State-of-the-art and challenges in the analysis of renewable gases.

The development of renewable and low-carbon gases for injection into the gas grid obtained by different processes such as anaerobic digestion, pyrogasification, hydrothermal gasification, and methanation, followed by upgrading steps, increases the demand for analysis and characterization in order to fully manage their integration into the gas value chain. If the analysis of the main compounds (methane, carbon dioxide, hydrogen, and carbon monoxide) is well described, the analysis of impurities in renewable gases remains more challenging due to their various natures and quantities. After a brief description of renewable and low-carbon methane production processes, the review focuses on the methods used for the analysis of the different compounds in renewable gases, from the main ones to impurities at ppbv levels. Gas chromatography (GC), coupled with different detectors, is the preferred technique, enabling the analysis and quantification of siloxanes, terpenes, oxygenates, and sulfur compounds. Recently, comprehensive two-dimensional GC has been applied to renewable gases, increasing the number of compounds detected. Non-chromatographic techniques are also reviewed. As sampling is of major importance in the search for reliable analyses, a whole section is devoted to this aspect. Among the available methods, pre-concentration on adsorbent tubes emerges as the most relevant solution.

Characterization of Flavor Compounds in Distilled Spirits: Developing a Versatile Analytical Method Suitable for Micro-Distilleries.

Over the last few years, the development of micro-distilleries producing diverse spirits with various flavors has been observed. Versatile analytical techniques for the characterization of aroma compounds in such alcoholic beverages are therefore required. A model mixture embodying a theoretical distilled spirit was made according to the data found in literature to compare usual extraction techniques. When it was applied to the model liquor, the headspace solid phase microextraction (HS-SPME) extraction method was preferred to the liquid-liquid extraction (LLE), solid phase extraction (SPE) and stir bar/headspace sorptive extraction (SBSE/HSSE) methods according to efficiency, cost, and environmental criteria. An optimization study using the model mixture showed that the extraction was optimal with a divinylbenzene/carboxen/poly(dimethylsiloxane) DVB/CAR/PDMS fiber, during 60 min, at 35 °C and with the addition of 10% NaCl. This method was successfully applied to three different commercial liquors and led to the identification of 188 flavor compounds, including alcohols, esters, lactones, carbonyls, acetals, fatty acids, phenols, furans, aromatics, terpenoids, alkenes, and alkanes.

Gas Digital Microfluidic Platform: Application to Highly Volatile Compound Preconcentration.

Digital microfluidics platforms (DMFPs) have shown their efficiency in sample handling, using elementary operations that may be combined to perform complex applications. In this article, we present a new platform for gaseous samples handling involving a two-step digital preconcentration using the miniaturized preconcentrators of the DMFP. Choosing n-pentane at very low concentrations as a model for highly volatile compounds, poorly retained on the sorbent, the DMFP allowed bypassing the limit set by the breakthrough volume by repeating an elementary operation. It enabled a 5-fold increase of preconcentration factors in comparison to a single preconcentration step and an easier monitoring of the model compound. Promising applications are expected, as this system could be adapted to most volatile compound analysis devices, including micro gas chromatographs, to replace the current single-step preconcentration systems. By switching to two-step preconcentration with a DMFP, i.e., a digital preconcentration, it would be possible to get more concentrated samples through the column for easier trace analysis.

Corona charged aerosol detector non-uniform response factors of purified alcohol ethoxylated homologues using liquid chromatography.

Surfactants are used in various applications: cosmetics, pharmaceuticals, petrochemicals, environmental, etc. Many of these compounds are polydisperse, and because of this intrinsic polydispersity, it is essential to have a universal detector with a uniform response to quantify them in a simple way. Indeed, Charged Aerosol Detector (CAD) was presented as a universal detector with a uniform response. Thus, in the present study, the CAD response, in a High-Performance Liquid Chromatography - CAD configuration (HPLCCAD), was evaluated using purified alcohol ethoxylated surfactants. A semi-preparative liquid chromatography step using a Hydrophilic interaction chromatography (HILIC) bare silica column (150 mm, 4.6 mm, 2.6 µm) was implemented to prepare eleven homologues of BrijC10, a nonionic surfactant. These homologues differed only by the number of ethylene oxide units. BrijC10 homologues were analyzed by HPLCCAD, using a HILIC bare silica column (150 mm, 2.1 mm, 2.6 µm) to determine the HPLCCAD response factors of purified homologues. From the calibration curves (from 100 to 500 mg.kg-1), their response factors were estimated: differences in response factors were observed and a maximum difference in response factors of 3.6 was obtained. Thus, it could be concluded that CAD hyphenated to HILIC separation did not present a uniform response for this homologue's distribution.

