Gas Chromatographic Determination Research Articles

Solvent-Focused Gas Chromatographic Determination of Thymol and Carvacrol Using Ultrasound-Assisted Dispersive Liquid-Liquid Microextraction through Solidifying Floating Organic Droplets (USA-DLLME-SFO).

An ultrasound-assisted dispersive liquid-liquid microextraction by solidifying floating organic droplets, coupled to a form of temperature-programmed gas chromatography flame ionization detection, has been developed for the extraction and determination of thymol and carvacrol. This method utilizes undecanol as the extraction solvent, offering advantages such as facilitating phase transfer through solidification and enhancing solvent-focusing efficiency. The optimal gas chromatography conditions include a sample injection volume of 0.2 µL, a split ratio of 1:10, and a flow rate of 0.7 mL min-1. The extraction conditions entail an extraction solvent volume of 20 µL, a disperser solvent (acetone) volume of 500 µL, pH 7.0, 7.0% NaCl (3.5 M), a sample volume of 5.0 mL, an ultrasound duration of 10 min, and a centrifuge time of 7.5 min (800 rpm). These conditions enable the achievement of a high and reasonable linear range of 3.5 to 70. 0 μg mL-1 for both thymol and carvacrol. The detection limits are found to be 0.95 and 0.89 μg mL-1, respectively, for thymol and carvacrol. The obtained relative standard deviations, 2.7% for thymol and 2.6% for carvacrol, demonstrate acceptable precision for the purpose of quantitative analysis.

Switchable hydrophilicity solvent-based hollow fibre liquid-liquid microextraction – headspace gas chromatography for determination of benzene and its derivatives in water samples


 
 
 
 A novel, cost-effective, simple and environmentally friendly method was developed for separating, preconcentrating and quantifying volatile analytes. That approach utilised switchable hydrophilicity solvent-based hollow fiber liquid-liquid microextraction in combination with headspace gas chromatography. The extraction was carried out from 1 l of water solution. 100 μl of nonanoic acid, immobilised within a polypropylene capillary, was selected as an extraction solvent. After the extraction, the capillary with the extract was transferred to a headspace vial, and headspace gas chromatographic analysis was performed. To facilitate the transition of volatile analytes to the headspace for subsequent analysis, nonanoic acid was converted to hydrophilic nonanoate by adding a sodium hydroxide solution.
 The effectiveness of the suggested strategy was demonstrated in the determination of benzene and its derivatives in water samples. Various parameters affecting the extraction and headspace gas chromatographic determination were investigated and optimised. Under the optimal conditions, the analytical characteristics of the proposed technique were determined.
 Using this approach, the limits of quantification for all analytes were found to be below the maximum acceptable concentration.
 
 
 

Problematic issues of rationing and identification of the fat phase of dairy products

The purpose of the work: to identify problematic issues of rationing and detection of adulteration of milk and dairy products with fats of non-dairy origin of the fat phase and to propose ways to improve the rationing and application of methods of quality control of milk and dairy products in the practice of control and supervisory measures. To obtain the necessary data, legislative, regulatorytechnical and regulatory — methodological documentation, scientific publications and dissertations for the period from 2018 to 2023 were used. It has been established that at present, the detection of falsification of milk and dairy products within the framework of control and supervisory measures has a number of difficulties, which are related both to the legality of the use of existing control methods and regulatory framework, and to the informativeness of the control methods used and the relevance of the regulatory framework. To solve this issue, it is necessary to introduce new more inf into institutions that ensure the activities of Rospotrebnadzor new more informative control methods. One of which is the gas chromatographic determination of the triglyceride content in the fat fraction of the product, which makes it possible to detect the introduction of non-dairy components of less than 30 % and the use of animal fats as substitutes for milk fat. One of these methods is the determination of triglycerides of the fat fraction of the product, based on the extraction of lipids from the product sample, followed by direct gas chromatographic determination of their content. To evaluate products, it is necessary to adjust the regulatory documentation applicable to milk and dairy products, including the inclusion of clear identification indicators of the fat phase of milk fat in TR CU 033/2013 « On the safety of milk and dairy products».

