GC × GC-HRMS with complementary ionization methods in the suspect screening analysis of fragrance allergens: overwhelming or justified?

Modern gas chromatography-mass spectrometry (GC-MS) allows for the analysis of complex samples, such as fragrances. However, identifying all the constituents in natural fragrance mixtures, especially allergens that need to be listed on product labels, is a significant challenge. This is primarily due to the high complexity of the sample and the fact that electron ionization, the most commonly used ionization method in GC-MS, produces numerous nonspecific fragment ions, often resulting in the absence or very low abundance of the molecular ion. These factors affect confidence in assigning the analyte. In this study, we demonstrate that the combination of GC × GC separation, with high mass resolution and accurate mass measurements, as well as chemical ionization in addition to traditional electron ionization, becomes an efficient tool for reliable qualitative analysis of a mixture containing 100 fragrance allergens, even when many of them are closely related species or isomers. The proposed approach expands the applicability of the comprehensive GC × GC-HRMS method, which includes complementary ionization techniques, from studies on anthropogenic priority pollutants and emerging contaminants to the analysis of natural products. Although targeted qualitative and quantitative analysis of allergens in the modern laboratories is well organized, GC × GC-HRMS, being a useful complement to routine quality control of volatile allergens in fragrances, definitely gives an additional contribution to the analytical cases when conventional 1D-GC-MS faces some problems or uncertainties.

Forensic significance of VOCs profiling in decayed ante- and post-mortem injuries by GC×GC-TOF/MS.

Accurately identifying and differentiating the types of injuries in decomposed corpses is a major challenge in forensic identification. Forensic investigations involving decomposed cadavers pose challenges in determining the cause of death. Traditional methods often lack conclusive evidence. However, the implementation of advanced analytical techniques, such as comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC × GC-TOF/MS), shows promise in overcoming these limitations, but the potential in this area remains limited. Therefore, this study aims to bridge this gap by exploring the potential of GC × GC-TOF/MS in the analysis of volatile organic compounds (VOCs) changes within decaying ante- and post-mortem injuries.The research emphasizes the forensic significance of VOCs changes in decomposed cadavers. We used GC × GC-TOF/MS analysis to identify the specific volatile compounds in putrefied corpse tissue samples from mice. The GC × GC-TOF/MS analysis results showed that under winter conditions, PC1 explained 57.16% of the variance, and PC2 explained 25.23% of the variance; while under summer conditions, PC1 explained 71.89% of the variance, and PC2 explained 24.49% of the variance. This demonstrates the potential of GC × GC-TOF/MS in identifying specific VOCs present in tissue samples that can serve as potential biomarkers for distinguishing between antemortem and postmortem injury. GC × GC-TOF/MS analysis revealed distinct VOC patterns in both conditions. Comprehensive use of GC × GC-TOF/MS analysis enhances accuracy in identifying and characterizing ante- and post-mortem injuries in decomposed cadavers. This study can significantly contribute to the field of forensic medicine and improve the accuracy of forensic investigations.

Impact of deodorisation time and temperature on the removal of different MOAH structures: a lab-scale study on spiked coconut oil.

Vegetable fats and oils are prone to contamination by mineral oil hydrocarbons due to the lipophilic and ubiquitous character of the latter. As the aromatic fraction of these hydrocarbons, MOAH, is associated with carcinogenicity, mutagenicity, and detrimental effects on foetal development, finding strategies to limit or reduce their contamination is highly relevant. Deodorisation (i.e. a refining step) has shown the ability to remove MOAH < C25 in vegetable fats and oils, but there is little information about the structures removed. Therefore, the present study investigated the impact of deodorisation conditions on the removal of different structures of MOAH in spiked coconut oil. An inscribed central composite design was built with time and temperature as variables (0.5-4h, 150-240 °C), while pressure (3 mbar) and steam flow (1 g water/g oil per hour) were kept constant. The analysis of MOAH in the oil was performed using a fully automated liquid chromatography coupled with two parallel comprehensive two-dimensional gas chromatography systems with flame ionisation and time-of-flight mass spectrometric detection. Response surfaces plotting the MOAH loss according to time and temperature were built for different MOAH fractions. The latter were defined based on the number of aromatic rings (>3 or ≤3) and the number of carbon atoms present (C16-C20, C20-C24, C24-C35, C35-C40). It was found that at 200 °C, compounds < C24, including weakly alkylated triaromatics, could be reduced to below the limit of quantification, while at 230 °C, it was possible to remove >60% of the C24-C35 fraction, including pentaromatics of low alkylation.

