A dilute-and-inject liquid-gas chromatography-mass spectrometry method for the analysis of sixteen polycyclic aromatic hydrocarbons in extra-virgin olive oil.

BACKGROUND: Polycyclic aromatic hydrocarbons (PAHs) represent a diverse group of organic compounds characterized by the fusion of two or more benzene rings arranged in various structural forms. Due to their harmful effects on human health, it is essential to implement monitoring systems and preventive measures to regulate human exposure. Given the affinity of PAHs for lipids, extensive research has been focused on their presence in vegetable oils. This study aimed to develop an on-line liquid-gas chromatography (LC-GC) method (using tandem mass spectrometry) with minimized solvent consumption for the determination of 16 PAHs in extra-virgin olive oil (EVOO). RESULTS: A side-by-side comparison of the selected-ion-monitoring and the pseudo multiple-reaction-monitoring (p-MRM) acquisition modes was performed, in terms of specificity and detectability. The results obtained using the p-MRM mode were superior, and for this reason it was selected. The method was linear over the concentration range 1-200 µg kg-1 (except in five cases, over 2-200 and 5-200 µg kg-1 ranges). Accuracy (at the 2 µg kg-1 and 20 µg kg-1 concentration levels) was in the 86.9-109.3 % range, with an RSD <10 %. Intra-day and inter-day precision (at 2 µg kg-1 and 20 µg kg-1 concentration levels) were in the 1.2-9.7 % and 3.2-10.8 % ranges, respectively. For all the PAHs, a negative matrix effect was observed. Three out of sixteen PAHs were detected in three EVOOs (among ten samples), albeit at the low ppb level. Limits of quantification were satisfactory in relation to EU legislation on the presence of PAHs in vegetable oils. SIGNIFICANCE: A dilute-and-inject LC-GC-tandem mass spectrometry method is herein proposed fulfilling EU legislation requirements; sample preparation was very simple, inasmuch that it involved only a dilution step, thus avoiding extraction, clean-up, and thus a high consumption of organic solvents. In fact, considering both oil dilution and the LC mobile phase, less than 8 mL of solvents were used.

Flow-modulation comprehensive two-dimensional enantio-gas chromatography: A valid and flexible alternative to heart-cutting multidimensional enantio-gas chromatography.

The present research is focused on the proposal of use of flow-modulation comprehensive two-dimensional enantio-gas chromatography (FM eGC × GC) as a valid, flexible, and possibly superior alternative to heart-cutting multidimensional enantio-GC (eMDGC). The latter, a technique of demonstrated utility, is used specifically for the targeted separation of chiral compounds, whereas FM eGC × GC can produce both targeted and high-resolution untargeted information in a single run. It is clearly possible to use eMDGC for untargeted analysis, often with a flame ionization detector (stand-by analysis), to monitor a first-dimension (1D) separation, of much lower peak capacity compared to FM eGC × GC. If eMDGC is used with mass spectrometry (MS), it is normally exploited to monitor the second-dimension (2D) separation. The analytical instrument consisted of automated solid-phase microextraction (SPME), and a low duty-cycle FM eGC × GC system (with time-of-flight MS), equipped with an enantioselective 1D column (2,3-di-O-methyl-6-t-butyl silyl ß-cyclodextrin derivative) and a 2D polyethylene glycol one. Ten Marsala wines were subjected to analysis, for the determination of chiral lactones (many at the low ppb level, due to the high concentration capacity of SPME) and for general analyte profiling. In many instances, highly complex chromatograms were attained, with statistical analysis (ANOVA-simultaneous component analysis and partial least squares discriminant analysis) used for sample differentiation.

Determination of mineral oil hydrocarbon contamination in Citrus essential oils by using on-line liquid-gas chromatography: critical aspects.

The present manuscript reports and discusses critical issues related to the determination of mineral oil hydrocarbon contamination in Citrus essential oils (EOs); an on-line liquid-gas chromatography system equipped with a Y-interface was used (with no additional off-line step for pre-concentration). In total, eighteen samples were analyzed, specifically eleven cold-pressed (CP) and seven distilled EOs. With regard to the CP EOs, various degrees of mineral oil saturated hydrocarbon (MOSH) contamination were detected, ranging between 10.7 and 338.4 mg kg-1 (only one sample was MOSH-free); different MOSH sub-fractions were determined, with the > C25- ≤ C35 sub-fraction always present, with an average concentration of 74.5 mg kg-1. Based on the EO composition, different sample amounts were injected to avoid the overloading of the LC column and consequently the GC one, thus leading to different limits of quantification (LoQ), which were either 2 mg kg-1 (for bergamot EO) or 5 mg kg-1 (for all the other investigated samples). For all samples, the mineral oil aromatic hydrocarbon level was always lower than the LoQ.