Gas Chromatographic Determination of Residual Concentrations of a Mixture of Organochlorine Pesticides in Food Products

Purpose of research. The aim of the work is to optimize the conditions for gas chromatographic determination of a mixture of eight organochlorine pesticides: aldrin, hexachlorobenzene, heptachlor, α-hexachlorocyclohexane, γ-hexachlorocyclohexane, dichlorodiphenyltrichloromethylmethane, dichlorodiphenyldichloroethane and dichlorodiphenyldichloroethylene.Methods. For chromatographic studies of organochlorine pesticides we used a Shimadzu GC-2010Plus gas chromatograph (Shimadzu, Japan) equipped with an automatic equilibrium vapor sample dispenser NT200N, electron-capture detector based on 63Ni and quartz capillary nonpolar column "Chromatek" SPB-5 (30 m, 0.32 mm, film thickness on the basis of phenyl(5%) and dimethyl(95%) polysiloxanes 0.5 μm) with an operating temperature range of 60°C 320/340°C. The chromatograms were processed in the application LabSolutions GPC.Results. On the basis of experimentally obtained data the optimal conditions for gas chromatographic determination and separation of eight-component mixture of organochlorine pesticides were selected, namely: the value of mobile phase flow division 1:10, carrier gas flow rate – 1.0 ml/min, two-stage temperature programmable column mode from 160 to 240°C with the rate of increase of 5°C/min. The metrological characteristics of the analysis and validation of the results of the proposed technique with the method of high-performance liquid chromatography were evaluated. Good reproducibility of chromatography results with the possibility of detection of organochlorine pesticides at the level of 10-6 – 10-5 μg/cm3 was proved. Application of Fisher's test has shown absence of significant differences in reproducibility of sampled populations the investigated methods of chromatographic analysis of COPCs are equally accurate. Extraction sample preparation of samples of real objects was proposed, the calculated extraction degrees >84% allow to recommend the technique for quantitative determination of analytes.Conclusion. The method of gas chromatographic analysis was tested for determination of organochlorine pesticides in samples of drinking water and baby puree (Russia) by additive method. Exceeding the norms of residual contents of organochlorine pesticides in the samples of the food products under study was not detected.

Isolation and determination of phenolic acids in rowanberry fruits (Sorbus L.) by gas chromatography

Species of the genus Sorbus L. (rowan) are woody plants growing in the Northern Hemisphere; they are of interest as decorative, food and medicinal plants. Rowan fruits contain a unique complex of macro- and microelements, as well as biologically active substances, including phenolic compounds. Complexity of the composition of plant samples requires the development of highly selective and sensitive methods for determining the content of organic components of different classes. A method for determining phenolic acids in rowan fruits is proposed. The method is based on two-stage chemical modification of the acids, and involves preparing methyl esters under acidic methanolysis conditions, liquid extraction with toluene, intermediate re-extraction into an aqueous alkaline solution, subsequent silylation with N, O-bis-(trimethylsilyl)trifluoroacetamide (BSTFA) and gas chromatographic determination of the obtained derivatives using a flame ionization or mass spectrometric detector. Conditions for extraction of phenolic acids from rowan fruits were studied according to the following parameters: type of extractant, sample to the extractant mass ratio, and duration of extraction (mechanical stirring). The stage of gas chromatographic determination of obtained phenolic acid derivatives was optimized, and their chromatographic characteristics established. The possibility of achieving practically complete separation of aliphatic acids and other accompanying components of a non-acidic nature from phenolic compounds in the course of sample preparation was demonstrated; which significantly increased both the selectivity and sensitivity of the determination of analytes. The range of determined content of phenolic acids (4-hydroxybenzoic acid, 2-hydroxybenzoic acid, 4-hydroxy-3-methoxy-benzoic acid, 4-hydroxycinnamic acid, 4-hydroxy-3-methoxy-cinnamic acid) in rowan fruits was 0.005–0.5 mg/g, the limit of detection was 0.001–0.002 mg/g, the relative error was 10–15%, the sample weight was 0.5 g, the total duration of the analysis was 4 hours.

One-Step Preparation of Fiber-Based Chlorzoxazone Solid Dispersion by Centrifugal Spinning.