The influence of drying and storage conditions on the volatilome and cannabinoid content of Cannabis sativa L. inflorescences.

The increasing interest in hemp and cannabis poses new questions about the influence of drying and storage conditions on the overall aroma and cannabinoids profile of these products. Cannabis inflorescences are subjected to drying shortly after harvest and then to storage in different containers. These steps may cause a process of rapid deterioration with consequent changes in precious secondary metabolite content, negatively impacting on the product quality and potency. In this context, in this work, the investigation of the effects of freeze vs tray drying and three storage conditions on the preservation of cannabis compounds has been performed. A multi-trait approach, combining both solid-phase microextraction (SPME) two-dimensional gas chromatography coupled to mass spectrometry (SPME-GC × GC-MS) and high-performance liquid chromatography (HPLC), is presented for the first time. This approach has permitted to obtain the detailed characterisation of the whole cannabis matrix in terms of volatile compounds and cannabinoids. Moreover, multivariate statistical analyses were performed on the obtained data, helping to show that freeze drying conditions is useful to preserve cannabinoid content, preventing decarboxylation of acid cannabinoids, but leads to a loss of volatile compounds which are responsible for the cannabis aroma. Furthermore, among storage conditions, storage in glass bottle seems more beneficial for the retention of the initial VOC profile compared to open to air dry tray and closed high-density polyethylene box. However, the glass bottle storage condition causes formation of neutral cannabinoids at the expenses of the highly priced acid forms. This work will contribute to help define optimal storage conditions useful to produce highly valuable and high-quality products.

Comprehensive Two-Dimensional Gas Chromatography with a TOF MS Detector-An Effective Tool to Trace the Signature of Grape Varieties.

Varietal volatile compounds are characteristic of each variety of grapes and come from the skins of the grapes. This work focuses on the development of a methodology for the analysis of free compounds in grapes from Trincadeira, Cabernet Sauvignon, Syrah, Castelão and Tinta Barroca from the 2021 and 2022 harvests, using HS-SPME-GC × GC-TOFMS. To achieve this purpose, a previous optimization step of sample preparation was implemented, with the optimized conditions being 4 g of grapes, 2 g of NaCl, and 2 mL of H2O. The extraction conditions were also optimized, and it was observed that performing the extraction for 40 min at 60 °C was the best for identifying more varietal compounds. The fiber used was a triple fiber of carboxen/divinylbenzene/polydimethylsiloxane (CAR/DVB/PDMS). In addition to the sample preparation, the analytical conditions were also optimized, enabling the adequate separation of analytes. Using the optimized methodology, it was possible to identify fifty-two free volatile compounds, including seventeen monoterpenes, twenty-eight sesquiterpenes, and seven C13-norisoprenoids. It was observed that in 2021, more free varietal volatile compounds were identifiable compared to 2022. According to the results obtained through a linear discriminant analysis (LDA), the differences in volatile varietal signature are observed both among different grape varieties and across different years.

Non-target screening and prioritization of organic contaminants in seawater desalination and their ecological risk assessment.

