Long-term escape behavior and release mechanism of organic emissions from asphalt materials.

In the context of carbon neutrality and carbon peaking, investigating the long-term escape behavior and release mechanism of organic emissions from asphalt materials can contribute to the development of environmentally sustainable asphalt pavements. In this study, the long-term emission behavior and release mechanism of organic emissions from asphalt materials were unraveled by combining the headspace gas chromatography-mass spectrometry (HS-GC-MS), differential scanning calorimetry (DSC), fluorescence microscopy (FM), and Fourier transform infrared spectroscopy (FTIR) tests. The results demonstrate that the pressure aging vessel (PAV) test and the ultraviolet (UV) aging test can result in a notable reduction in the concentration of organic emissions from asphalt materials, respectively. This indicates that asphalt pavements can potentially release a substantial quantity of organic emissions during their long-term service life. Besides, the aging mechanism of asphalt materials is established to unravel the release mechanism of organic emissions from asphalt materials. Aging increases the probability of organic emissions being released and volatilized from asphalt materials, which leads to the organic emissions from asphalt materials being more likely to be released and volatilized. Consequently, the aging process facilitates a greater release and volatilization of organic emissions from asphalt materials, resulting in a decrease in the detected concentration of these emissions after aging.

Combination of real-time and hyphenated mass spectrometry for improved characterisation of exhaled breath biomarkers in clinical research.

Exhaled breath volatilomics is a powerful non-invasive tool for biomarker discovery in medical applications, but compound annotation is essential for pathophysiological insights and technology transfer. This study was aimed at investigating the interest of a hybrid approach combining real-time proton transfer reaction-time-of-flight mass spectrometry (PTR-TOF-MS) with comprehensive thermal desorption-two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (TD-GCxGC-TOF-MS) to enhance the analysis and characterization of VOCs in clinical research, using COVID-19 as a use case. VOC biomarker candidates were selected from clinical research using PTR-TOF-MS fingerprinting in patients with COVID-19 and matched to the Human Breathomic Database. Corresponding analytical standards were analysed using both a liquid calibration unit coupled to PTR-TOF-MS and TD-GCxGC-TOF-MS, together with confirmation on new clinical samples with TD-GCxGC-TOF-MS. From 26 potential VOC biomarkers, 23 were successfully detected with PTR-TOF-MS. All VOCs were successfully detected using TD-GCxGC-TOF-MS, providing effective separation of highly chemically related compounds, including isomers, and enabling high-confidence annotation based on two-dimensional chromatographic separation and mass spectra. Four VOCs were identified with a level 1 annotation in the clinical samples. For future applications, the combination of real-time PTR-TOF-MS and comprehensive TD-GCxGC-TOF-MS, at least on a subset of samples from a whole study, would enhance the performance of VOC annotation, offering potential advancements in biomarker discovery for clinical research.

Identification of floral aroma components and molecular regulation mechanism of floral aroma formation in Phalaenopsis.

BACKGROUND: Most Phalaenopsis cultivars have almost no aroma, with a few exceptions. Phalaenopsis presents significant challenges in fragrance breeding due to its weak aroma and low fertility. It is therefore necessary to identify the aroma components and key regulatory genes in Phalaenopsis cultivars like 'Orange Beauty', 'Brother Sara Gold', 'Purple Martin', 'H026', 'SK16', 'SX098', and 'SH51', to improve the aroma of the common Phalaenopsis. RESULTS: Floral aroma components were tested on nine Phalaenopsis species, using smell identification and headspace gas chromatography-mass spectrometry. The result showed that alcohols, esters, and alkenes were the key specific components in the different species and cultivar aromas and the aroma intensity and component content of cultivars with different colors were different. The main components of the floral aromas in Phalaenopsis were alcohols (including eucalyptol, linalool, citronellol, and 1-hexanol), esters (including hexyl acetate, leaf acetate, and dibutyl phthalate), alkenes (including pinene and sabinene) and arenes (like fluorene). The transcriptome of flowers in the bud stage and bloom stage of P. 'SH51' was sequenced and 5999 differentially expressed genes were obtained. The contributions of the phenylpropionic acid/phenyl ring compound and the terpene compound to the aroma were greater. Sixteen genes related to phalaenopsis aroma were found. TC4M, PAL, CAD6, and HR were related to phenylpropanoid synthesis pathway. SLS, TS10, and P450 were related to the synthesis pathway of terpenes. TS10 and YUCCA 10 were involved in tryptophan metabolism. CONCLUSION: This is the first report on the floral aroma components and regulatory genes in Phalaenopsis. The proposed method and research data can provide technical support for Phalaenopsis breeding. © 2024 Society of Chemical Industry.

