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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!

Discover even more

about combined analytical systems from Metrohm

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».

Curious to learn even more?

Check out our webinar:

«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.