Direct extraction with acetonitrile of hemp seed oil for the analysis of pesticides by using comprehensive two-dimensional gas chromatography-triple quadrupole mass spectrometry.

The method herein described involves a rapid and limited-volume (0.5 mL of acetonitrile) solvent-extraction sample preparation process, for pesticide determination in hemp seed oil. The extraction method was characterized by the absence of both clean-up or pre-concentration steps. The extracts were directly analyzed through cryogenic-modulation comprehensive two-dimensional gas chromatography coupled to triple quadrupole mass spectrometry. The novelty characterizing the present research [compared to a previous one (Arena et al., 2023)] is related to the extension of the number of pesticides (97), and to the investigation of a more challenging matrix, contained in a vegetable oil of increasing interest among consumers. Linearity, limits of detection and quantification, accuracy, precision, recovery, and matrix effect were measured. Particular emphasis was devoted to the matrix effect, with the co-extracted matrix amount defined. Three international regulations (Canada, California, Europe) were considered, and the obtained limits of quantification were found to be too high in five (Canada) and twelve (Europe) cases, for a total number of 15 pesticides. The analysis of ten commercial samples showed the presence of seven pesticide residues in four of them, at concentration levels ranging from 0.02 to 0.98 mg kg-1, with most over the regulation residue limits.

A dilute-and-inject low-pressure gas chromatography-tandem mass spectrometry method for phthalate determination in extra virgin olive oil.

The goal of this study was to develop a method for the determination of nine phthalic acid esters in extra virgin olive oils using low-pressure gas chromatography-triple-quadrupole mass spectrometry. Sample preparation was simple, environmental friendly, and rapid inasmuch that it involved only dilution (< 1 mL of hexane). The low-pressure gas chromatography analyses were performed by using a 5 m wide-bore column. The limit of quantification for the phthalates ranged from 0.06 to 1.14 mg kg-1 . Both intra- and interday precisions were measured, with coefficient of variation values ranging from 0.2% to 11.7%. The trueness of the method was measured by evaluating accuracy at the initial stage of the work and after 2 months, with values ranging between -8.7% and 12.1%. Moreover, blind accuracy was comprised between -11.6% and 14.2%. The method involves the use of simplified instrumentation and reduced analysis times (nearly two times faster) compared to a previously published comprehensive two-dimensional gas chromatography-triple-quadrupole mass spectrometry method, leading to a reduction of energy and helium consumption. The approaches were compared in analytical terms and for the environmental impact. In total, 23 olive oil samples were analyzed, with at least one phthalate detected in all but one sample.

Potential of GC-Combustion-MS as a Powerful and Versatile Nitrogen-Selective Detector in Gas Chromatography.

Here, we show the potential and applicability of the novel GC-combustion-MS approach as a nitrogen-selective GC detector. Operating requirements to achieve reproducible and compound-independent formation of volatile NO species as a selective N-signal during the combustion step are described. Specifically, high temperatures (≥1000 °C) and post-column O2 flows (0.4 mL min-1 of 0.3% O2 in He) turned out to be necessary when using a vertical oven without makeup flow (prototype #1). In contrast, the use of a horizontal oven with 1.7 mL min-1 He as an additional makeup flow (prototype #2) required milder conditions (850 °C and 0.2 mL min-1). A detection limit of 0.02 pg of N injected was achieved, which is by far the lowest ever reported for any GC detector. Equimolarity, linearity, and peak shape were also adequate. Validation of the approach was performed by the analysis of a certified reference material obtaining accurate (2% error) and precise (2% RSD) results. Robustness was tested with the analysis of two complex samples with different matrices (diesel and biomass pyrolysis oil) and N concentration levels. Total N determined after the integration of the whole chromatograms (524 ± 22 and 11,140 ± 330 µg N g-1, respectively) was in good agreement with the reference values (497 ± 10 and 11,000 ± 1200 µg N g-1, respectively). In contrast, GC-NCD results were lower for the diesel sample (394 ± 42 µg N g-1). Quantitative values for the individual and families of N species identified in the real samples by parallel GC-MS and additional GC × GC-MS analyses were also obtained using a single generic internal standard.