From grape to wine: A thorough compound specific isotopic, enantiomeric and quali-quantitative investigation by means of gas chromatographic analysis.

In this study, multiple analytical approaches, including simultaneous enantiomeric and isotopic analysis, were employed to thoroughly investigate the volatile fraction in Moscato giallo grape berries and wines. For the qualitative and quantitative profiling, a fast GC-QqQ/MS approach was successfully utilized. However, prior to isotopic analysis, the extracts underwent an additional concentration step, necessitating an assessment of isotopic fractionation during the concentration process. Once the absence of carbon isotopic fractionation was confirmed, this research aimed to develop a suitable gas chromatographic method for the simultaneous detection of both enantiomeric and isotopic ratios of target monoterpenoids in Moscato giallo samples. To address the limitations associated with a one-dimensional approach, multidimensional gas chromatography was employed to enhance separation before IRMS and qMS detections. Utilizing a Deans switch transfer device, the coupling of an apolar column in the first dimension and a chiral cyclodextrin-based stationary phase in the second dimension proved effective for this purpose. The data obtained from the analysis of Moscato giallo samples allowed for the assessment of natural isotopic and enantiomeric distributions in grapes and wines for the first time in the literature. Significant enantiomeric excesses were observed for the target terpenoids investigated. Regarding isotopic distribution, a consistent trend was observed for all detected target terpenols, including the linalool enantiomers. To date, this study represents the first investigation of simultaneous δ13C and chiral investigation of the main terpenoids in oenological products in the literature.

Sequential Fermentation in Red Wine cv. Babic Production: The Influence of Torulaspora delbrueckii and Lachancea thermotolerans Yeasts on the Aromatic and Sensory Profile.

This research aimed to analyze the impact of two different non-Saccharomyces yeast species on the aromatic profile of red wines made from the cv. Babic (Vitis vinifera L.) red grape variety. The grapes were obtained from two positions in the Middle and South of Dalmatia. This study compared a control treatment with the Saccharomyces cerevisiae (Sc) strain as a type of sequential inoculation treatment with Lachancea thermotolerans (Lt x Sc) and Torulaspora delbrueckii (Td x Sc). The focus was on the basic wine parameters and volatile aromatic compound concentrations determined using the SPME-Arrow-GC/MS method. The results revealed significant differences in cis-linalool oxide, geraniol, neric acid, and nerol, which contribute to the sensory profile with floral and rose-like aromas; some ethyl esters, such as ethyl furoate, ethyl hexanoate, ethyl lactate, ethyl 2-hydroxy-3-methylbutanoate, ethyl 3-hydroxy butanoate, diethyl glutarate, and diethyl succinate, contribute to the aromatic profile with fruity, buttery, overripe, or aging aromas. A sensory evaluation of wines confirmed that Td x Sc treatments exhibited particularly positive aromatic properties together with a more intense fullness, harmony, aftertaste, and overall impression.

Evaluation of Terpene Decomposition in Kaffir Lime Juice during Storage Using Gas Chromatography-Mass Spectrometry and Proton Transfer Reaction-Mass Spectrometry.

Kaffir lime juice, often treated as production waste, can be a good source of terpenes. These compounds undergo various decomposition processes under the influence of external factors, especially during transportation and storage. In this paper, it was possible to monitor changes in the terpene profile of kaffir lime juice under different storage conditions, namely, 4 °C, 20 °C, and 35 °C. The identification of key decomposition products was achieved using gas chromatography-mass spectrometry (GC-MS) and a data mining protocol. It was followed by tracing those products in different storage conditions using a high-throughput proton transfer reaction mass spectrometry (PTR-MS) approach. Based on our findings, degradation pathways were presented, showing that the main products resulting from storage are p-cymene, p-cymenene, terpinene-4-ol, and α-terpineol. It was shown that conversion to p-cymenene occurs after 5 days of storage. Terpinene-4-ol and α-terpineol were found to be the final products of the conversion at all temperatures. Changes in the composition of terpenes are important from the point of view of their bioactive properties.