Analysis of multiclass organic pollutant in municipal landfill leachate by dispersive liquid-liquid microextraction and comprehensive two-dimensional gas chromatography coupled with mass spectrometry.

We propose a simple, fast, and inexpensive method for the analyses of 72 organic compounds in municipal landfill leachate, based on dispersive liquid-liquid microextraction and comprehensive two-dimensional gas chromatography coupled with mass spectrometry. Forty-one organic compounds belonging to several classes including hydrocarbons, mono- and polyaromatic hydrocarbons, carbonyl compounds, terpenes, terpenoids, phenols, amines, and phthalates, covering a wide range of physicochemical properties and linked to municipal landfill leachate, were quantitatively determined. Another 31 organic compounds such as indoles, pyrroles, glycols, organophosphate flame retardants, aromatic amines and amides, pharmaceuticals, and bisphenol A have been identified based on their mass spectra. The developed method provides good performances in terms of extraction recovery (63.8-127%), intra-day and inter-day precisions (< 7.7 and < 13.9 respectively), linearity (R2 between 0.9669 and 0.9999), detection limit (1.01-69.30 µg L-1), quantification limit (1.87-138.6 µg L-1), and enrichment factor (69.6-138.5). Detailed information on the organic pollutants contained in municipal landfill leachate could be obtained with this method during a 40-min analysis of a 4-mL leachate sample, using only 75 µL of extraction solvent.

A promising "metastable" liquid crystal stationary phase for gas chromatography.

The liquid crystal state is an ordered physical state between a solid and a liquid. Previous research, in gas chromatography, proved that it provides a geometric selectivity, which allows the separation of geometric position isomers and cis-trans isomers that are difficult to separate on conventional gas chromatography stationary phases (polydimethyl siloxane derived and polyethylene glycol stationary phases). However, their use was generally very limited by the rather high temperature at which they must be operated, normally above the solid-liquid crystal transition temperature. In the present study we are interested in a new synthesized material, 1,4- bis (4-bromohexyloxy benzoate) phenyl (BHOBP). The first characterizations of BHOBP were carried out by thermogravimetric analysis, hot-stage optical microscopy and differential scanning calorimetry to control the thermal stability of the BHOBP as well as the nematic texture of the mesophase highlighted in a well-defined temperature range (120 °C-200 °C). When heated, the solid compound led to a stable liquid crystal state. Its cooling has revealed "a new metastable physical state, which is the supercooled liquid crystal phase". After these first characterizations, the new material was used as a stationary phase for gas chromatography. The BHOBP was deposited in a capillary column by the dynamic method. The inverse gas chromatography study of the column revealed a solid-stable nematic phase transition temperature, in agreement with the first characterization methods. The stable liquid crystal phase showed good resolutions in the analysis of some geometric isomers of low volatility as PAHs. The presence of the supercooled liquid crystal state in the chromatographic column has also been confirmed. This new metastable state is particularly interesting because it enlarged the scope of this material by improving the resolution of several mixtures. Thus, the separation of highly volatile mixtures of geometric isomers (e.g. cis and trans-decalin) was achieved only through this metastable mesophase confirming its unique selectivity. The metastable liquid crystal, used at 80 °C, has also exhibited an original behavior by its stability after several weeks of use at the same temperature, maintaining constant retention factors and selectivity.

Chromatographic behavior and characterization of polydisperse surfactants using Ultra-High-Performance Liquid Chromatography hyphenated to High-Resolution Mass Spectrometry.