An amorphous fiber-based solid dispersion of chlorzoxazone was prepared for the first time by employing centrifugal spinning, using polyvinylpyrrolidone as the fiber-forming polymer. After optimization of the spinning parameters, the obtained fibers were characterized using a set of analytical techniques, both in a solid- and solution-state. Morphological characterization revealed a slightly aligned, defect-free fibrous structure with an average fiber diameter of d = 3.07 ± 1.32 μm. The differential scanning calorimetric results indicated a crystalline-to-amorphous transition of the active substance during the centrifugal spinning process, while gas chromatographic determinations revealed a residual ethanol content of 0.42 ± 0.04%. UV spectroscopy indicated the incorporation of chlorzoxazone in the fibrous structures, with an average active substance content of 15.91 ± 0.36 w/w%. During small-volume dissolution studies, the prepared fiber mats presented immediate disintegration upon contact with the dissolution media, followed by rapid dissolution of the active substance, with 84.8% dissolved at 1 min and 93.7% at 3 min, outperforming the micronized, pure chlorzoxazone. The obtained results indicate that centrifugal spinning is a low-cost, high-yield, viable alternative to the currently used methods to prepare fiber-based amorphous solid dispersions of poorly soluble drugs. The prepared chlorzoxazone-loaded microfibers could be used as a buccal dosage form for the systematic delivery of chlorzoxazone and could potentially lead to a rapid onset of action and longer efficacy of the muscle relaxant drug.

THE INFLUENCE OF PENICILLIUM FUNGI ISOLATED FROM SOYBEAN ROOTS ON THE SYMBIOTIC SYSTEM “GLYCINE MAX – BRADYRHIZOBIUM JAPONICUM” AND CROP PRODUCTIVITY

Objective. Identify new strains of Penicillium endophytic fungi by morphological and cultural properties, study their influence on the symbiotic system “Glycine max – Bradyrhizobium japonicum” and soybean productivity. Methods. Microbiological (cultivation of endophytic fungi, preparation of spore suspensions, determination of spore titre in suspensions, light microscopy), gas chromatographic (determination of nitrogenase activity of soybean nodules), vegetation and field small-plot experiments (study of the effect of endophytic fungi on symbiotic and morphometric parameters of soybean plants and crop yield when growing on sod-podzolic soil), statistical. Results. New strains of Penicillium endophytic fungi are attributed to the species P. funiculosum Thom, P. variabile Sopp, P. glauco-lanosum Chalabuda, and P. steckii Zaleski based on their morphological and cultural characteristics. Under the conditions of the vegetation experiment, the positive influence of the studied strains on the symbiotic parameters of soybeans was shown. A tendency towards an increase in the number of nodules versus the control in all variants, an increase in the mass of nodules in the variants when soybean seeds were treated with spores of P. variabile 20173 and P. funiculosum 20312 by 28.4 % and 36.4 %, respectively, an increase in the nitrogenase activity of nodules by 29.8–38.5 % in variants with the use of P. stekii 2204, P. glauco-lanosum 20401, P. variabile 20173 was registered. The results of the study of soybean symbiotic parameters under the conditions of the field experiment generally confirmed the corresponding data of the vegetation experiment. Inoculation of soybean seeds with spores of Penicillium endophytic fungi contributed to an increase of the morphometric parameters of plants, namely: height — by 4.6–6.2 cm in all variants of the experiment, above-ground mass of dried plants — by 11.1–19.0 % when treated with P. stekii 2204, P. glauco-lanosum 20401, P. variabile 20173, mass of dry roots — by 13.2 % and 18.4 % with P. funiculosum 20312 and P. variabile 20173. The results of the field experiment proved the positive influence of new strains of endophytic fungi on soybean yield: when soybean seeds were inoculated with P. variabile 20173, P. funiculosum 20312 and P. stekii 2204, the increase in grain productivity was on average from 11.8 % to 17.3 %. The weight of 1000 grains increased by 3.8–5.1 % in variants using P. variabile 20173, P. glauco-lanosum 20401, P. stekii 2204. Conclusion. Penicillium endophytic fungi, which belong to the species P. funiculosum, P. variabile, P. glauco-lanosum and P. stekii, were isolated from the tissues of soybean roots. It was found that Penicillium endophytic fungi have a positive influence on the functioning of the symbiotic system “Glycine max – Bradyrhizobium japonicum” and soybean yield.