Volatile Compounds for Discrimination between Beef, Pork, and Their Admixture Using Solid-Phase-Microextraction-Gas Chromatography-Mass Spectrometry (SPME-GC-MS) and Chemometrics Analysis.

This study addresses the prevalent issue of meat species authentication and adulteration through a chemometrics-based approach, crucial for upholding public health and ensuring a fair marketplace. Volatile compounds were extracted and analyzed using headspace-solid-phase-microextraction-gas chromatography-mass spectrometry. Adulterated meat samples were effectively identified through principal component analysis (PCA) and partial least square-discriminant analysis (PLS-DA). Through variable importance in projection scores and a Random Forest test, 11 key compounds, including nonanal, octanal, hexadecanal, benzaldehyde, 1-octanol, hexanoic acid, heptanoic acid, octanoic acid, and 2-acetylpyrrole for beef, and hexanal and 1-octen-3-ol for pork, were robustly identified as biomarkers. These compounds exhibited a discernible trend in adulterated samples based on adulteration ratios, evident in a heatmap. Notably, lipid degradation compounds strongly influenced meat discrimination. PCA and PLS-DA yielded significant sample separation, with the first two components capturing 80% and 72.1% of total variance, respectively. This technique could be a reliable method for detecting meat adulteration in cooked meat.

Plastic Quantification and Polyethylene Overestimation in Agricultural Soil Using Large-Volume Pyrolysis and TD-GC-MS/MS.

Quantification of microplastics in soil is needed to understand their impact and fate in agricultural areas. Often, low sample volume and removal of organic matter (OM) limit representative quantification. We present a method which allows simultaneous quantification of microplastics in homogenized, large environmental samples (>1 g) and tested polyethylene (PE), polyethylene terephthalate (PET), and polystyrene (PS) (200-400 µm) overestimation by fresh and diagenetically altered OM in agricultural soils using a new combination of large-volume pyrolysis adsorption with thermal desorption-gas chromatography-tandem mass spectrometry (TD-GC-MS/MS). Characteristic MS/MS profiles for PE, PET, and PS were derived from plastic pyrolysis and allowed for a new mass separation of PET. Volume-defined standard particles (125 × 125 × 20 µm3) were developed with the respective weight (PE: 0.48 ± 0.12, PET: 0.50 ± 0.10, PS: 0.31 ± 0.08 µg), which can be spiked into solid samples. Diagenetically altered OM contained compounds that could be incorrectly identified as PE and suggest a mathematical correction to account for OM contribution. With a standard addition method, we quantified PS, PET, and PEcorrected in two agricultural soils. This provides a base to simultaneously quantify a variety of microplastics in many environmental matrices and agricultural soil.

Analysis of Lipoprotein Signaling in Iris Melanocytes.

Lipids are compounds involved in many biologic functions including cell structure, metabolism, energy storage and are involved in signaling. A prominent lipid in these functions is cholesterol. Cholesterol also plays a part in the signaling of melanocytes, which contain melanosomes. The maturation of these melanosomes happens during melanocyte growth. The deficit of melanogenesis or melanosome maturation is associated with ocular albinism in the eye. Aberrations of melanosome maturation are also associated with pigment dispersion syndrome. Albinism and pigment dispersion manifestations are systemic. Both melanogenesis and melanocyte maturation are affected by cholesterol metabolism. Cholesterol signaling is a part of many pathways in the body, and evaluating these signals can have implications in systemic disease processes of melanogenesis and melanosome maturation, like ocular albinism and pigment dispersion. Cholesterol is carried by lipoprotein particles. Low-density lipoprotein (LDL) is usually the transport vehicle for cholesterol to reach tissues and organelles. The LDL uptake on cells often sends out a cascade of internal signaling within the cells. We describe here LDL signaling related to lipase activity changes using enzymatic methods with a kit. We describe analyses of cholesterol esters and free cholesterol with liquid chromatography and gas chromatography with or in tandem with mass spectrometry (GC-MS and LC-MS/MS). These analyses will provide insight into melanosome maturation and melanogenesis. The methods described here are applicable to all melanocytes within the body of a model mammalian organism.

The behavior of pharmaceutically active compounds and contrast agents during wastewater treatment - Combining sampling strategies and analytical techniques: A critical review.