Surfactants are widely used in various petrochemical applications. Thus, it is essential to have highly efficient analytical tools to monitor the different classes of surfactants commonly used. Three among the four known classes of surfactants were studied in the present work: anionic (i.e. alkylbenzene sulfonate, alkyl ether carboxylic acid), nonionic (i.e. alkylcyclohexyl alcohol ethoxylated, alkyl alcohol ethoxylated) and cationic (i.e. alkyl trimethylammonium). Thanks to high-resolution mass spectrometry (HRMS), a useful mass list was created including 119 m/z values (error in mass around 5 ppm). This list was the foundation of a HRMS database, which, for the sake of simplicity, will be further denoted only "database". To avoid ion competition and streamline attribution of structural formulas for isobar molecules, a suitable chromatographic method was used before MS. The retention behavior of six surfactants (trimethyloctadecylammonium bromide, myristyltrimethylammonium bromide, Brij®C10, Triton X-100 reduced, glycolic acid ethoxylate lauryl ether, 4-dodecylbenzenesulfonic acid) was evaluated under three separation modes: reversed-phase liquid chromatography (RPLC), hydrophilic interaction chromatography (HILIC) and mixed-mode chromatography (combination of anion-exchange and reversed-phase mechanisms). In RPLC mode, six columns were tested including C4, C18, C30, polar-embedded C18, PFP and phenyl chemistries. Two HILIC columns were also tested including bare silica and urea chemistries. An anion-exchange combined with RPLC mechanism was investigated as mixed-mode mechanism. Using ammonium formate at 10 mM as buffer provided the best signal in HRMS. In liquid chromatography, acid conditions (pH 3.5) were preferred, to avoid peak tailing due to residual silanols. The mixed-mode separation mode clearly appears as the best compromise for the characterization of the three surfactants classes. Nevertheless, the orthogonality observed for the separations obtained in HILIC and RPLC modes offers some possibilities for further multidimensional separations.

Identification of traditional East Asian handmade papers through the multivariate data analysis of pyrolysis-GC/MS data.

An analytical approach based on the multivariate analysis of on-line pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) data is proposed for the identification of traditional East Asian handmade papers from different fiber material origins. This approach utilized several biomarkers detected during the Py-GC/MS analysis of paper samples. At first, the total ion chromatogram (TIC) was taken as the response and then the extracted ion chromatograms (EICs) were considered to improve the discrimination of papers. The influence of different data pretreatments (raw responses vs. normalized values) including different weightings of the variables (weighting as 1 vs. weighting as 1/STD, where STD stands for standard deviation) for principal component analysis was also investigated. The results showed that compared to the commonly used microscopy techniques, the Py-GC/MS technique proved to be able to discriminate against handmade paper materials that have similar microscopic morphologies such as Morus species vs. Broussonetia species. The data pretreatment influenced PCA modeling: the analysis based on normalized values showed more interpretable PCA group features for Moraceae species. PCA without weighting resulted unsurprisingly in discrimination through the presence of high intensity response biomarkers, while when applying weight as 1/STD, a PCA loading plot was shown to provide a group of compounds, most of them being present at low levels, to be discriminating. Additionally, the characteristic EICs can provide a data matrix for statistical analysis avoiding the interference from a co-eluting compound and background compared to the data matrix obtained from the TIC. As a result, a quick Py-GC/MS based handmade paper identification procedure using PCA modeling of the characteristic EICs was proposed for the first time in the identification of traditional East Asian handmade papers. This procedure could be very beneficial for cultural heritage applications.

Miniaturization of breath sampling with silicon chip: application to volatile tobacco markers tracking.

This work presents the performances of silicon micro-preconcentrators chips for breath sampling. The silicon chips were coupled to a handheld battery powered system for breath sampling and direct injection in a laboratory gas chromatography mass spectrometry system through thermal desorption (TD). Performances of micro-preconcentrators were first compared to commercial TD for benzene trapping. Similar chromatographic peaks after gas chromatographic separation were observed while the volume of sample needed was reduced by a factor of 5. Repeatability and day to day variability of the micro-preconcentrators were then studied for a 500 ppb synthetic model mixture injected three times a day four days in a row: 8% and 12% were measured respectively. Micro-preconcentrator to micro-preconcentrator variability was not significant compared to day to day variability. In addition, micro-preconcentrators were tested for breath samples collected in Tedlar® bags. Three analyses of the same breath sample displayed relative standard deviations values below 16% for eight of the ten most intense peaks. Finally, the performances of micro-preconcentrators for breath sampling on a single expiration were illustrated with the example of volatile tobacco markers tracking. The signals of three smoking markers in breath, benzene, 2,5-dimethylfuran, and toluene were studied. Concentrations of benzene and toluene were found to be 10 to 100 higher in the breath of smokers. 2,5-dimethylfuran was only found in the breath of smokers. The elimination kinetics of the markers were followed as well during 4 h: a fast decrease of the signal of the three markers in breath was observed 20 min after smoking in good agreement with what is described in the literature. Those results demonstrate the efficiency of silicon chips for breath sampling, compared to the state of the art techniques. Thanks to miniaturization and lower sample volumes needed, micro-preconcentrators could be in the future a key technology towards portable breath sampling and analysis.