A method for the determination of 70 pesticides in extra virgin olive oil based on a limited-volume solvent extraction step prior to comprehensive two-dimensional gas chromatography-tandem mass spectrometry.

The goal of the present research was to develop a method based on a miniaturized solvent extraction step (using only 500 µL of acetonitrile, with no further clean-up or concentration processes) prior to cryogenic-modulation comprehensive two-dimensional gas chromatography-tandem mass spectrometry for the determination of seventy pesticides in extra virgin olive oil, exploiting the enhanced specificity and sensitivity of this technique. Limits of quantification were always below European legislation residue limits, intra-day precision was between 0.3 and 4.9% (at the 50 and 100 µg kg-1 concentration levels), inter-day precision was between 1.6 and 6.1% (at the 100 µg kg-1 concentration level), recovery (at the 20, 50, and 100 µg kg-1 concentration levels) was in the 14-120% range, accuracy at the initial stage of the work (within repeatability conditions) was between 79 and 110%, while accuracy after 3 months (within intermediate precision conditions) was between 91 and 121% (at the 50 and 100 µg kg-1 concentration levels). Finally, the matrix effect was always positive, between 16 and 197%. The method was applied to the investigation of twenty samples, and eleven of these were found to be contaminated.

Direct analysis of phthalate esters in vegetable oils by means of comprehensive two-dimensional gas chromatography combined with triple quadrupole mass spectrometry.

Phthalic acid esters (PAEs), known as phthalates, have a variety of industrial applications, mainly related to their ability to increase plastic softness,flexibility, and durability. With regard to toxicological aspects, several studies suggest that phthalates would act as endocrine-disrupting chemicals, and they have been correlated to several forms of cancer. Since the analysis of PAEs in food is challenging, the aim of this study was the development of a simple and direct method, with no sample preparation (only dilution withsolvent), for the analysis of targeted phthalates in vegetable oils, by using cryogenic-modulation comprehensive two-dimensional gas chromatography combined with triple quadrupole mass spectrometry. The method was characterized by good repeatability values, limit of quantification values ranging between 0.06 and 2.10 mg/kg, accuracy values ranging from -9.2 to 10.4%, and a matrix effectranging from -4 to 78%.The developed technique was used for the analysis of 27 vegetable oils.

Flow-modulated comprehensive two-dimensional gas chromatography combined with time-of-flight mass spectrometry: use of hydrogen as a more sustainable alternative to helium.

The present research is focused on the use and evaluation of hydrogen, as a more sustainable alternative to helium, within the context of fast flow modulation comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry. In such a respect, a comparison was made between the two mobile phases in terms of speed and overall chromatography performance. All experiments were carried out by using the following column set: low polarity with dimensions 10 m × 0.25 mm ID × 0.25 µm df and medium polarity with dimensions 2 m × 0.10 mm ID × 0.10 µm df. Fundamental gas chromatography parameters (efficiency, resolution) were measured under different experimental conditions, using the two carrier gases. Efficiency was measured in both the first and second dimensions, using a probe compound under isothermal conditions; after defining the optimum carrier gas conditions, a mixture containing 20 pesticides was analyzed to measure resolution, again in the first and second dimensions, using a temperature program. It was found (as expected) that a similar chromatography performance could be attained when using hydrogen, albeit with a circa 25% reduction in analysis time. Signal-to-noise ratios of the pesticides were calculated, using both carrier gases, with such values generally reduced (on average by 14%) when using hydrogen. Finally, a comparison was made between mass spectral profiles obtained analyzing the pesticides and fatty acid methyl esters using the two mobile phases. Even though mass spectral differences were observed, the ion profiles could be considered generally similar.

On-line coupling of supercritical fluid extraction with enantioselective supercritical fluid chromatography-triple quadrupole mass spectrometry for the determination of chiral pesticides in hemp seeds: A proof-of-principle study.

The present research can be considered as a proof-of-principle study focused on the determination of chiral pesticides using a supercritical fluid extraction instrument coupled on-line with an enantioselective supercritical fluid chromatography-triple quadrupole mass spectrometry. To the best of Authors' knowledge, this is the first description of an on-line approach for the extraction and determination of chiral pesticides. Metalaxyl, benalaxyl and dimethenamid were investigated in nine hemp seed samples belonging to four varieties of Cannabis sativa; only in one case a pesticide was found at levels above the method limit of quantification (LoQ), though within the EU maximum residue level value. The figures-of-merit determined were linearity, precision, limit of detection (LoD), and LoQ. Regression coefficients were between 0.9856 and 0.9973, the LoDs were in the 0.04-0.41 µg kg-1 range, the LoQs were in the 0.12-1.38 µg kg-1 range, while coefficients of variation were between 1 and 3% (10 µg kg-1 level).

