The chemical transition of the laboratory to accelerate ecological, industrial and technological transformation

Ismahane REMONNAY (Département des Expertises Scientifiques
et Techniques - Veolia, France).

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In September 2023, the 5th International Conference on Chemicals Management (ICCM5), held in Bonn under the aegis of SAICM and UNEP, and bringing together researchers, NGOs, representatives of the private sector and governments, established a historic agreement defining a new global framework for improving chemicals management: the Bonn Agreement "Global Framework on Chemicals GFC" which should, like the Paris Agreement, initiate changes in regulations, standards and stakeholder expectations. Based on 28 objectives and setting out a roadmap for each country, these agreement aim for a transition to a sustainable and safer chemical alternative, by tackling the life cycle of chemical products in a collaborative manner, from production to waste. Why initiate a chemical transition within laboratories?

Exemplarity, transparency, credibility, regulatory acceleration, mistrust of science and understanding what is meant by "chemical transition" ... Approaches, standards and frameworks for ecological transition, sustainability, green/sustainable/safe chemistry... are multiplying to accompany an often marketing approach based on the terminology "Green Laboratory, Laboratory of the Future, Sustainable Laboratory...". To avoid greenwashing and the questioning of measurement reliability, the output of laboratories, it is therefore essential to initiate a clear and transparent chemical transition in laboratories, based on various actions: from training to the design and choice of materials/equipment, analytical protocols and measurement.

The chemical transition, a "construction approach", aims to facilitate discussions and collaboration in the construction of the approach so that a global vision of the chemical cycle is taken into account, leaving no blind spots.

Green Sample Preparation Solutions based on
Miniaturization and Automation

Frank DAVID (RIC technologies, Belgium).

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Sample preparation is often considered as the step with the highest impact on the greenness of a complete analytical procedure. During the past years, numerous scientific papers have been published describing sample preparation techniques that reduce or even eliminate the use of solvents and toxic chemicals, that reduce the required sample size, and that are consuming less energy due to miniaturization. However, these new sample preparation methods do not always find their way to routine laboratories. Reasons for this can be based on the fact that no evidence is given that the new method delivers equivalent results (method not fully validated), but in a lot of cases the low implementation rate is also due to combinations of resistance to change, perceptions, and even biased assumptions. A traditional example of this is the assumption that stir bar sorptive extraction (SBSE) cannot be used on water samples containing some suspended organic material.

In this presentation, examples will be given how classical methods can be replaced by miniaturized and automated methods while analytical criteria such as limits of quantification, linearity and repeatability are maintained. Important bottlenecks will be discussed, and possible solutions presented. Applications include the analysis of priority pollutants in water samples, mineral oil analysis, profiling of aroma compounds and fatty acid methyl ester analysis in foods.

Automated extraction and analysis of drugs from biological fluids by Coated Blade Spray - Mass Spectrometry (CBS - MS)

Shane STEVENS (Restek Corporation, USA).

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Many methods of ambient ionization mass spectrometry have been proposed as alternatives to LC-MS/MS offering advantages in analysis speed/turnaround time, minimal sample preparation and simplicity in workflow. Most; however, are very susceptible to matrix effects resulting in reduced sensitivity, reproducibility, and instrument contamination.

Coated blade spray (CBS) is an easy-to-use solid phase microextraction (SPME)-based technology which combines sample extraction with direct ionization to a mass spectrometer. One coated blade is used to collect analytes of interest with subsequent introduction to MS by generating a Taylor cone.

The device comprises a small, thin, conductive substrate having a blade-shape with a flat surface terminating at a point. As a SPME device, the blade is coated at the terminal end with an extraction sorbent bed.

The CBS workflow reduces complexity, cost, and waste associated with other SPE methods. The SPME-based nature of CBS performs a selective extraction of desired analytes from the bulk sample matrix, resulting in very clean samples and improved instrument uptime. The Taylor cone is generated by applying a DC potential and adding a microliter-scale volume of solvent. CBS-MS eliminates the need for chromatographic separation, resulting in significant reductions in solvent consumption and analysis time.

In this work we demonstrate CBS-MS assays of drugs in biological fluids utilizing a modified laboratory pipetting robot to automate all functions associated with analyte collection as well as serving as the interface to a MS for analysis. We also present a modified pipettor capable of reorienting a blade from a vertical position required for extraction to a horizontal position required for MS analysis.

Optimization of the extraction of the walnut oil volatiles using dynamic
headspace hyphenated to GC-MS: Adsorbent comparison.

Agnès CHARTIER (Institute of Organic and Analytical Chemistry
- University of Orleans, France).

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Walnut oil is a highly valued vegetable oil due to its nutritional and medicinal properties. These properties are mainly attributed to the mono and polyunsaturated fatty acids, and to the presence of minor compounds such as antioxidants, amino acids and volatile compounds that are responsible for its organoleptic properties.

Unfortunately, this oil is not very stable and has a limited shelf life. Aging markers are correlated to the oxidation of the unsaturated fatty acids, which lead to the formation of various volatile compounds. These volatiles encompass five major chemical family such as acids, alcohols, aldehydes, ketones and furans.