Human odor and forensics: Towards Bayesian suspect identification using GC × GC-MS characterization of hand odor.

A new method for identifying people by their odor is proposed. In this approach, subjects are characterized by a GC × GC-MS chromatogram of a sample of their hand odor. The method is based on the definition of a distance between odor chromatograms and the application of Bayesian hypothesis testing. Using a calibration panel of subjects for whom several odor chromatograms are available, the densities of the distance between chromatograms of the same person, and between chromatograms of different persons are estimated. Given the distance between a reference and a query chromatogram, the Bayesian framework provides an estimate of the probability that the corresponding two odor samples come from the same person. We tested the method on a panel that is fully independent from the calibration panel, with promising results for forensic applications.

Active modulation in neat carbon dioxide packed column comprehensive two-dimensional supercritical fluid chromatography.

After demonstrating in a first paper the feasibility of SFCxSFC without decompression of the mobile phase, a modified interface has been developed in order to perform active modulation between the two SFC dimensions. In this paper, it is shown that the new interface enabled independent control of modulation parameters in SFCxSFC and performed a band compression effect of solutes between the two SFC dimensions. The effectiveness of this new modulation process was studied using a Design of Experiments. The SFCxSFC prototype was applied to the analysis of a real oil sample to demonstrate the benefits of the active modulator; in comparison to our previous results obtained without active modulation, better separation was obtained with the new interface owing to the peak compression occurring in the modulator.

Human odor and forensics. Optimization of a comprehensive two-dimensional gas chromatography method based on orthogonality: How not to choose between criteria.

The use of comprehensive two-dimensional gas chromatography coupled with mass spectrometry would be a real asset for the forensic profiling of human hand odor. This paper focuses on the optimization of a comprehensive gas chromatography method using a synthetic mixture of 80 compounds representative of human hand odor composition. In order to rank the candidate column sets, instead of using a unique criterion, we used a chemometric tool called desirability which is based on Derringer functions and enables to consider several criteria simultaneously and hence to get the best compromise. Nine criteria including six orthogonality criteria were used to evaluate the quality and the efficiency of the separation. The desirability analysis lead to a straightforward ranking and an accurate overview of the results in two situations, with an objective of routine analysis and without. In both cases, the DB-1MS×DB-1701 set was found to be best suited for the separation of the considered mixture, however with different gradients.

Supercritical Fluid Chromatography of Drugs: Parallel Factor Analysis for Column Testing in a Wide Range of Operational Conditions.

Retention mechanisms involved in supercritical fluid chromatography (SFC) are influenced by interdependent parameters (temperature, pressure, chemistry of the mobile phase, and nature of the stationary phase), a complexity which makes the selection of a proper stationary phase for a given separation a challenging step. For the first time in SFC studies, Parallel Factor Analysis (PARAFAC) was employed to evaluate the chromatographic behavior of eight different stationary phases in a wide range of chromatographic conditions (temperature, pressure, and gradient elution composition). Design of Experiment was used to optimize experiments involving 14 pharmaceutical compounds present in biological and/or environmental samples and with dissimilar physicochemical properties. The results showed the superiority of PARAFAC for the analysis of the three-way (column × drug × condition) data array over unfolding the multiway array to matrices and performing several classical principal component analyses. Thanks to the PARAFAC components, similarity in columns' function, chromatographic trend of drugs, and correlation between separation conditions could be simply depicted: columns were grouped according to their H-bonding forces, while gradient composition was dominating for condition classification. Also, the number of drugs could be efficiently reduced for columns classification as some of them exhibited a similar behavior, as shown by hierarchical clustering based on PARAFAC components.

Sampling method development and optimization in view of human hand odor analysis by thermal desorption coupled with gas chromatography and mass spectrometry.