The impact of desalination brine on the marine environment is a global concern. Regarding this, salinity is generally accepted as the major environmental factor in desalination concentrate. However, recent studies have shown that the influence of organic contaminants in brine cannot be ignored. Therefore, a non-targeted screening method based on comprehensive two-dimensional gas chromatography-quadrupole mass spectrometry (GC × GC-qMS) was developed for identifying organic contaminants in the desalination brine. A total of 404 compounds were tentatively identified from four seawater desalination plants (three reverse osmosis plants and one multiple effect distillation plant) in China. The identified compounds were prioritized based on their persistence, bioaccumulation, ecotoxicity, usage, and detection frequency. Twenty-one (21) compounds (seven phthalates, ten pesticides, four trihalomethanes) were then selected for further quantitative analysis and ecological risk assessment, including compounds from the priority list along with substances from the same chemical classes. Ecologically risky substances in brine include diisobutylphthalate and bis(2-Ethylhexyl) phthalate, atrazine and acetochlor, and bromoform. Most of the contaminants come from raw seawater, and no high risk contaminants introduced by the desalination process have been found except for disinfection by-products. In brine discharge management, people believed that all pollution in raw seawater was concentrated by desalination process. This study shows that not all pollutants are concentrated during the desalination process. In this study, the total concentration of pesticide in the brine increased by 58.42%. The concentration of ∑PAEs decreased by 13.65% in reverse osmosis desalination plants and increased by 10.96% in the multi-effect distillation plant. The concentration of trihalomethane increased significantly in the desalination concentrate. The change in the concentration of pollutants in the desalination concentrate was related to the pretreatment method and the chemical characteristics of the contaminants. The method and results given in this study hinted a new idea to identify and control the environmental impact factors of brine.

The Characterization of the Key Aroma Compounds in Non-Smoked Bacon by Instrumental and Sensory Methods.

The aroma profiles in non-smoked bacon were investigated via GC-O-MS, GC × GC-TOFMS, and GC-IMS. GC-O-MS is advantageous for detecting aldehydes. GC × GC-TOFMS is more sensitive to hydrocarbons and alcohols, while GC-IMS detects a balanced range of categories. Only 9 of the 239 detected volatiles were identifiable by all three methods. Therefore, the combination of all three methods proved to be the most effective way to comprehensively analyze the aroma profiles of bacon. Recombination and omission tests were performed using aroma compounds with a flavor dilution (FD) factor greater than 27; five volatiles were identified as key aroma compounds in non-smoked bacon, including hexanal, (E,E)-2,4-decadienal, 1-octen-3-ol, dihydro-5-pentyl-2(3H)-furanone, and 3-methyl-butanoic acid. Among these, hexanal and 1-octen-3-ol exhibited relatively high FD factors and odor activity values (OAVs), so they were confirmed as the primary contributors. Meanwhile, seven volatiles contributed to the unique aroma of non-smoked bacon in different regions. The difference in the aroma of bacon in different regions is mainly due to the content of various volatiles rather than the type. A comprehensive analysis of the aroma in non-smoked bacon can reveal theoretical information for improving the process and quality control of the product.

Characterization and comparison of flavors in fresh and aged fermented peppers: Impact of different varieties.

The flavor profiles of fresh and aged fermented peppers obtained from four varieties were thoroughly compared in this study. A total of 385 volatile compounds in fermented pepper samples were detected by flavoromics (two-dimensional gas chromatography-time-of-flight mass spectrometry). As fermentation progressed, both the number and the total concentration of volatile compounds changed, with esters, alcohols, acids, terpenoids, sulfur compounds, and funans increasing, whereas hydrocarbons and benzenes decreased. In contrast to the fresh fermented peppers, the aged fermented samples exhibited lower values of pH, total sugars, and capsaicinoids but higher contents of organic acids and free amino acids. Furthermore, the specific differences and characteristic aroma substances among aged fermented peppers were unveiled by multivariate statistical analysis. Overall, 64 volatiles were screened as differential compounds. In addition, Huanggongjiao samples possessed the most abundant differential volatiles and compounds with odor activity values > 1, which were flavored with fruity, floral, and slightly phenolic odors. Correlation analysis demonstrated that the levels of 23 key aroma compounds (e.g., ethyl 2-methylbutyrate, 1-butanol, and ethyl valerate) showed a significantly positive correlation with Asp, Glu and 5 organic acids. By contrast, there is a negative association between the pH value and total sugar. Overall, aging contributed significantly to the flavor attributes of fermented peppers.

Nontarget screening analysis of organic compounds in river sediments: a case study in the Taipu River of the Yangtze River Delta Region in China.