Optimization and Production of Aceclofenac-Loaded Microfiber Solid Dispersion by Centrifugal Spinning.

Aceclofenac-loaded polyvinylpyrrolidone fiber-based amorphous solid dispersion was produced successfully by centrifugal spinning. The solution concentration and rotational speed were optimized to produce the fiber-based drug carrier system, with a determined production rate of 12.7 g/h dry solid fibers. The obtained fibers were bead-free and smooth-surfaced with an average diameter of 7.5 ± 2.5 μm. Gas chromatographic determinations revealed that ethanol, as a residual solvent, was well below the regulatory limit of 0.5%. Differential scanning calorimetric investigation and infrared spectroscopic measurements were used to track the physicochemical changes that intervene during fiber formation in the solid state. The results revealed that the rapid evaporation of the solvent was accompanied by a probable crystalline to amorphous transition of the active substance during centrifugal spinning. In vitro dissolution studies revealed an instantaneous disintegration of the fibrous structure and a rapid release of the active substance, with the microfibrous webs greatly outperforming the crystalline active substance, especially in the early time-points. This implies that centrifugal spinning offers a viable scale-up production process to prepare drug-loaded fiber-based solid dispersions.

Eco-friendly thermosensitive magnetic-molecularly-imprinted polymer adsorbent in dispersive solid-phase microextraction for gas chromatographic determination of organophosphorus pesticides in fruit samples

A thermosensitive magnetic-molecularly-imprinted polymer (TMMIP) was successfully prepared in an aqueous medium. The TMMIP was applied as an effective adsorbent in dispersive solid-phase microextraction for the selective enrichment of five organophosphorus pesticides (OPPs; diazinon, fenitrothion, fenthion, parathion-ethyl, and ethion) before analysis by gas chromatography. The polymerization was performed using mixed-valence iron hydroxide nanoparticles as the magnetic support, N-isopropyl acrylamide as the thermosensitive monomer, ethion as the template, and methacrylic acid as the functional monomer. The adsorption and desorption mechanisms of OPPs depend on their interactions with the adsorbents and solution temperature. Our methodology provides good linearity (0.50–2000 µgL-1), with a correlation determination of R2 > 0.9980, low limit of detection (0.25–0.50 µgL-1), low limit of quantitation (0.50–1.50 μg L−1), and high precision (%RSD < 7%). The developed method demonstrates excellent applicability for accurately and efficiently determining OPP residuals in fruit and vegetable samples with good recoveries (93–117%).

Preconcentration of Volatile Organic Compounds on Carbon Magnetic Sorbents in the Analysis of Air by Using the Configuration Change of the Sorbent Bed during the Transition from Sorption to Thermodesorption GC-FID

The new scheme of the rapid preconcentration of volatile organic substances followed by the thermodesorption and gas chromatographic determination by using a flame ionization detector is proposed for the analysis of air. The scheme implies a change in the geometry of the adsorbent layer in a column during the transition from adsorption to thermal desorption steps. The extraction of analytes is carried out in a wide tube, allowing quantitative adsorption at higher flow rates of the analyzed air passed through the magnetic sorbent held in a thin layer retained by a permanent magnet without any supporting frits. Novel magnetic adsorbents composed of magnetite or a zirconia/magnetite core and pyrocarbon shell are developed for this application. At the end of the adsorption step, the magnet moved out of the system, and the adsorbent transferred under the gravity force into a narrow tube, which provides the more efficient heating of the adsorbent and minimal blurring of the analyte zones during the subsequent thermal desorption. The proposed scheme allows a significant reduction (approximately 10 times) of the time required for the preconcentration of analytes, which is illustrated by the GC determination of alcohols (butanol-1, pentanol-1), phenol, and o-cresol in the air.