Forensic profiling of human odor is challenging and would be useful to support information provided by dogs in courts of justice. Analyses of volatile compounds constitutive of human odor are commonly performed with gas chromatography coupled with mass spectrometry. All developed methods and sampling prototypes have to be easy to use in the field by crime scene investigators. This paper will focus on techniques for human hand odor sampling prior to analysis by a thermodesorption device coupled with gas chromatography and mass spectrometry. Thermodesorption and gas chromatography methods were developed using a sorbent phase spiked with a mixture of 80 compounds representative of human hand odor. Then, the crucial sampling step was performed indirectly with a homemade device based on air suction and trapping on a sorbent. This indirect sampling device was evaluated with the same synthetic mixture for optimization. An innovative polymer sorbent called Sorb-Star® was compared to classic Tenax TA® packed tubes. Sorb-Star® provided similar recovery to Tenax TA® packed tubes and a smaller pooled coefficient of variation (6 vs 13%). Thus, it appeared to be fully suited to the indirect sampling of human hand odor. The developed methods were successfully applied to real samples, the ultimate aim being the comparison of a suspect's sample to a sample collected from a crime scene.

Synergetic Use of Principal Component Analysis Applied to Normed Physicochemical Measurements and GC × GC-MS to Reveal the Stabilization Effect of Selected Essential Oils on Heated Rapeseed Oil.

Lipid oxidation leads to the formation of volatile compounds and very often to off-flavors. In the case of the heating of rapeseed oil, unpleasant odors, characterized as a fishy odor, are emitted. In this study, 2 different essential oils (coriander and nutmeg essential oils) were added to refined rapeseed oil as odor masking agents. The aim of this work was to determine a potential antioxidant effect of these essential oils on the thermal stability of rapeseed oil subject to heating cycles between room temperature and 180 °C. For this purpose, normed determinations of different parameters (peroxide value, anisidine value, and the content of total polar compounds, free fatty acids and tocopherols) were carried out to examine the differences between pure and degraded oil. No significant difference was observed between pure rapeseed oil and rapeseed oil with essential oils for each parameter separately. However, a stabilizing effect of the essential oils, with a higher effect for the nutmeg essential oil was highlighted by principal component analysis applied on physicochemical dataset. Moreover, the analysis of the volatile compounds performed by GC × GC showed a substantial loss of the volatile compounds of the essential oils from the first heating cycle.

Combination of partial least squares regression and design of experiments to model the retention of pharmaceutical compounds in supercritical fluid chromatography.

This work presents a first attempt to establish a model of the retention behaviour for pharmaceutical compounds in gradient mode SFC. For this purpose, multivariate statistics were applied on the basis of data gathered with the Design of Experiment (DoE) methodology. It permitted to build optimally the experiments needed, and served as a basis for providing relevant physicochemical interpretation of the effects observed. Data gathered over a broad experimental domain enabled the establishment of well-fit linear models of the retention of the individual compounds in presence of methanol as co-solvent. These models also allowed the appreciation of the impact of each experimental parameter and their factorial combinations. This approach was carried out with two organic modifiers (i.e. methanol and ethanol) and provided comparable results. Therefore, it demonstrates the feasibility to model retention in gradient mode SFC for individual compounds as a function of the experimental conditions. This approach also permitted to highlight the predominant effect of some parameters (e.g. gradient slope and pressure) on the retention of compounds. Because building of individual models of retention was possible, the next step considered the establishment of a global model of the retention to predict the behaviour of given compounds on the basis of, on the one side, the physicochemical descriptors of the compounds (e.g. Linear Solvation Energy Relationship (LSER) descriptors) and, on the other side, of the experimental conditions. This global model was established by means of partial least squares regression for the selected compounds, in an experimental domain defined by the Design of Experiment (DoE) methodology. Assessment of the model's predictive capabilities revealed satisfactory agreement between predicted and actual retention (i.e. R2=0.942, slope=1.004) of the assessed compounds, which is unprecedented in the field.

Origin, Analytical Characterization, and Use of Human Odor in Forensics.