Sediments are the vital fate of organic compounds, and the recognition of organic compounds in sediments is constructive in providing comprehensive and long-term information. In this study, a three-step nontarget screening (NTS) analysis workflow using comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC × GC-TOFMS) revealed the extensive existence of organic compounds in the Taipu River sediment. Organic compounds (705) were detected and divided into four structure-related groups or eight use-related classes. In the Taipu River's mainstream, a significant difference was found in the composition profiles of the identified organic compounds among various sites, demonstrating the organic compounds were more abundant in the midstream and downstream than in the upstream. Meanwhile, the hydrodynamic force was recognized as a potential factor influencing organic compounds' occurrence. Based on multiple statistical analyses, the shipping and textile printing industries were considered the significant contributors to the identified organic compounds. Considering the principles of the priority substances and the current status of the substances, two traditional pollutants and ten emerging organic compounds were recognized as the priority organic compounds for the Taipu River. Conclusively, this study established a workflow for NTS analysis of sediment samples and demonstrated the necessity of NTS analysis to evaluate the impact of terrestrial emissions of organic compounds on the aquatic environment.

Short- and medium-chain chlorinated paraffins in breast milk in Shanghai, China: Occurrence, characteristics, and risk assessment.

As novel contaminants, short-chain chlorinated paraffins (SCCPs) and medium-chain chlorinated paraffins (MCCPs) have been of great concern in the past several years. Shanghai was one of the provinces with the largest chlorinated paraffins (CPs) emission in China; nevertheless, there is currently little information on the human exposure to SCCPs and MCCPs, particularly MCCPs. In this study, 25 breast milk samples were collected in Shanghai from 2016 to 2017. The concentrations of SCCPs and MCCPs were determined using two-dimensional gas chromatography coupled with orbitrap high-resolution mass spectrometry (GC × GC-orbitrap-HRMS) to investigate their characteristics and assess the associated health risks for breast-fed infants. Compared with the previous studies in other areas, the current study presented the higher CPs concentrations, with median concentrations of SCCPs and MCCPs up to 771 and 125 ng/g lipid weight (lw), respectively. The exposure profiles of the CPs were characterized by C10 and Cl6-7 as the predominant congeners of SCCPs, while C14 and Cl7-9 were identified as the dominant groups of MCCPs. CP-42 and CP-52 were identified as potential sources of CPs found in breast milk samples collected in Shanghai. The concentrations of MCCPs exhibited a positive correlation (p value < 0.05) with the dietary consumption of meat and poultry. No significant positive correlations were observed for SCCPs and MCCPs with polychlorinated dibenzodioxins/furans (PCDD/Fs) congeners. A preliminary exposure assessment showed that SCCPs in breast milk potentially posed high risks to the breast-fed infants in Shanghai.

Characterization of odor profiles of pea milk varieties and identification of key odor-active compounds by molecular sensory science approaches using soybean milk as a reference.

This study investigated the odor profiles of four pea milk varieties based on sensory evaluation, electronic nose (E-nose), and gas chromatography-mass spectrometry (GC-MS) with soybean milk as a reference. Compared to soybean milk, pea milk exhibited lower intensity of beany, oil-oxidation, and mushroom flavors as well as higher intensity of grassy/green and earthy flavors. ZW.6 pea milk was selected for further identification of key odor-active compounds using molecular sensory science approaches. Using headspace solid phase microextraction (HS-SPME), solvent-assisted flavor evaporation (SAFE), and dynamic headspace sampling (DHS) combined with comprehensive gas chromatography-olfactometry-mass spectrometry (GC × GC-O-MS), 102 odor-active compounds were detected in ZW.6 pea milk. Among these, 19 compounds exhibiting high flavor dilution (FD) factors were accurately quantitated. Ten key odor-active compounds were ultimately identified through aroma recombination and omission experiment. Aldehydes and alcohols significantly contribute to the odor profile of pea milk.

Evaluation of normalization strategies for GC-based metabolomics.