The evolution over time of these different constituents induces a modification of the organoleptic properties of the walnut oil. Some of these compounds are difficult to trap before analysis. The use of experimental design made it possible to carry out the optimization parameters involved in a DHS-TDU-GC-MS method.

Different adsorbents such as Tenax, Carbopack, and mixed beds were tested and compared. This study has highlighted selective adsorbents with the aim of obtaining the profile of volatiles emanating from different nut oils from varied terroirs, and for some of them having an “organic” designation. From this study, markers of the aging walnut oil have been identified.

Hydrogen as a carrier gas in GCMS, an upcoming
inevitability or an opportunity

David BENANOU (Scientific and Technical Expertise Department
- Veolia, France).

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Helium is the second lightest and second most abundant element in the observable universe and is also the most widely used carrier gas for conventional gas chromatography and especially for gas chromatography-mass spectrometry. In recent years, the availability of helium has decreased and its cost has increased significantly. In 2021, the U.S. domestic helium reserve accounted for 30% of the world's helium and this reserve is expected to run out of helium by 2030.

This context of potential shortage and load increase, which until now seemed negligible, is prompting many chromatographers around the world to consider switching to the use of hydrogen.

We will present the chromatographic advantages inherent to the use of hydrogen in gas chromatography-mass spectrometry, its possible critical points and limitations and its "urban legends". An exhaustive economic assessment of the use of helium and hydrogen in different laboratories will be presented.

Blood Lipidomics and Metabolomics of Colorectal Cancer
by GC×GC–LR/HR-TOFMS

Jeff FOCANT (ULiège University, Belgium).

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Colorectal cancer (CRC) ranks as the third most frequently diagnosed cancer and the second leading cause of cancer-related deaths. The current endoscopic-based or stool-based diagnos-tic techniques are either highly invasive or lack sufficient sensitivity.

Thus, there is a need for less invasive and more sensitive screening approaches. We, therefore, conducted a study on 64 human serum samples representing three different groups (adenocarcinoma, adenoma, and control) using cutting-edge GC×GC–LR/HR-TOFMS techniques.

We analyzed samples with two different specifically tailored sample preparation approaches for lipidomics (fatty acids) (25 μL serum) and metabolomics (50 μL serum). In-depth chemometric screening with super-vised and unsupervised approaches and metabolic pathway analysis were applied to both datasets.

A Lipidomics study revealed that specific PUFA (ω-3) molecules are inversely asso-ciated with increased odds of CRC, while some PUFA (ω-6) analytes show a positive correla-tion. With the metabolomics approach, some proteogenic amino acids (Ala, Glu, Met, Thp, Tyr, Val), Myo-inositol, and 3- hydroxybutyric acid were found to be dysregulated in CRC.

This unique study provides a more comprehensive insight into molecular-level changes associated with CRC and allows for a comparison of the efficiency of two different analytical approaches for CRC screening using the same serum samples and single instrumentation.

Evaluation of different head space techniques for flavor
trapping and profiling of meat alternative samples

Emilie USUREAU (Small Molecule Analysis at Center for Analytical Innovation
- DSM-Firmenich, Pays-Bas).

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An important part of the acceptance of consumers in meat alternatives is their cooking experience. The smell released during baking or frying contributes to the overall perception of the product.

Often meat alternatives have a less appreciated smell during frying compared to meat burgers and knowing what kind of volatiles are responsible for that makes it possible to mitigate and work on improvements steps, increasing consumer acceptance.

Many headspace techniques are currently available to capture volatile organic compounds but there is so far no approach disclosed in literature or commercially available for fast profiling of volatile released during frying of the meat and meat alternative burgers.

In this lecture, the outcome of experiments where off-line air sampling for trapping the volatiles on adsorbent material, and on-line SPME sampling for volatiles profiling in fried meat and meat alternative burgers, followed by desorption and Gas Chromatography High Resolution Mass Spectrometry (GC-HRMS) analysis are presented.

To get the story complete: from manual SBSE extraction to a fully automated Twister TM workflow

Christophe DEVOS (RIC technologies, Belgium).

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Stir Bar Sorptive Extraction (SBSE) or, under its commercial name Twister TM extraction, has been the main topic of the first five editions of this technical meeting. Over the last two decades, SBSE has proven to be a highly powerful tool to extract organic compounds from different sample matrices at very low trace level quantities. SBSE has been successfully applied in many different areas of analytical chemistry including environmental, food, consumer product, toxicological, pharmaceutical and life science analysis in research center and in the industry worldwide. A recent search in Science Direct, resulted in more than 4000 “hits” for SBSE, reflecting the huge impact of sorptive based extraction in analytical chemistry.

As solventless sample preparation technique, stir bar sorptive extraction also plays a perfect role in the world of Green Analytical Chemistry and definitely deserves attention during this meeting focusing on trends towards more green analytical tools in the laboratory. Based on our contacts and discussion with our customers, RIC and Gerstel asked themselves how Twister TM extraction, that offers extremely high sensitivity, high extraction yields and high flexibility, can further evolve. One frequent comment for many years was the lack of “full automation” of a SBSE procedure. Although the two step procedure with (manual) extraction and automated thermal desorption is not really labor intensive, several customers were looking forward to a fully automated procedure.