Untargeted profiling and differentiation of geographical variants of wine samples using headspace solid-phase microextraction flow-modulated comprehensive two-dimensional gas chromatography with the support of tile-based Fisher ratio analysis.

The volatile fraction of food, also called the food volatilome, is increasingly used to develop new fingerprinting approaches. The characterization of the food volatilome is important to achieve desired flavor profiles in food production processes, or to differentiate different products, with winemaking being one popular area of interest. In the present research, headspace solid-phase microextraction (HS SPME) coupled to flow-modulated comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (FM GC×GC-TOFMS) was used to characterize geographical-based differences in the volatilome of five white "Grillo" wines (of Sicilian origin), comprising the five sample classes. All wines were produced with the same vinification method in 2019. To minimize the influence of minor bottle-to-bottle differences, three bottles of the same wine were randomly selected, and three samples were collected per bottle, resulting in nine sample replicates per wine. Particular emphasis was devoted to the operational conditions of a novel low duty cycle flow modulator. A fast FM GC×GC-TOFMS method with a modulation period of 700 ms and a re-injection period of 80 ms was developed. Following, the instrumental software was exploited to identify class-distinguishing analytes in the dataset via tile-based Fisher ratio analysis (i.e., ChromaTOF Tile). A tile size of 10 modulations (7 s) on the first dimension and 45 spectra (300 ms) on the second dimension was used to encompass average peak widths and to account for minor retention time shifting. Off-line software was used to apply an ANOVA test. A p-value of 0.01 was applied in order to select the most important class-distinguishing analytes, which were input to principal component analysis (PCA). The PCA scores plot showed distinct clustering of the wines according to geographical origin, although the loadings revealed that only a few analytes were necessary to differentiate the wines. However, a comprehensive flavor profile assessment underscored the importance of all the information output by the ChromaTOF Tile software.

Occurrence of Mineral Oil Hydrocarbons in Omega-3 Fatty Acid Dietary Supplements.

Omega-3 fatty acid dietary supplements have become increasingly popular with consumers due to their multiple health benefits. In this study, the presence of mineral oil hydrocarbons (MOH) was investigated in seventeen commercial samples of such supplements, characterized by different formulations. The analyses were performed using on-line liquid chromatography-gas chromatography (with flame ionization detection), which is considered the most efficient method for the determination of MOH in foodstuffs. Analyte transfer was performed by using the retention gap technique, with partially concurrent solvent evaporation. Various degrees of mineral oil saturated hydrocarbon contamination (from 2.4 ppm to 375.7 ppm) were found, with an average value of 49.9 ppm. Different C-number range contaminations were determined, with the >C25-≤C35 range always found with an average value of 26.9 ppm. All samples resulted free of mineral oil aromatic hydrocarbons, except for two samples in which a contamination was found at the 9.9 and 6.6 ppm levels, respectively.

Use of a low-cost, lab-made Y-interface for liquid-gas chromatography coupling for the analysis of mineral oils in food samples.

Consumers are daily exposed to a range of mineral oil hydrocarbons via food consumption. Major sources of MOH in food are packaging and additives, processing aids, and lubricants. In 2019, an EU guidance was released covering specific directions for sampling and analysis of mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH) in food and food contact materials within the frame of Recommendation (EU) 2017/84 for the monitoring of mineral oils. The parameters required by the guide are increasingly stringent, and coping with this type of analysis is now very challenging. It is within such a context that the present research is confined, inasmuch that it is focused on the construction of a low-cost, lab-made Y-interface for liquid-gas chromatography coupling used for the determination of MOSH and MOAH in foodstuffs. The response ratios of alkanes comprised between C10 and C50 were measured and were comprised between 0.9 and 1.1, with a maximum coefficient of variation of 4% (n = 5). Intermediate precision was evaluated for the fat/oil category during a period of 48 days obtaining a value of 10%. Qualitative and quantitative analysis of both MOSH and MOAH were performed in a single run and in a fully-automated manner. Seventeen different foods were analyzed in order to cover the categories reported in the EU guide. Saturated hydrocarbon contamination was detected only in a few samples (in the range 1-153 ppm); MOAH contamination was found only in one sample (sunflower oil: 15 ppm).