Increasing consumption of pharmaceuticals and the respective consequences for the aquatic environment have been the focus of many studies over the last thirty years. Various aspects in this field were investigated, considering diverse pharmaceutical groups and employing a wide range of research methodologies. Various questions from the perspectives of different research areas were devised and answered, resulting in a large mix of individual findings and conclusions. Collectively, the results of the studies offer a comprehensive overview. The large variety of methods and strategies, however, demands close attention when comparing and combining information from heterogeneous projects. This review critically examines the application of diverse sampling techniques as well as analytical methods in investigations concerning the behavior of pharmaceutically active compounds (PhACs) and contrast agents (CAs) in wastewater treatment plants (WWTPs). The combination of sampling and analysis is discussed with regard to its suitability for specific scientific problems. Different research focuses need different methods and answer different questions. An overview of studies dealing with the fate and degradation of PhACs and CAs in WWTPs is presented, discussing their strategic approaches and findings. This review includes surveys of anticancer drugs, antibiotics, analgesics and anti-inflammatory drugs, antidiabetics, beta blockers, hormonal contraceptives, lipid lowering agents, antidepressants as well as contrast agents for X-ray and magnetic resonance imaging.

Characterization of flavor volatiles in raw and cooked pigmented onion (Allium cepa L) bulbs: A comparative HS-GC-IMS fingerprinting study.

Variations in volatile flavor components in pigmented onion bulbs (purple, white, and yellow) before and after cooking were characterized by headspace gas chromatography-ion migration spectrometry (HS-GC-IMS) to investigate their odor traits. Results showed that 39 and 45 volatile flavor compounds were identified from pigmented onion bulbs before and after cooking via the HS-GC-IMS fingerprinting, respectively. Sulfurs (accounting for 50.65%-63.42%), aldehydes (13.36%-22.11%), and alcohols (11.32%-17.94%) ranked the top three prevailing compound categories in all pigmented onions (both raw and cooked). Compared to the raw colored onion bulbs, the relative proportion of sulfurs in cooked onions decreased, whereas the relative proportion of alcohols, esters, pyrazines, and furans increased. Two reliable prediction models were established through orthogonal partial least squares-discriminant analysis (OPLS-DA), and 8 and 22 distinctive odor compounds were sieved out by variable importance in projection (VIP>1.0) as volatile labels, respectively. Both principal component analysis (PCA) and clustering heatmap exhibited favorable distinguishing effects for various pigmented onion bulbs before and after cooking. These results might offer insights into understanding the odor characteristics of different pigmented onions.

Determination of eleven components in rat plasma by UPLC-MS/MS and GC-MS for pharmacokinetic studies after oral administration of Citri Reticulatae Pericarpium extract.

Citri Reticulatae Pericarpium (CRP) is used as common health-care food and traditional Chinese medicine (TCM), which exerts pharmacological effects, such as anti-cardiovascular, anti-tumor, anti-oxidant, anti-inflammatory, anti-virus, hepatoprotective, blood pressure-lowering and neuroprotective. In this study, reliable, and sensitive ultra-high performance liquid chromatography/tandem mass spectrometry (UPLC-MS/MS) and gas chromatography-mass spectrometry (GC-MS) methods were developed and validated for the determination of eleven active components in rat plasma after oral administration of the CRP extract. The results of this method exhibited that the specificity, linearity (r > 0.999), precision and accuracy (the coefficient of variation (CV) < 11.5 %), recovery (52.9-107.9 %), matrix effects (63.8-107.5 %), and stability (CV < 10.8 %) met all requirements for the quantitation of plasma samples. The pharmacokinetic results showed that the Tmax of flavone glycosides was less than 0.7 h, and that of polymethoxyflavones and volatile components were within 1-7 h. Meanwhile, the area-under-the-curve (AUC) and concentration maximum (Cmax) of hesperidin, nobiletin, tangeretin, and D-limonene were higher than those of the other components, suggesting that the plasma exposure levels of these constituents were higher in CRP. The present research lays a foundation for elucidating the therapeutic material basis and provides a reference for further scientific research and clinical application of CRP.

A feasibility study of sample re-collection in the analysis of selected volatile compounds in breath samples using GC×GC-TOFMS.