Corrigendum to “Deep Eutectic Solvent-based green extraction and gas chromatography determination of phthalates released from food contact materials” [J. Food Compos. Anal. 118 (2023) 1–9

Corrigendum to “Deep Eutectic Solvent-based green extraction and gas chromatography determination of phthalates released from food contact materials” [J. Food Compos. Anal. 118 (2023) 1–9

Rapid Gas-Chromatographic Determination of Phenol and Cresols in Water by Extractive Freezing-Out

Rapid Gas-Chromatographic Determination of Phenol and Cresols in Water by Extractive Freezing-Out

Rapid Gas-Chromatographic Determination of Phenol and Cresols in Water by Extractive Freezing-Out

A rapid procedure for the determination of phenol and cresol isomers in drinking, sea, and polluted domestic wastewater is developed based on a single-stage extraction of analytes by extractive freezing-out under sample centrifugation conditions. In combination with gas chromatography, the procedure provides the minimum detection limits for each of phenols in 10 mL of water at a level of 0.0005 µg/mL. The duration of sample preparation does not exceed 30 min; the consumption of the ethoxyethane extractant is 1.4 mL. In comparison with liquid–liquid and solid-phase extraction traditionally used at the stage of sample preparation, the proposed procedure is simpler and more environmentally friendly. The stages of filtering samples and dehydrating extracts are excluded; the amount of chemical glassware is minimized.

Deep Eutectic Solvent-based green extraction and gas chromatography determination of phthalates released from food contact materials

A sensitive and efficient green emulsification liquid-liquid microextraction (ELLME) method using deep eutectic solvents (DES) for extraction of phthalates released from food contact materials (FCMs) was optimized for GC-MS determination of Butyl Benzyl Phthalate (BBP) and Di-2-Ethylhexyl Phthalate (DEHP). The optimal DES system for phthalate extraction was determined to be Choline Chloride:Phenol (1:2 molar ratio). Tetrahydrofuran (THF) was utilized as the emulsifier solvent. The effects of vortex agitation times and centrifugation times on extraction efficiency were investigated. The method yielded quantification limits (LOQ) of 0.036 and 0.005 mgL-1 for BBP and DEHP, respectively. Repeatability relative standard deviations (RSDr) of 2.9% and 2.2% were obtained for BBP and DEHP, respectively, while corresponding medium precision relative standard deviations (RSDR) were 2.8% and 3.2%. Recovery rates from spiked samples were 94.8% for BBP and 95.1% for DEHP. Finally, determination of BBP and DEHP released from contact materials into water and beverage samples at various temperatures confirmed the applicability of the method for assessment of phthalates and their migration from FCMs.

Gas Chromatographic Determination of Fatty and Organic Acid Composition in Selenium-Protein Dietary Supplement

Topicality. The use of selenium-protein dietary supplements (SPDS) is relevant from a medical and economic point of view, as it can provide consumers with the required amount of selenium, and increase the value and attractiveness of food products. The diet of a modern person is very diverse in the composition of fatty ingredients. Of all natural fats, dairy is the most complex and unique one in its chemical composition. SPDS “Syvoselen Plus” contains up to 10% fat in its composition, therefore, studies of its composition are of certain scientific interest in view of the above. In many scientific studies, gas chromatography is used to determine the composition of not only the fat fraction of additives containing vegetable oils and animal fats, but also organic acids. The study of the fat fraction and the fraction of organic acids of additives by this method allows determining and predicting the composition of similar fractions in the final product from SPDS. This, in turn, allows for comprehensive control of the quality and composition of such final products. The aim of the article is to determine the quantitative and qualitative composition of fatty and organic acids in the SPDS “Syvoselen Plus” by the gas chromatography method, and to compare the results of the determination with the indicators of a hypothetical ideal fat. When writing the article, statistical and physico-chemical research methods were used, namely, the gas chromatography method, with the help of which the following problems are solved: the composition of the fat fraction of SPDS is determined quantitatively and qualitatively; the degree of correspondence of the main indicators of the fat “Syvoselen Plus” to the hypothetical ideal is established; the composition of organic acids in the additive is determined. Results. The fatty acid composition of milk fat, milk whey and SPDS was studied. Dietary supplement “Syvoselen Plus” contains a significant amount of palmitic (3117.71 mg/kg), stearic (1618.61 mg/kg), oleic (1397.95 mg/kg) and meristic (1296.69) mg/kg) fatty acids, which is confirmed by chromatograms of fat fractions of milk fat and SPDS. The main indicators of hypothetically ideal, milk, whey fats and DDBS were presented. As a result, it was established that the composition of fat, which is most similar to the ideal one, among the objects of the study, has SPDS “Syvoselen Plus” (the indicator of the ratio of the sum of oleic and linoleic acids to the sum of pentadecanoic and stearic acids coincides with the indicator of ideal fat, and the indicators of the ratio of linoleic to linolenic acids and linoleic to oleic acids are close to the values of the indicators of ideal fat). The study of the composition of organic acids of SPDS was carried out. Fractions of succinic, azelaic, and levulinic organic acids are predominant, which may be due to the type of dairy products from which the serum was obtained, the storage conditions of dairy products and the serum itself, the type of microorganisms that carry out the fermentation process and can produce various organic acids, and the production process of dairy products and their composition. Conclusions and discussion. The analysis of the fatty acid composition and the quality content of organic acids in “Syvoselen Plus” dietary supplement confirmed the feasibility of using a dietary supplement in health food technologies, since the latter contains enough polyfunctional fatty and organic acids.