INTRODUCTION: For many samples studied by GC-based metabolomics applications, extensive sample preparation involving extraction followed by a two-step derivatization procedure of methoximation and trimethylsilylation (TMS) is typically required to expand the metabolome coverage. Performing normalization is critical to correct for variations present in samples and any biases added during the sample preparation steps and analytical runs. Addressing the totality of variations with an adequate normalization method increases the reliability of the downstream data analysis and interpretation of the results. OBJECTIVES: Normalizing to sample mass is one of the most commonly employed strategies, while the total peak area (TPA) as a normalization factor is also frequently used as a post-acquisition technique. Here, we present a new normalization approach, total derivatized peak area (TDPA), where data are normalized to the intensity of all derivatized compounds. TDPA relies on the benefits of silylation as a universal derivatization method for GC-based metabolomics studies. METHODS: Two sample classes consisting of systematically incremented sample mass were simulated, with the only difference between the groups being the added amino acid concentrations. The samples were TMS derivatized and analyzed using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC × GC-TOFMS). The performance of five normalization strategies (no normalization, normalized to sample mass, TPA, total useful peak area (TUPA), and TDPA) were evaluated on the acquired data. RESULTS: Of the five normalization techniques compared, TUPA and TDPA were the most effective. On PCA score space, they offered a clear separation between the two classes. CONCLUSION: TUPA and TDPA carry different strengths: TUPA requires peak alignment across all samples, which depends upon the completion of the study, while TDPA is free from the requirement of alignment. The findings of the study would enhance the convenient and effective use of data normalization strategies and contribute to overcoming the data normalization challenges that currently exist in the metabolomics community.

Solid-phase microextraction coupled to comprehensive multidimensional gas chromatography for food analysis.

Solid-phase microextraction and comprehensive multidimensional gas chromatography represent two milestone innovations that occurred in the field of separation science in the 1990s. They have a common root in their introduction and have found a perfect coupling in their evolution and applications. This review will focus on food analysis, where the paradigm has changed significantly over time, moving from a targeted analysis, focusing on a limited number of analytes at the time, to a more holistic approach for assessing quality in a larger sense. Indeed, not only some major markers or contaminants are considered, but a large variety of compounds and their possible interaction, giving rise to the field of foodomics. In order to obtain such detailed information and to answer more sophisticated questions related to food quality and authenticity, the use of SPME-GC × GC-MS has become essential for the comprehensive analysis of volatile and semi-volatile analytes. This article provides a critical review of the various applications of SPME-GC × GC in food analysis, emphasizing the crucial role this coupling plays in this field. Additionally, this review dwells on the importance of appropriate data treatment to fully harness the results obtained to draw accurate and meaningful conclusions.

Applying a risk assessment guided evaluation for verifying comprehensive two-dimensional gas chromatography to analyse complex pharmaceuticals.

The reliability of analytical results is critical and indispensable when applied in regulated environments such as the pharmaceutical industry. Therefore, analytical workflows must be validated. However, validation guidelines are often designed for quantitative targeted analysis and rarely apply to qualitative untargeted approaches. In this study, we employ a risk assessment approach to identify critical parameters which might influence the qualitative results derived by online derivatisation - comprehensive two-dimensional gas chromatography coupled to a high-resolution time-of-flight mass spectrometer (GC × GC-HR-ToF-MS) for the analysis of the active pharmaceutical ingredient (API) sodium bituminosulfonate (SBS). To show the complexity and feasibility of such an approach, we focus on investigating three potential risk factors: sample preparation, vapourability, and the thermal stability of sulfonates. Through the individual evaluation of these potential risk factors due to the application of sample preparation approaches and thermal gravimetric analysis (TGA), we demonstrate the high derivatisation efficiency and repeatability of the online derivatisation method and confirm the absence of derivatisation-induced side reactions. In addition, we also show the potential thermal instability of an incompletely derivatised API. To address the limitation of these individual assessments, we applied a holistic evaluation step with negative electrospray ionisation Fourier transform ion cyclotron resonance mass spectrometry (ESI( -) FT-ICR MS) as an orthogonal technique. This confirms that most of the API is detected via the presented GC-based method. Thereby, we demonstrated the practical feasibility of the risk assessment-based approach to ensure the validity of the qualitative data for a complex untargeted method.

Comprehensive investigation on non-volatile and volatile flavor compounds in the Morchella sextelata and Morchella importuna by UPLC-MS/MS and GC × GC-TOF-MS.