In this study, we aimed to assess the feasibility of re-collecting breath samples using the Centri® (Markes International, Bridgend, UK) followed by two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC×GC-TOFMS) analysis. The work was conducted in two main phases. In the first phase, we evaluated the re-collection performance by analyzing two sets of standards, including a Grob mix primary solution and a standard mixture of 20 selected volatile compounds (VCs) covering different classes of organic species commonly found in breath samples. The intra-day and inter-day precision (reported as relative standard deviation (RSD),%) for the re-collection of the Grob mix primary solution were in the range of 1 % to14 % and 3 % to12 %, respectively. The re-collection accuracy ranged from 78 % to 97 %. The intra-day RSD for the re-collection of the standard mixture of selected VCs was within 20 % for all compounds, except for acetone and nonane. The precision was within 25 % for all compounds, except for nonane, n-hexane, 1,4-dichlorobenzene, and decane, which exhibited less than 36 % RSD. The re-collection accuracy was in the range of 67 % to 129 %. In the second phase of the study, the re-collection performance in breath analysis was evaluated via five repetitive splitting and re-collection of six breath samples obtained from healthy adults, realizing a total of 30 breath analyses. Initially, we evaluated the re-collection performance by considering all features obtained from breath analysis and then focused on the 20 VCs commonly found in breath samples. The re-collection accuracy for total breath features ranged from 86 to 103 %, and the RSDs were in the range of 1.0 % to 10.4 %. For the selected VCs, the re-collection accuracy of all compounds, except for undecane and benzene, was in the range of 71 % to 132 %.

Profiling the volatile compounds of Peganum harmala L. Based on multiple sample preparation coupled with gas chromatography-mass spectrometry analysis and explored its antidepressants-like activity.

Peganum harmala L., a traditional medicinal plant in China, is renowned for its significant alkaloid content in seeds and roots exhibiting a wide range of pharmacological activities, including antidepressant, antiseptic, and antiviral. However, the volatile composition of the herb remained unclear. Apart from that, the extraction of volatile compounds through essential oil presents challenges due to the low yield and the degradation of volatile active compounds at high temperatures. This study used multiple sample preparation methods including headspace (HS), needle trap device (NTD), and liquid-liquid extraction (LLE) coupled with gas chromatography-mass spectrometry (GC-MS) to analyze the volatile compounds from the areal part of P. harmala L.. A total of 93 compounds were identified with NTD facilitating the first detection of harmine among the volatile organic compounds. Through network pharmacology and protein interaction analysis, the compounds' potential therapeutic targets of the compounds were explored, and 23 key targets were obtained (AKT1, ALB, PTGS2, MAOA, etc). KEGG pathway enrichment analysis indicated significant involvement in neuroactive ligand-receptor interactions and serotonergic synapses. The results enhanced the understanding of P. harmala's pharmacological mechanisms and supported its ethnopharmacological use.

Exploring microbial and moist-heat effects on Pu-erh tea volatiles and understanding the methoxybenzene formation mechanism using molecular sensory science.

Piling fermentation (PF) is crucial for Pu-erh tea aroma, yet its microbial and moist-heat impact on aroma quality is poorly understood. Solid-phase microextraction, solvent-assisted flavor evaporation, and gas chromatography-mass spectrometry were used to detected and analyses the samples of sun-green green tea, sterile PF and spontaneous PF. Microbiological action promotes the formation of stale aromas. Moist-heat action promotes the formation of plum-fragrance and sweet aroma. 20 microbial markers and 28 moist-heat markers were screened from 184 volatile components. Combining odor activity values and gas chromatography-olfactometry, 22 aroma-active compounds were screened (1,2,3-trimethoxybenzene, linalool, 1,2,4-trimethoxybenzene …), and analyzed during PF processing. Aroma omission and addition experiments verified its importance. Gallic acid addition experiments successfully verified that microorganisms are the main contributors to the synthesis of methoxybenzenes. Finally, Blastobotrys, Rasamsonia, and Thermomyces showed positive correlation with the synthesis of 1-ethyl-4-methoxybenzene, 1,2,4-trimethoxybenzene, 1,2,3-trimethoxybenzene, and 1,2-dimethoxybenzene. The formation mechanism of Pu-erh tea's aroma was clarified. Exploring microbial and moist-heat effects on Pu-erh tea volatiles and understanding the methoxybenzene formation mechanism using molecular sensory science.

A fast thermal desorption unit for micro thermal desorption tubes, Part I: Development of the system and proof of concept measurements with hyper-fast gas chromatography.