Investigation and optimization of methane purification method for natural gas by two-column gas chromatography: A preliminary test for doubly substituted isotopologue (13CH3D) measurements

In this study, optimization of the methane purification method by gas chromatography (GC) is described for the determination of methane clumped isotope compositions of natural gas. Methane was purified under the carrying of helium on the assembly line composed of a vacuum apparatus and two-column gas chromatography. Once methane was detected by the passive thermal conductivity detector (TCD) on the GC, it was collected through a silica trap immersed in liquid nitrogen. Optimum conditions of chromatographic column diameter (1/4 inch outside diameter), temperature (25 °C), and flow rate (50.8 ml min-1) have been determined. When N2/CH4 (by volume) is&amp;lt;8.7%, the purification experiment can be undertaken once, while a double purification experiment is required when natural gas samples have an N2/CH4 of 8.7-78.0%. The purification method yielded a purity of 98.4-98.8% with a recovery of 97.3-98.7% on purified methane samples verified by GC determination. N2 was the main source that contributed to the loss of the purity, however, the N-bearing isobaric interferences (14NH3+ and 14NH4+) in purified samples presented&amp;lt;1‰ intensity compared to the methane isotopologues (13CH4+ and 13CH3D+), thus we concluded that these interferences have no impact on clumped isotope determinations. The conventional δ13CVPDB and δDVSMOW values of purified methane samples were consistent with those of pure methane. A preliminary measurement of Δ13CH3D (working gas) of purified samples revealed differences of -0.27‰, which was within the internal precision of the measurement. The entire process of a single purification can be completed within two hours. Our proposed method could be used for the clumped isotope purification of natural gas with higher than ~50% methane.

FORMALDEHYDE ANALYSIS BY SPME ON-FIBER DERIVATIZATION: A STUDY OF THE KINETIC MODELS OF ADSORPTION FOR DIVINYLBENZENE

Solid-phase microextraction (SPME) via on-fiber derivatization with O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine (PFBHA) and gas chromatographic determination is considered a technique of choice in many analytical fields for formaldehyde (FA) monitoring. Vapor phase adsorption models of experimentally loaded PFBHA on porous divinylbenzene (DVB) SPME were investigated at 60 °C, 35 cm s-1 of air velocity, in a 1-64 min range: with the fiber completely exposed, loaded PFBHA was about 276 µg. Among the models tested, i.e. heat transfer, pseudo-second-order (PSO), Elovich, intra-particle diffusion, extra-particle diffusion and Langmuir, PFBHA adsorption was best fit by the PSO model, showing agreement with experimental data (272 µg). The sampling rate of FA in our conditions, obtained with a permeation tube system, was in agreement with literature (17.4 and 18.3 mL min-1, respectively). Thus, an overall standardization of the sampling phase is presented, leaving the sampling time as the most crucial parameter to be set for future applications.

