Comprehensive Two-Dimensional Gas Chromatography with Peak Tracking for Screening of Constituent Biodegradation in Petroleum UVCB Substances.

Petroleum substances, as archetypical UVCBs (substances of unknown or variable composition, complex reaction products, or biological substances), pose a challenge for chemical risk assessment as they contain hundreds to thousands of individual constituents. It is particularly challenging to determine the biodegradability of petroleum substances since each constituent behaves differently. Testing the whole substance provides an average biodegradation, but it would be effectively impossible to obtain all constituents and test them individually. To overcome this challenge, comprehensive two-dimensional gas chromatography (GC × GC) in combination with advanced data-handling algorithms was applied to track and calculate degradation half-times (DT50s) of individual constituents in two dispersed middle distillate gas oils in seawater. By tracking >1000 peaks (representing ∼53-54% of the total mass across the entire chromatographic area), known biodegradation patterns of oil constituents were confirmed and extended to include many hundreds not currently investigated by traditional one-dimensional GC methods. Approximately 95% of the total tracked peak mass biodegraded after 64 days. By tracking the microbial community evolution, a correlation between the presence of functional microbial communities and the observed progression of DT50s between chemical classes was demonstrated. This approach could be used to screen the persistence of GC × GC-amenable constituents of petroleum substance UVCBs.

The role of comprehensive two-dimensional gas chromatography in mineral oil determination.

Mineral oil hydrocarbons (MOH) contain a wide structural diversity of molecules, for which the reference method of analysis is the online coupled liquid chromatography-gas chromatography with flame ionization detection (LC-GC-FID). These compounds are very heterogeneous from a toxicological viewpoint, and an accurate risk assessment when dealing with a MOH contamination can only be performed if sufficient information is available on the types of structures present (i.e., number of carbons, degree of alkylation, number of aromatic rings). Unfortunately, the separation performances of the current LC-GC-FID method are insufficient for such characterization, not even mentioning the possible coelution of interfering compounds which additionally hinder MOH determination. Comprehensive two-dimensional gas chromatography (GC × GC), while mostly used for confirmation purposes in the past, starts to prove its relevance for overcoming the weaknesses of the LC-GC method and reaching even better the analytical requirements defined in the latest EFSA opinion. The present paper therefore aims at highlighting how GC × GC has contributed to the understanding of the MOH topic, how it has developed to meet the requirements of MOH determination, and how it could play a role in the field for overcoming many of the current analytical and toxicological challenges related to the topic.

Advances in the application of comprehensive two-dimensional gas chromatography in metabolomics.

Due to excellent separation capacity for complex mixtures of chemicals, comprehensive two-dimensional gas chromatography (GC × GC) is being utilized with increasing frequency for metabolomics analyses. This review describes recent advances in GC × GC method development for metabolomics, organismal sampling techniques compatible with GC × GC, metabolomic discoveries made using GC × GC, and recommendations and best practices for collecting and reporting GC × GC metabolomics data.

Comprehensive Two-dimensional Gas Chromatography Time-of-flight Mass Spectrometry to Assess the Presence of α,α-Trehalose and Other Disaccharides in Apple and Peach.

INTRODUCTION: Carbohydrates are important constituents in fruits. Among the carbohydrates, disaccharides have rarely been studied in apple and peach. Indeed, the abiotic stress biomarker and preservation agent α,α-trehalose is a disaccharide. OBJECTIVES: To establish a comprehensive method based on two-dimensional gas chromatography combined with time-of-flight MS detection (GC × GC-ToF/MS) to analyse the disaccharide composition of apple and peach. METHODS: The sample preparation was based on aqueous-methanolic extraction of the analytes, followed by oxime formation and trimethylsilylation of the disaccharides. First, three columns were tested with standards on the one-dimensional system. Next, to perform the sample analysis using GC × GC-MS (which offers significant advantages over conventional GC because it allows higher separation efficiencies), various column configurations were assessed on the two-dimensional system to obtain enhanced separation and low detection limits. The column sets tested included non-polar/semi-polar, semi-polar/polar and polar/non-polar. RESULTS: Using the method that proved to be more efficient, namely the method developed with the semi-polar/non-polar configuration, ten disaccharides were identified, based on analytical standards, retention index and mass spectra. These compounds were quantified in several varieties of apple and peach fruit using the developed GC × GC method and linear curve calibration, resulting in substantial differences among the fruits. However, cultivars within the fruits exhibited no significant differences. CONCLUSION: The proposed method allowed for the identification and quantification of several disaccharides in apple and peach, including the biomarker α,α-trehalose.

Detailed Speciation of Semi-Volatile and Intermediate-Volatility Organic Compounds (S/IVOCs) in Marine Fuel Oils Using GC × GC-MS.