A system consisting of a thermal desorption unit (TDU) and micro thermal desorption tubes (µTD-tubes, 1.4 mm I.D., 10mg Tenax TA) for fast desorption of analytes was developed for the efficient combination of hyper fast gas chromatography with thermal desorption. The fast desorption is achieved by a significantly reduced thermal mass compared to conventional thermal desorption tubes. Therefore, extremely fast heating and cooling cycles are possible. Proof of concept measurements combining the new setup with a flow-field thermal gradient gas chromatograph (FF-TG-GC) and FID detection show good precision and linearity with R2≥0.995 in the analysis of an n-alkane mix (C8-C20). Thermal desorption occurs within 12s. The impact of reduced µTD-tube dimensions on desorption time, full width at half maximum (FWHM), breakthrough volumes, tube flow rates ergo linear velocities, porosity and back pressure is discussed.

Simple on-site extraction and GC-MS analysis of rotenone and degradation products for monitoring invasive fish eradication treatments in fresh and brackish waters.

The introduction of invasive fish species to aquatic ecosystems has been demonstrated to cause disastrous ecological effects. Current conservation strategies regard rotenone-containing piscicide formulations, such as commercial product CFT Legumine, as a potentially viable alternative to the cumbersome traditional approaches to fish eradication. This consideration relies on the fast degradation of rotenone and its relatively rapid dissipation from the environment. Piscicide treatments in fragile aquatic ecosystems should thus monitor not only rotenone concentrations following application, but also other byproducts and degradation products. We present a methodology for the analysis of rotenoids in fresh and brackish waters that addresses two main challenges: the accurate determination of applied concentrations in different salinity concentrations by performing a simplified on-site solid-phase extraction, overcoming the fast degradation of rotenone in sample storage conditions, and the selective analysis of rotenoid byproducts and degradation products by gas chromatography coupled to mass spectrometry. Limits of quantification were below the ecological no-effect concentration of rotenone (2 µg/L) and average recoveries exceeded 80%. Accuracy (compared to expected values) and precision (deviation of replicates) ranged from 78 to 103% and 3 to 14%, respectively, across various rotenoid concentrations. These metrics are more than satisfactory for the intended application of this simplified procedure. The method was applied to piscicide-treated samples, revealing significant and fast degradation of parent rotenoids in storage conditions, as well as a non-negligible accumulation of rotenone in the particulate fraction of water that could impact the effectivity of eradication efforts.

Investigating a new approach for magnetic ionic liquids: Dispersive liquid-liquid microextraction coupled to pyrolysis gas-chromatography-mass spectrometry to determine flame retardants in sewage sludge samples.

This study addresses the analysis of emerging contaminants, often using chromatographic techniques coupled to mass spectrometry. However, sample preparation is often required prior to instrumental analysis, and dispersive liquid-liquid microextraction (DLLME) is a viable strategy in this context. DLLME stands out for its ability to reduce sample and solvent volumes. Notably, dispersive liquid-liquid microextraction using magnetic ionic liquids (MILs) has gained relevance due to the incorporation of paramagnetic components in the chemical structure, thereby eliminating the centrifugation step. A pyrolizer was selected in this work to introduce sample onto the GC column, since the MIL is extremely viscous and incompatible with direct introduction through an autosampler. This study is the first to report the use of a DLLME/MIL technique for sample introduction through a pyrolizer in gas chromatography coupled to mass spectrometry (GC-MS). This approach enables the MIL to be compatible with gas chromatography systems, resulting in optimized analytical and instrument performance. The analysis of polybrominated diphenyl ether flame retardants (PBDEs) was focused on the PBDE congeners 28, 47, 99, 100, and 153 in sewage sludge samples. The [P6,6,6,14+]2[MnCl42-] MIL was thoroughly characterized using UV-Vis, Fourier transform infrared spectroscopy (FTIR), and Raman spectroscopy, as well as thermal analysis. In the chromatographic method, a pyrolyzer was used in the sample introduction step (Py-GC-MS), and critical injection settings were optimized using multivariate approaches. Optimized conditions were achieved with a temperature of 220 °C, a pyrolysis time of 0.60 min, and an injection volume of 9.00 µL. DLLME optimization was performed through central compound planning (CCD), and optimized training conditions were achieved with 10.0 mg of MIL, 3.00 µL of acetonitrile (ACN) as dispersive solvent, extraction time of 60 s, and volume of a sample of 8.50 mL. Precision was observed to range from 0.11 % to 12.5 %, with limits of detection (LOD) of 44.4 µg L-1 for PBDE 28, 16.9 µg L-1 for PBDE 47 and PBDE 99, 33.0 µg L-1 for PBDE 100 and 375 µg L-1 for PBDE 153. PBDE 28 was identified and analyzed in the sludge sample at a concentration of 800 µg L-1. The use of MIL in dispersive liquid-liquid microextraction combined with pyrolysis gas chromatography-mass spectrometry enables identification and quantification of PBDEs in sewage sludge samples at concentrations down to the µg L-1 level.

