions (anions) in solution.

TitrIC can deliver all necessary data required to calculate the ion balance out of one sample. Both anions and cations are analyzed by IC, and the carbonate concentration (indicative of the acid capacity of water) is determined by titration.

If the value for the difference in the above equation is almost zero, then this indicates that you have accurately determined the major anions and cations in your sample.

Advantages of a combined system like TitrIC

  • Utmost accuracy: all results come from the same sample beaker

  • Completely automated, leaving analysts more time for other tasks

  • One shared sample changer saves benchtop space and costs

  • Save time with parallel titration and IC analysis

  • Flexibility: use titration, direct measurement, or IC either alone or combined with the other techniques

  • Single database for all results and calculation of the ionic balance, which is only possible with such a combined system, and gives further credibility to the sample results

Even more possibility in sample analysis

TitrIC has been developed especially for automated drinking water analysis but can be adapted to suit any number of analytical requirements in food, electroplating, or pharmaceutical industries. Your application determines the parameters that are of interest.

If the combination of direct measurement, titration, and IC does not suit your needs, perhaps a combination of voltammetry and ion chromatography in a single, fully automatic system might be more fitting. Luckily, there is the VoltIC Professional from Metrohm which fulfills these requirements.

Check out our website to learn more about this system:

As you see, the possibility of combining different analysis techniques is almost endless. Metrohm, as a leading manufacturer of instruments for chemical analysis, is aware of your analytical challenges. For this reason, we offer not only the most advanced instruments, but complete solutions for very specific analytical issues. Get the best out of your daily work in the laboratory!

Read our article

in LC/GC’s The Column November 2020 edition:

Environmental Analysis with Integrated Ion Chromatography, Titration, and Direct Measurement

Post written by Jennifer Lüber, Jr. Product Specialist Titration/TitrIC at Metrohm International Headquarters, Herisau, Switzerland.

Measuring herbicides in drinking water

Measuring herbicides in drinking water

It’s springtime in the northern hemisphere, and with rising temperatures comes increased use of herbicides on agricultural crops and in public spaces. In March 2015, the International Agency for Research on Cancer (IARC) published a report which stated that one such herbicide, glyphosate, was «probably carcinogenic to humans». Ever since, the use of this chemical has been highly controversial. In some countries, including the USA, there are already limit values in effect for the weed killer.

Carcinogenic or not?

Glyphosate is a broad-spectrum herbicide used globally in agriculture. Alongside farming, the chemical is also used to kill weeds in domestic gardens and in public and private spaces kept free from «vegetal invasion», such as railway tracks.

Glyphosate has been used since the 1970s in pesticides and was previously thought to be harmless at typical levels of exposure. However, since the International Agency for Research on Cancer (IARC) – the specialized cancer-research agency of the WHO – found that glyphosate was «probably carcinogenic to humans» (Group 2A) in a report published in March 2015, the chemical repeatedly made headlines [1].

Experts were then divided over whether glyphosate should be reapproved after the expiry of its EU market approval on June 30, 2016. This is because the European Food Safety Authority (EFSA) only recently arrived at the opposed conclusion that it is unlikely that glyphosate is genotoxic or poses a carcinogenic threat [2]. The approval of glyphosate was initially extended by 18 months, but is now allowed to remain in use in the EU until at least the end of 2022 [3].

Determination of glyphosate in drinking water

Because chemicals used in farming can seep through the ground and enter the ground water, limit values are in effect in some countries concerning the concentration of glyphosate in drinking water.

Glyphosate and its metabolite AMPA (aminomethylphosphonic acid) are usually determined by HPLC with post-column derivatization and subsequent fluorescence detection (EPA Method 547), or alternatively by ion chromatography coupled with a mass-selective detector.

Methodology using IC

The following segments explain the initial results of the determination of glyphosate and AMPA in drinking water in the low µg/L range using ion chromatography (IC) with pulsed amperometric detection. The detection limits for glyphosate and AMPA previously attained with pulsed amperometric detection were around ≥ 50 µg/L [4].

Given this improvement in terms of sensitivity, the method outlined here represents a promising approach to the screening of water and food samples for glyphosate and AMPA.

Instrumentation

All determinations were performed with an IC system consisting of a 940 Professional IC Vario ONE with an IC Amperometric Detector and an 858 Professional Sample Processor for automatic sample injection (Figure 1).

Figure 1. Glyphosate and AMPA were determined with the ProfIC IC Vario 1 Amperometry system.

Glyphosate and AMPA were separated on the high-capacity anion separation column Metrosep Carb 2 – 150/4.0, and subsequently detected via flexIPAD (FLEXible Integrated Pulsed Amperometric Detection) using a gold working electrode as a measuring mode in the amperometric detector. The profile of the potential curve produced in one measuring cycle in flexIPAD mode is presented in Figure 2.

Figure 2. Pulse profile of the flexIPAD method: A measuring cycle lasts 0.9 s; measurement of the current is performed during the phase shown in red.

Experiment

The Metrosep Carb 2 column is used mainly for separating and determining carbohydrates, sugar alcohols, alcohols, etc. Its high column capacity, combined with the high pH value of the eluent (approximately pH 10), results in a large difference in retention time for AMPA and glyphosate. This is because, with a pH value of 10, all three acid groups are deprotonated in part of the glyphosate, meaning that it is partially present as a trivalent anion while the metabolite AMPA, which is missing the carboxyl group, is present as a divalent anion.

Results

Figure 3 shows the chromatogram of the determination of AMPA and glyphosate under the conditions used in this application. An aqueous standard solution was injected containing 10 µg/L each of both components.

Figure 3. Separation of AMPA and glyphosate: a standard solution containing 10 µg/L of each component in ultrapure water was analyzed.

The detection limits for both components were determined using the signal/noise (S/N) ratio, i.e., the ratio of the peak height to the baseline noise. At the detection limit, the S/N ratio is 3; with smaller values, secured detection is not possible. The detection limit found for AMPA was considerably lower than 1 µg/L, while the limit for glyphosate was approximately 1 µg/L.

Figure 4 shows a chromatogram of a drinking water sample mixed with 2 µg/L glyphosate and AMPA.

Figure 4. Determination of AMPA and glyphosate in drinking water which was mixed with 2 µg/L of each component.

Summary

For the first time, glyphosate and its primary metabolite AMPA were determined in drinking water in the low µg/L range using ion chromatography with pulsed amperometric detection (flexIPAD). This puts at our disposal a reliable and – compared with HPLC with a mass-selective detector – very inexpensive method for determining the glyphosate and AMPA content in water and foodstuffs. With a detection limit of approximately 1 µg/L, the adherence to limit values for glyphosate can be verified in the USA, Canada, and Australia, among others.

If you want to learn even more about how to measure glyphosate and AMPA via ion chromatography and amperometric detection, download our free white paper «Glyphosate and AMPA in drinking water».

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«Glyphosate and AMPA analysis»

References

[1] IARC Monographs Volume 112 (2015). Retrieved from http://monographs.iarc.fr/ENG/Monographs/vol112/mono112-09.pdf on June 27, 2016.

[2] EFSA press news, 151112 (2015). Retrieved from http://www.efsa.europa.eu/en/topics/factsheets/glyphosate151112 on June 27, 2016.

[3] European Commission: Status of glyphosate in the EU. Retrieved from https://ec.europa.eu/food/plant/pesticides/glyphosate_en on May 25, 2020.

[4] F. Sanchez-Bayo, R. V. Hyne, and K. L. Desseille (2010) Anal. Chim. Acta, 675 125–131.

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