Ship emissions contribute substantial air pollutants when at berth. However, the complexity and diversity of the marine fuels utilized hinder our understanding and mapping of the characteristics of ship emissions. Herein, we applied GC × GC-MS to analyze the components of marine fuel oils. Owing to the high separation capacity of GC × GC-MS, 11 classes of organic compounds, including b-alkanes, alkenes, and cyclo-alkanes, which can hardly be resolved by traditional one-dimensional GC-MS, were detected. Significant differences are observed between light (-10# and 0#) and heavy (120# and 180#) fuels. Notably, -10# and 0# diesel fuels are more abundant in b-alkanes (44~49%), while in 120# and 180#, heavy fuels b-alkanes only account for 8%. Significant enhancement of naphthalene proportions is observed in heavy fuels (20%) compared to diesel fuels (2~3%). Hopanes are detected in all marine fuels and are especially abundant in heavy marine fuels. The volatility bins, one-dimensional volatility-based set (VBS), and two-dimensional VBS (volatility-polarity distributions) of marine fuel oils are investigated. Although IVOCs still take dominance (62-66%), the proportion of SVOCs in heavy marine fuels is largely enhanced, accounting for ~30% compared to 6~12% in diesel fuels. Furthermore, the SVOC/IVOC ratio could be applied to distinguish light and heavy marine fuel oils. The SVOC/IVOC ratios for -10# diesel fuel, 0# diesel fuel, 120# heavy marine fuel, and 180# heavy marine fuel are 0.085 ± 0.046, 0.168 ± 0.159, 0.504, and 0.439 ± 0.021, respectively. Our work provides detailed information on marine fuel compositions and could be further implemented in estimating organic emissions and secondary organic aerosol (SOA) formation from marine fuel storage and evaporation processes.

Structural Identification and Quantification of Chlorinated Paraffins in Fish Samples Using Comprehensive Two-Dimensional Gas Chromatography with Negative Chemical Ionization Quadrupole Time-of-Flight Mass Spectrometry and Comparison to a Direct Injection-Atmospheric Pressure Chemical Ionization-Orbitrap/Mass Spectrometry Method.

This study presents a comprehensive two-dimensional gas chromatography with negative chemical ionization quadrupole time-of-flight mass spectrometry (GC × GC-NCI-QTOF/MS) method, which allows for a precise chromatographic separation of short-chain chlorinated paraffins (SCCPs) and medium-chain chlorinated paraffins (MCCPs). A new reversed-phase column setup was used, which allows for more accurate separation of MCCPs compared to known GC × GC methods. In a pilot study, 25 freshwater fish samples were analyzed with this method to characterize chlorinated paraffin (CP) compositions. The CP composition was similar in the samples, an observation that is important for the development of a suitable routine method. MCCP contamination was considerably higher than SCCP contamination, with concentrations of 1.3-410 ng/g of wet weight and 0.67-6.5 ng/g of wet weight, respectively. These results were compared to those obtained using a second method, direct injection-atmospheric pressure chemical ionization (APCI)-Orbitrap/mass spectrometry (MS). GC × GC separation was considered to be advantageous for accurate quantification of CP contamination.

Detailed qualitative analysis of honeybush tea (Cyclopia spp.) volatiles by comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry and relation with sensory data.

The volatile composition of honeybush (Cyclopia) species was studied by comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC-TOF-MS). Headspace-solid phase micro-extraction (HS-SPME) was used to extract the volatile compounds from tea infusions prepared from the three species C. genistoides, C. maculata and C. subternata. A total of 287 compounds were identified, 101 of which were confirmed using reference standards, while the remainder were tentatively identified using mass spectral and retention index (RI) data. The identification power of TOF-MS enabled the tentative identification of 147 compounds for the first time in honeybush tea. The majority of the compounds identified were common to all three Cyclopia species, although there were differences in their relative abundances, and some compounds were unique to each of the species. In C. genistoides, C. maculata and C. subternata 265, 257 and 238 compounds were identified, respectively. Noteworthy was the tentative identification of cinnamaldehyde in particular C. maculata samples, which points to the likely contribution of this compound to their distinct sensory profiles. This study emphasises the complexity of honeybush tea volatile composition and confirms the power of GC×GC combined with TOF-MS for the analysis of such complex samples.

Comprehensive two-dimensional gas chromatography-mass spectrometry combined with multivariate data analysis for pattern recognition in Ecuadorian spirits.

The current methodology used in quality control of Ecuadorian beverages such as Pájaro azúl, Puro and Pata de vaca is carried out by using conventional gas chromatography; however, it does not allow the fingerprinting of these Ecuadorian spirit beverages and their possible cases of adulteration. In order to overcome this drawback, comprehensive two-dimensional gas chromatography-mass spectrometry (GC × GC-MS) was combined with multivariate data analysis, revealing that compounds like citronellal, citronellol, geraniol, methyl anthranilate, (-)-trans-α-bergamotene, (-)-cis-α-bergamotene and D-limonene can be considered key elements for pattern recognition of these traditional beverages and product adulteration cases. Thus, the two-dimensional chromatographic fingerprints obtained by GC × GC-MS coupled with chemometric analysis, using Principal Component Analysis and Fisher-ratio can be considered as a potential strategy for adulteration recognition, and it may used as a quality assurance system for Ecuadorian traditional spirits.