Gas chromatographic determination of fatty acid composition in breast milk of mothers with different health conditions

AbstractHuman milk (HM) of healthy, well-nourished, lactating mothers is a unique and ideal source of nutritive factors, like hormones, cytokines, chemokines, growth factors that ensures the proper growth and development of infants. Among the main components of HM, fat is an important energy source and a regulatory factor. The quality of milk fat depends on its fatty acid (FA) composition. Gas chromatography coupled with flame ionisation detection is one of the most common methods for analysis of the FA profile of HM. The aim of this study was to evaluate the FA composition of HM, collected from mothers with different health conditions (normal Body Mass Index (nBMI); overweight and obese) using GC-FID method. The results showed that saturated FAs were present in the highest amount in the HM samples, of which palmitic acid was the main representative. The major monounsaturated FA was oleic acid, while linoleic acid was the most abundant of the polyunsaturated FAs (PUFA). Overweight and obese women have lower levels of PUFA in their breast milk. The data were subjected to principal component and quadratic discriminant analysis (QDA). QDA classified nBMI and overweight and obese mother milk samples with 88.24% accuracy. Significant differences were found between normal and overweight and obese HM samples in case of C10:0 and C18:3 FAs. Higher maternal BMI was associated with a higher n-6/n-3 PUFA ratio.

Needle extraction device for rapid and quantitative gas chromatographic determination of volatile chlorinated hydrocarbons and benzene in soil

A rapid and quantitative analytical method for volatile chlorinated hydrocarbons and benzene, such as chloroethylene, dichloromethane, and carbon tetrachloride, in soil samples was developed using a needle-type extraction device packed with activated carbon-based adsorbents. The soil sample of 10 g was placed in a glass cartridge and fixed with quartz wool to make sure not to move during the extraction process. After the internal standard solution was spiked into the soil sample, the cartridge was sealed with a polytetrafluoroethylene adapter, and the needle extraction device was used to collect the headspace gas. Analytes were purged from the soil sample and collected on the adsorbent, while pure nitrogen gas was introduced to the soil sample during the sample collection. The sampling time was approximately 10 min for 100 mL of gas sampling. After the sampling process, the extraction needle was directly inserted into a heated injection port of gas chromatography equipped with flame ionization detector (GC-FID) or that hyphenated to mass spectrometry (GC–MS). The extracted VOCs were thermally desorbed and simultaneously introduced to a GC capillary column for subsequent separation and determination. The limit of detection and limit of quantification of all the examined analytes was less than 20 and 60 ng/10 g soil in GC-FID and less than 2.5 and 7.5 ng/10 g soil in the case of GC–MS. Linear calibration curves were obtained up to 10 μg/10 g soil for all the analytes. The relative standard deviations of the ratio of analyte peak area and internal standard peak area were less than 10%. The recovery and sensitivity of analytes confirmed in the proposed method were compared with that obtained with a standard method conventionally employed.

Hydrophobic Natural Eutectic Solvents for the Gas Chromatographic Determination of Suspected Allergens in Fragrances by Dispersive Liquid-Liquid Microextraction

The fragrance industry plays a key role in the global economy, producing a wide range of personal care and household products. However, some fragrance ingredients have been linked to allergic reactions in sensitive people, and their concentrations are regulated at the European level. For this reason, reliable, rapid, and sustainable analytical methods are needed to rapidly detect and quantify these compounds. Recently, a new class of hydrophobic eutectic solvents (HES) has been introduced; they consist of natural terpenoids or phenolic compounds that can be used as hydrogen bond donors (HBD) and acceptors (HBA), and they are more suitable for GC applications due to their higher volatility. In this study, a dispersive liquid–liquid microextraction (DLLME) approach is proposed for the analysis and quantification of a range of allergens in hydroalcoholic perfumes. The optimized method requires only 50 µL of a natural HES (thymol–eugenol), which is readily dispersed by vortexing in 2 mL of sample. After centrifugation, the HES rich phase is diluted in 400 µL EtOH and directly injected into the GC-FID system. The proposed method has been successfully applied in the analysis and quantification of commercial fragrances, demonstrating good enrichment of target allergens and suitability for aqueous matrices analysis.