Morchella sextelata and Morchella importuna are the main cultivars of morel. However, the key compounds affecting their flavors (taste and odor) are currently unknown. Here, an ultra performance tandem mass spectrometry combined with two-dimensional gas chromatography-time-of-flight mass spectrometry method was used to detect and relatively quantify the metabolites in both morel cultivars. A total of 631 non-volatile compounds and 242 volatile compounds were identified. The odor activity value was calculated to assess the contribution of key odor volatile. The results indicated that M. importuna had a sweeter flavor than M. sextelata. The former posed more prominent mushroom flavor than the latter based on the correlation analysis of the metabolites. The flavor differences of the two morel cultivars are highly relevant with the content of lipids, carbohydrates, amino acids and derivatives, alcohols and ketones. This study provides new insights into the theoretical basis for the flavor differences in both morel cultivars.

Distinct emissions of biogenic volatile organic compounds from temperate benthic taxa.

INTRODUCTION: Biogenic volatile organic compounds (BVOCs) are emitted by all organisms as intermediate or end-products of metabolic processes. Individual BVOCs perform important physiological, ecological and climatic functions, and collectively constitute the volatilome-which can be reflective of organism taxonomy and health. Although BVOC emissions of tropical benthic reef taxa have recently been the focus of multiple studies, emissions derived from their temperate counterparts have never been characterised. OBJECTIVES: Characterise the volatilomes of key competitors for benthic space among Australian temperate reefs. METHODS: Six fragments/fronds of a temperate coral (Plesiastrea versipora) and a macroalga (Ecklonia radiata) from a Sydney reef site were placed within modified incubation chambers filled with seawater. Organism-produced BVOCs were captured on thermal desorption tubes using a purge-and-trap methodology, and were then analysed using GC × GC - TOFMS and multivariate tests. RESULTS: Analysis detected 55 and 63 BVOCs from P. versipora and E. radiata respectively, with 30 of these common between species. Each taxon was characterised by a similar relative composition of chemical classes within their volatilomes. However, 14 and 10 volatiles were distinctly emitted by either E. radiata or P. versipora respectively, including the halogenated compounds iodomethane, tribromomethane, carbon tetrachloride and trichloromonofluoromethane. While macroalgal cover was 3.7 times greater than coral cover at the sampling site, P. versipora produced on average 17 times more BVOCs per cm2 of live tissue, resulting in an estimated contribution to local BVOC emission that was 4.7 times higher than E. radiata. CONCLUSION: Shifts in benthic community composition could disproportionately impact local marine chemistry and affect how ecosystems contribute to broader BVOC emissions.

Effects of pile-fermentation on the aroma quality of dark tea from a single large-leaf tea variety by GC × GC-QTOFMS and electronic nose.

Aroma is one of the significant quality factors of dark tea (DT). However, for a single large-leaf tea variety, there are few studies analyzing the effect of pile-fermentation on the aroma quality of DT. The GC × GC-QTOFMS, electronic nose (E-nose) and GC-olfactometry (GC-O) techniques were employed to analysis the difference of tea products before and after pile-fermentation. A total of 149 volatile metabolites (VMs) were identified, with 92 VMs exhibiting differential characteristics. Among these, 31 VMs with OAV > 1.0 were found to be correlated with E-nose results (|r| > 0.8). Additionally, GC-O analysis validated seven major differential metabolites. Notably, naphthalene, 2-methylnaphthalene, and dibenzofuran were found to enhance the woody aroma, while (Z)-4-heptenal, 2-nonenal and 1-hexanol were associated with an increase in mushroom, fatty and sweet odors, respectively. Moreover, 1-octen-3-ol was linked to reducing pungent fishy smell. These findings could provide a certain theoretical basis for understanding the influence of pile-fermentation on the aroma quality of dark tea.

Catchment area, fate, and environmental risks investigation of micropollutants in Danish wastewater.

This study aimed to investigate the spatial distribution of micropollutants in wastewater related to catchment area, and their environmental risks and fate. About 24-h flow proportional effluent (n = 26) wastewater samples were collected from eight WWTPs across Denmark. From five of these WWTPs corresponding influent samples (n = 20) were collected. Samples were enriched by multi-layer solid phase and analysed by liquid chromatography-high-resolution mass spectrometry and comprehensive two-dimensional gas chromatography with high-resolution mass spectrometry detection. We detected and quantified 79 micropollutants from a list of 291 micropollutants in at least one influent or effluent wastewater sample. From this we found that 54 micropollutants decreased in concentrations during wastewater treatment, while O-desmethylvenlafaxine, carbamazepine, amitriptyline, benzothiazole, terbutryn, and citalopram increased in concentrations through the WWTP.The toxicity of effluent wastewater samples was assessed by EC50 using Raphidocelis subcapitata (R. subcapitata) and LC50 using the crustacean Daphnia magna (D. Magna), for which six micropollutants were detected above the predicted no-effect concentration. Our study demonstrates that catchment area influences the micropollutant composition of wastewater. Out of 19 pharmaceuticals, the measured concentration in influent wastewater was predicted within a factor of 10 from sale numbers and human excretion, which demonstrates the strong influence of catchment area on micropollutant composition.