In this presentation, we will, as a world premiere, introduce you to the AutoTwister: a fully automated system that allows unattended operation of the complete SBSE procedure. Both immersion and headspace extraction can be performed, followed by the necessary rinsing and drying steps, and thermal desorption, on-line with GC analysis. This approach is complementary to the well-known off-line procedure. Its performance will be illustrated by some typical examples, demonstrating the power of SBSE.

Determination of haloanisoles and halophenols in wine and in materials likely to carry contamination.

Rémy FULCHIC (Château Leoville las cases, France).

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Wine is a matrix that can easily pick up all kinds of contaminants present in the materials with which it comes into contact, or in the environments in which it is stored. Numerous molecules are known to be responsible for organoleptic deviations, notably haloanisoles, which irreversibly cause musty odors and tastes at very low concentrations, just a few ng/L.

This contamination can occur throughout the winemaking and ageing process, and even after bottling via the cork, which is sometimes responsible for the famous corky taste when it releases 2.4.6-Trichloroanisole into the bottle.

At Château Léoville Las Cases, a Gironde vineyard located in the Médoc in the Saint-Julien appellation, the in-house laboratory regularly analyzes new materials used in buildings, corks and mains water for haloanisoles (2.4.6- trichloroanisole, 2.3.4.6-tetrachloroaisole, 2.4.6-tribromoanisole and pentachloroanisole) and their corresponding halophenol precursors.

The latter do not present a direct olfactory risk, but they can be biomethylated into anisoles by certain molds, and therefore present a real risk if they are present, bearing in mind that vats or cellars are humid environments highly conducive to mold growth.

Their simultaneous determination is carried out by SBSE-GC-TOF, either directly for water and wine, or after extraction with ASE (Accelerated Solvent Extraction) for solid matrices. Phenols are acetylated during the SBSE phase, to improve extraction yield and thus the sensitivity of the method, as well as the chromatographic behavior of the compounds.

Automatic Robot for Preparation of Organic Samples:
ARPOS - TD-GC-MS/MS

Noemi SANTIAGO SANCHEZ (Labaqua, Espagne).

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Pesticides, PAHs, PCBs and other contaminants coming from the human activity are transported and heavily presented in soil. Usually the extraction techniques for this type of compounds in solid samples are tedious and use large amounts of organic solvents in order to reach the quantification limits required by the regulations. This entails a high economic cost of material and time.

For this reason, there is a need to automate this process due to it is a completely manual extraction and currently there are a high number of soil samples that require to analyse organic compounds. Labaqua, in collaboration with GERSTEL, has developed a robot that get to automate this extraction, eliminating in this way most of the manual process for organic compounds analysis.

In addition this automation increases considerably the productivity of the analysis. ARPOS is able to add all the extraction reagents, as well as homogenizing, concentration and reconstitution of the sample in a fully automatic way, so that the sample is ready for direct analysis by TDU-GC-MS/MS. Furthermore, the chromatography analysis of the extracted sample by TDU-GC-MSMS allows the injection of a large volume of extract, achieving in this way a high sensibility and a low limit of detection of organic compounds.

By means of a validation of the process carried out in Labaqua, its repeatability and reproducibility has been demonstrated, achieving a high profitability of the process. Therefore, ARPOS robot is presented as a bet on the future for the automation of large-scale sample analysis.

Of mice and wine, an approach using SBSE-GC-MS

Céline FRANC (Institut des Sciences de la Vigne et du Vin (ISVV)
- Villenave d'Ornon, France).

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Mousy off-flavour is a wine defect of modern concern among wine producers. Olfactory descriptors that characterise this particularly unpleasant defect include rodent urine (“dirty mouse cage”) and grilled foods such as popcorn, rice, crackers, and bread crust. These past years, wines spoiled by mousiness are increasing in frequency. This is often associated with rising pHs as well as certain oenological practices which significantly decrease the use of sulphur dioxide, thus favouring the development of microorganisms.

Three major molecules, 2-acetyl-1-pyrroline (APY), 2-acetyltetrahydropyridine (ATHP) and 2-ethyltetrahydropyridine (ETHP), were identified as responsible for mousiness in wines. However, to date, quantification data reported in the literature are limited due to analytical issues related to the nature of these compounds. Indeed, a simple and effective analytical method to determine trace levels of these three mousy N-heterocycles simultaneously was unavailable. To fill the gap and later understand the parameters influencing mousiness, a method using stir bar sorptive extraction (SBSE) followed by GC-MS analysis was developed.

After optimisation and performance evaluation, the quantification method was applied to analyse 6 control wines and 68 wines produced without added sulphites. This method was simultaneously adapted to microbiological media and used to monitor the production of the three mousy N-heterocycles based on the microorganism studied.

The SBSE-GC-MS analysis method proved its efficiency and paved the way to further studies aimed at understanding the conditions influencing the occurrence of mousiness in wine and the oenological parameters that modulate its expression.