Development of a Novel Microwave Distillation Technique for the Isolation of Cannabis sativa L. Essential Oil and Gas Chromatography Analyses for the Comprehensive Characterization of Terpenes and Terpenoids, Including Their Enantio-Distribution.

A microwave distillation method was optimized for the extraction and isolation of cannabis essential oil from fresh and dried hemp inflorescences. The developed method enabled us to obtain a distilled product rich in terpenes and terpenoid compounds, responsible of the typical and unique smell of the cannabis plant. The distillate from different hemp cultivars, including Kompolti, Futura 75, Carmagnola, Felina 32 and Finola were characterized by using a gas chromatograph equipped with both mass spectrometer and flame ionization detectors. In a single chromatographic run, the identity and absolute amounts of distilled compounds were determined. Peak assignment was established using a reliable approach based on the usage of two identification parameters, named reverse match, and linear retention index filter. Absolute quantification (mg g-1) of the analytes was performed using an internal standard method applying the flame ionization detector (FID) response factors according to each chemical family. An enantio-GC-MS method was also developed in order to evaluate the enantiomeric distribution of chiral compounds, an analytical approach commonly utilized for establishing the authenticity of suspicious samples.

Determination of multi-pesticide residues in vegetable products using a "reduced-scale" Quechers method and flow-modulated comprehensive two-dimensional gas chromatography-triple quadrupole mass spectrometry.

The aim of the present research was the development of an analytical method for the determination of multi-pesticide residues (88 target analytes) in four vegetable products (tomatoes, cucumbers, sweet red peppers and iceberg lettuce) using a "reduced-scale" QuEChERS (quick, easy, cheap, effective, rugged, and safe) extraction method and flow-modulated comprehensive two-dimensional gas chromatography-triple quadrupole mass spectrometry. In particular, the suitability of flow modulation [with relatively high second-dimension gas flow conditions (8 mL min-1)] for trace analyte determination was evaluated. The samples were prepared according to the QuEChERS procedure as reported by the official European Union method, namely EN 15662:2018, based on the use of 3 g of vegetable product. Matrix-matched calibration processes were carried out for all the samples. The figures-of-merit determined were recovery, linearity, precision, limits of detection (LoDs), and limits of quantification (LoQs). Specifically, recoveries were in the 53-160% range, regression coefficients were between 0.9156 and 0.9999, the LoDs were in the 0.1-6.3 µg kg-1 range, the LoQs were in the 3.0-21.0 µg kg-1 range, and coefficients of variation were between 1 and 28% (at the 50 µg kg-1 level).

Preliminary observations on the use of a novel low duty cycle flow modulator for comprehensive two-dimensional gas chromatography.

The present research is focused on the preliminary evaluation, in particular in relation to the advisable operational conditions, of a novel low duty cycle flow modulator. In such a respect, a fast comprehensive two-dimensional gas chromatography-mass spectrometry method is herein proposed. Applications on a C7-C30 series of alkanes, 64 fragrance allergens (plus 2 internal standards), and 5 perfumes, were carried out by using two different column sets, low-polarity + medium-polarity and low-polarity + low-polarity. In both cases, the first column was of dimensions 10 m × 0.25 mm ID × 0.25 µm df, while the second one was of dimensions 1 m × 0.10 mm ID × 0.10 µm df. A modulation period of 700 ms, with a re-injection period of 80 ms, was used in order to obtain a higher duty cycle (measured to be approx. 0.04). Absolute quantification of the allergens was carried out by using two internal standards, namely 1,4-dibromobenzene and 4,4'-dibromobiphenyl. In terms of limits of quantification the instrumental response was characterized by a wide variability, ranging between 9 ppb and 5.4 ppm for both column sets. A total number of 97 fragrance allergens were identified and quantified in five commercial perfumes.

A unique data analysis framework and open source benchmark data set for the analysis of comprehensive two-dimensional gas chromatography software.