Developing a strategy to characterize the odor prints of individuals should be relevant to support identification obtained using dogs in courts of justice. This article proposes an overview of the techniques used for the forensic profiling of human odor. After reviewing the origin of human odor-both genetic and physiological-the different analytical steps from sample collection to statistical data processing are presented. The first challenge is the collection of odor, whether by direct sampling with polymer patches, cotton gauze, etc., or indirect sampling with devices like Scent Transfer Unit. Then, analytical techniques are presented. Analyses are commonly performed with gas chromatography coupled with mass spectrometry. As they yield large amounts of data, advanced statistical tools are needed to provide efficient and reliable data processing, which is essential to give more probative value to information.

Multiple welding of long fiber epoxy vitrimer composites.

Vitrimers appear as a new class of polymers that exhibit mechanical strength and are insoluble even at high temperatures, like thermosets, and yet, like thermoplastics, they are heat processable, recyclable and weldable. The question arises whether this welding property is maintained in composite materials made of more than 50 vol% of reinforcing fibers. In this paper, we quantitatively analyze the bond strength of epoxy vitrimer-based composite plates made by resin transfer molding and compare them to their non-vitrimer counterparts made of a standard thermoset epoxy. It is demonstrated that only epoxy vitrimer samples show substantial bond strength and the ability to be repeatedly welded thanks to the exchange reactions, which promote improved surface conformity and chemical bonding between the adherands at the joint interface. This opens the way towards joining composite parts without adhesives nor mechanical fasteners.

Validation of a headspace trap gas chromatography and mass spectrometry method for the quantitative analysis of volatile compounds from degraded rapeseed oil.

Due to lipid oxidation, off-flavors, characterized by a fishy odor, are emitted during the heating of rapeseed oil in a fryer and affect the flavor of rapeseed oil even at low concentrations. Thus, there is a need for analytical methods to identify and quantify these products. To study the headspace composition of degraded rapeseed oil, and more specifically the compounds responsible for the fishy odor, a headspace trap gas chromatography with mass spectrometry method was developed and validated. Six volatile compounds formed during the degradation of rapeseed oil were quantified: 1-penten-3-one, (Z)-4-heptenal, hexanal, nonanal, (E,E)-heptadienal, and (E)-2-heptenal. Validation using accuracy profiles allowed us to determine the valid ranges of concentrations for each compound, with acceptance limits of 40% and tolerance limits of 80%. This method was then successfully applied to real samples of degraded oils.

Development of a capillary electrophoresis method for the analysis in alkaline media as polyoxoanions of two strategic metals: Niobium and tantalum.

Tantalum (Ta) and niobium (Nb) are two strategic metals essential to several key sectors, like the aerospace, gas and oil, nuclear and electronic industries, but their separation is really difficult due to their almost identical chemical properties. Whereas they are currently produced by hydrometallurgical processes using fluoride-based solutions, efforts are being made to develop cleaner processes by replacing the fluoride media by alkaline ones. However, methods to analyze Nb and Ta simultaneously in alkaline samples are lacking. In this work, we developed a capillary zone electrophoresis (CE) method able to separate and quantify Nb and Ta directly in alkaline media. This method takes advantage of the hexaniobate and hexatantalate ions which are naturally formed at pH>9 and absorb in the UV domain. First, the detection conditions, the background electrolyte (BGE) pH, the nature of the BGE co-ion and the internal standard (IS) were optimized by a systematic approach. As the BGE counter-ion nature modified the speciation of both ions, sodium- and lithium-based BGE were tested. For each alkaline cation, the BGE ionic strength and separation temperature were optimized using experimental designs. Since changes in the migration order of IS, Nb and Ta were observed within the experimental domain, the resolution was not a monotonic function of ionic strength and separation temperature. This forced us to develop an original data treatment for the prediction of the optimum separation conditions. Depending on the consideration of either peak widths or peak symmetries, with or without additional robustness constraints, four optima were predicted for each tested alkaline cation. The eight predicted optima were tested experimentally and the best experimental optimum was selected considering analysis time, resolution and robustness. The best separation was obtained at 31.0°C and in a BGE containing 10mM LiOH and 35mM LiCH3COO.The separation voltage was finally optimized, resulting in the separation of Nb, Ta, and IS in less than 2.5min, which is three times faster than any CE method ever reported for the separation of Nb and Ta (acidic media included). Some figures of merit of the method were determined such as linearity ranges and limits of quantitation. Finally, the method was successfully applied to the analysis of a real industrial sample.