Correlations for untargeted GC × GC-HRTOF-MS metabolomics of colorectal cancer.

INTRODUCTION: Modern comprehensive instrumentations provide an unprecedented coverage of complex matrices in the form of high-dimensional, information rich data sets. OBJECTIVES: In addition to the usual biomarker research that focuses on the detection of the studied condition, we aimed to define a proper strategy to conduct a correlation analysis on an untargeted colorectal cancer case study with a data set of 102 variables corresponding to metabolites obtained from serum samples analyzed with comprehensive two-dimensional gas chromatography coupled to high-resolution time-of-flight mass spectrometry (GC × GC-HRTOF-MS). Indeed, the strength of association existing between the metabolites contains potentially valuable information about the molecular mechanisms involved and the underlying metabolic network associated to a global perturbation, at no additional analytical effort. METHODS: Following Anscombe's quartet, we took particular attention to four main aspects. First, the presence of non-linear relationships through the comparison of parametric and non-parametric correlation coefficients: Pearson's r, Spearman's rho, Kendall's tau and Goodman-Kruskal's gamma. Second, the visual control of the detected associations through scatterplots and their associated regressions and angles. Third, the effect and handling of atypical samples and values. Fourth, the role of the precision of the data on the attribution of the ranks through the presence of ties. RESULTS: Kendall's tau was found the method of choice for the data set at hand. Its application highlighted 17 correlations significantly altered in the active state of colorectal cancer (CRC) in comparison to matched healthy controls (HC), from which 10 were specific to this state in comparison to the remission one (R-CRC) investigated on distinct patients. 15 metabolites involved in the correlations of interest, on the 25 unique ones obtained, were annotated (Metabolomics Standards Initiative level 2). CONCLUSIONS: The metabolites highlighted could be used to better understand the pathology. The systematic investigation of the methodological aspects that we expose allows to implement correlation analysis to various fields and many specific cases.

Characterization of the Key Aroma Compounds in Dong Ding Oolong Tea by Application of the Sensomics Approach.

The Dong Ding oolong tea (DDT), grown and produced in Taiwan, is widely appreciated for its unique flavor. Despite its popularity, research on the aroma components of DDT remains incomplete. To address this gap, this study employed a sensomics approach to comprehensively characterize the key aroma compounds in DDT. Firstly, sensory evaluation showed that DDT had a prominent caramel aroma. Subsequent analysis using gas chromatography-olfactory mass spectrometry (GC-O-MS) and comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-TOF-MS) identified a total of 23 aroma-active compounds in DDT. Notably, three pyrazine compounds with roasted notes, namely 2-ethyl-5-methylpyrazine, 2-ethyl-3,5-dimethylpyrazine, and 2,3-diethyl-5-methylpyrazine, along with seven floral- and fruit-smelling compounds, namely 6-methyl-5-hepten-2-one, 3,5-octadien-2-one, linalool, (E)-linalool oxide, geraniol, (Z)-jasmone, and (E)-nerolidol, were identified as the key aroma compounds of DDT. Omission experiments further validated the significant contribution of the three pyrazines to the caramel aroma of DDT. Moreover, the content of 2-ethyl-3,5-dimethylpyrazine, 2,3-diethyl-5-methylpyrazine, (Z)-jasmone, 6-methyl-5-hepten-2-one and 2-ethyl-5-methylpyrazine was found to be higher in the high-grade samples, while (E)-nerolidol, linalool, geraniol and 3,5-octadien-2-one were found to be more abundant in the medium-grade samples. These findings provide valuable information for a better understanding of the flavor attributes of DDT.