Enhancing gas chromatography-mass spectrometry resolution and pure analyte discovery using intra-chromatogram elution profile matching.

Chemometric decomposition methods like multivariate curve resolution-alternating least squares (MCR-ALS) are often employed in gas chromatography-mass spectrometry (GC-MS) to improve analyte identification and quantitation. However, these methods can perform poorly for analytes with a low chromatographic resolution (Rs) and a high degree of spectral contamination from noise and background interferences. Thus, we propose a novel computational algorithm, termed mzCompare, to improve analyte identification and quantitation when coupled to MCR-ALS. The mzCompare method utilizes an underlying requirement that the retention time and peak shape between mass channels (m/z) of the same analyte should be similar. By discovering the selective m/z for a given analyte in a chromatogram, a pure elution profile can be generated and used as an equality constraint in MCR-ALS. The performance of the mzCompare methodology is demonstrated with both experimental and simulated chromatograms. Experimentally, unresolved analytes with a Rs as low as 0.05 could be confidently identified with mzCompare assisted MCR-ALS. Furthermore, application of the mzCompare algorithm to a complex aerospace fuel resulted in the discovery of 335 analytes, a 44 % increase compared to conventional peak detection methods. GC-MS simulations of target-interferent analyte pairs demonstrated that the performance of MCR-ALS deteriorated below a Rs of ∼0.25. However, mzCompare assisted MCR-ALS showed excellent identification and acceptable quantitative accuracy at a Rs of ∼0.02. These results show that the mzCompare algorithm can help analysts overcome modeling ambiguities resulting from the chemometric multiplex disadvantage.

Chemical characterization of volatile organic compounds emitted by animal manure.

Animal manure is considered a valuable organic fertilizer due to its important nutrient content enhancing soil fertility and plant growth in agriculture. Besides its beneficial role as fertilizer, animal manure represents a significant source of volatile organic compounds (VOCs), playing a significant role in atmospheric chemistry. Understanding the composition of VOCs Understanding VOCs from animal manure is crucial for assessing their environmental impact, as they can cause air pollution, odors, and harm to human health and ecosystems. Laboratory studies enhance field measurements by providing a precise inventory of manure emissions, addressing gaps in existing literature. Both approaches complement each other in advancing our understanding of manure emissions. In this context, we conducted an experimental study involving various animal manures (cow, horse, sheep, and goat) taken from a farm in Grignon (near Paris, France). We employed atmospheric simulation chambers within a controlled laboratory environment. The analysis of VOCs involved the combination of Proton Transfer Reaction-Quadrupole ion guide-Time-of-Flight Mass Spectrometry (PTR-QiTOF-MS) and Thermal Desorption-Gas Chromatography-Mass Spectrometry (TD-GC-MS). Using PTR-QiTOF-MS, 368 compounds were detected and quantified within the manure samples. The complementary analysis by TD-GC-MS enhanced our identification of VOCs. Our findings revealed various chemical groups of VOCs, including oxygenated compounds (e.g., ethanol, cresol, acetaldehyde, etc.), nitrogenated compounds (ammonia, trimethylamine, etc.), sulfur compounds (methanethiol, dimethyl sulfide, etc.), aromatic compounds (phenols and indoles), terpenes (isoprene, D-limonene, etc.) and halogenated compounds. Cow manure exhibited the highest VOC emission fluxes, followed by goat, sheep, and horse manures. Notably, oxygenated VOCs were dominant contributors to total VOC emission fluxes in all samples. Statistical analysis highlighted the distinct nature of cow manure emissions, characterized by oxygenated compounds and nitrogenated compounds. In addition, goat manure was isolated from the other samples with high emissions of compounds having both oxygen and nitrogen atoms in their molecular formulas (e.g., CH3NO2). The experimental dataset obtained in this study provides an inventory reference for both VOCs and their emission fluxes in animal manures. Furthermore, it highlights odorant compounds and VOCs that serve as atmospheric aerosol precursor. Future studies can explore the effectiveness of various manure treatment methods to promote sustainable agriculture practices.