Comprehensive two-dimensional gas chromatography (GC × GC) is amongst the most powerful separation technologies currently existing. Since its advent in early 1990, it has become an established method which is readily available. However, one of its most challenging aspects, especially in hyphenation with mass spectrometry is the high amount of chemical information it provides for each measurement. The GC × GC community agrees that there, the highest demand for action is found. In response, the number of software packages allowing for in-depth data processing of GC × GC data has risen over the last couple of years. These packages provide sophisticated tools and algorithms allowing for more streamlined data evaluation. However, these tools/algorithms and their respective specific functionalities differ drastically within the available software packages and might result in various levels of findings if not appropriately implemented by the end users. This study focuses on two main objectives. First, to propose a data analysis framework and second to propose an open-source dataset for benchmarking software options and their specificities. Thus, allowing for an unanimous and comprehensive evaluation of GC × GC software. Thereby, the benchmark data includes a set of standard compound measurements and a set of chocolate aroma profiles. On this foundation, eight readily available GC × GC software packages were anonymously investigated for fundamental and advanced functionalities such as retention and detection device derived parameters, revealing differences in the determination of e.g. retention times and mass spectra.

A lab-developed interface for liquid-gas chromatography coupling based on the use of a modified programmed-temperature-vaporizing injector.

The main focus of the present research was the on-line coupling of two separation techniques, namely liquid chromatography (LC) and gas chromatography (GC). For such an analytical combination, a dedicated interface is required to remove solvent from the sample, leaving the latter in a sharp band at the head of the GC column. Considering such an objective, a lab-developed LC-GC interface is herein presented, based on the use of a six-port two-position valve and a programmed-temperature-vaporizing (PTV) injector. The PTV injector was derived from a commercial split/splitless injector body, heated using a resistance heating wire, and enabled a satisfactory recovery of low boiling compounds (≤ C13), working in the normal-phase mode. The lab-developed PTV injector allowed the use of a larger-volume liner (compared to the commercial one initially used), it being characterized by dimensions 95 mm length × 5.0 mm O.D. × 3.4 mm I.D. and a volume of 862 µL, thus facilitating the transfer of larger LC fractions. The developed system is fully automatized and controlled without the use of additional software. The interface was evaluated and used for the analysis of mineral oil saturated hydrocarbons in vegetable oils. Detection was carried out by using a flame ionization detector (FID), with quantification performed through external calibration, across the 5-1000 mg kg-1 range. The LC-GC-FID method linearity, limits of detection and quantification, accuracy and precision were measured. The resulting limits of detection and quantification values were 0.4 and 1.3 mg kg-1, respectively. The average accuracy at the 100 mg kg-1 level was 95.5% (ranging between 93.3 and 99.7%). Intra-day repeatability at levels of 5 and 100 mg kg-1 were 2.4% and 3.5%, respectively.

Towards the determination of an equivalent standard column set between cryogenic and flow-modulated comprehensive two-dimensional gas chromatography.

This preliminary research is focused on the task of defining an equivalent standard column set between cryogenic and flow-modulation comprehensive two-dimensional gas chromatography (GC × GC) combined with mass spectrometry (MS). Cryogenic modulation (CM) was carried out by using a loop-type device, while the flow modulator used was a seven-port wafer chip, equipped with an external accumulation loop. Initially, a common low-polarity + mid-polarity CM GC × GC column set was selected (30 m × 0.25 mm ID × 0.25 µm df + 1.5 m × 0.25 mm ID × 0.25 µm df), a method was developed, and a GC × GC-MS fingerprint was attained (on a sample of bio-oil derived from coconut fibers). After, a column set with the same stationary phases was selected for the flow modulation GC × GC-MS method (20 m × 0.18 mm ID × 0.18 µm df + 5 m × 0.32 mm ID × 0.25 µm df), with the capability to provide a-similar-as-possible separation. A side-by-side measurement of several chromatography parameters (efficiency, peak capacity, resolution, peak widths, retention factors, elution temperatures) was made.

In-Depth Qualitative Analysis of Lime Essential Oils Using the Off-Line Combination of Normal Phase High Performance Liquid Chromatography and Comprehensive Two-Dimensional Gas Chromatography-Quadrupole Mass Spectrometry.

The present research is focused on the in-depth qualitative analysis of three types of lime essential oil (EO), viz., Key (A and B) and Persian, using the off-line combination of normal phase high performance liquid chromatography (NP-HPLC) and comprehensive two-dimensional gas chromatography-quadrupole mass spectrometry (GC × GC-QMS). The first analytical dimension (NP-HPLC) was exploited for the isolation of the hydrocarbon constituents from the oxygenated ones. Each fraction was then reduced in volume and analyzed using (cryogenic modulation) GC × GC-QMS. Peak assignment was carried out through the combined use of mass spectral database and linear retention index matching processes. The powerful four-dimensional technology enabled the separation and identification of a very high number (153) of lime essential oil volatile compounds.