Mass Spectral Profiles Research Articles

In-bottle thin film solid phase microextraction coupled to flow modulated comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry for monitoring of organic pollutants in environmental waters

The monitoring of organic compounds in water is critical for assessing environmental health and the effectiveness of treatment processes. In this study, we present a robust and eco-friendly approach to environmental water analysis that integrates thin film solid phase microextraction (TF-SPME) with comprehensive two-dimensional gas chromatography and time-of-flight mass spectrometry (GC × GC-TOFMS). This method is designed to detect multiclass organic pollutants in environmental water, thus enabling applications such as detailed analyses of changes post-treatment processes. The supervised PCA results revealed distinct clustering of the three water sample classes - raw wastewater, outflow from WWTF, and river water - each occupying separate regions in the principal component space. Several organohalogen compounds were identified as key differentiators among the water samples, highlighting significant compositional differences across the analyzed classes. Notably, an increased abundance of certain chlorinated compounds was observed in raw wastewater before it underwent purification treatment at the WWTF. Additionally, the greenness evaluation of the in-bottle TF-SPME-GC × GC-TOFMS indicated whiteness scores of 96.7 % for the in-bottle TF-SPME-GC × GC-TOFMS method and 79.0 % for the LLE (US EPA 8270)-GC/MS method. This approach facilitates the identification of a wide array of organic compounds, characterized by diverse physicochemical properties, through their mass spectral profiles. We applied this method to various environmental water samples, including raw wastewater, effluent from wastewater treatment facilities, and river water, to assess the impact of treatment processes on organic pollutant levels. Our developed strategy effectively monitored alterations in several organic compounds within these environmental water samples. Our results demonstrate that TF-SPME coupled with GC × GC-TOFMS proves to be both straightforward and comparable in performance to other methods for analyzing low-level organic pollutants in water samples, making it a valuable tool for environmental monitoring and discovering new emerging contaminates.

Discriminating fingerprints of chronic neuropathic pain following spinal cord injury using artificial neural networks and mass spectrometry analysis of female mice serum

Spinal cord injury (SCI) often leads to central neuropathic pain, a condition associated with significant morbidity and is challenging in terms of the clinical management. Despite extensive efforts, identifying effective biomarkers for neuropathic pain remains elusive. Here we propose a novel approach combining matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) with artificial neural networks (ANNs) to discriminate between mass spectral profiles associated with chronic neuropathic pain induced by SCI in female mice. Functional evaluations revealed persistent chronic neuropathic pain following mild SCI as well as minor locomotor disruptions, confirming the value of collecting serum samples. Mass spectra analysis revealed distinct profiles between chronic SCI and sham controls. On applying ANNs, 100% success was achieved in distinguishing between the two groups through the intensities of m/z peaks. Additionally, the ANNs also successfully discriminated between chronic and acute SCI phases. When reflexive pain response data was integrated with mass spectra, there was no improvement in the classification. These findings offer insights into neuropathic pain pathophysiology and underscore the potential of MALDI-TOF MS coupled with ANNs as a diagnostic tool for chronic neuropathic pain, potentially guiding attempts to discover biomarkers and develop treatments.

Toward New Therapeutics for Visceral Leishmaniasis: Efficacy and Mechanism of Action of Amides Inspired by Gibbilimbol B.

The problems with current strategies to control canine visceral Leishmaniasis (CVL), which include the euthanasia of infected animals, and also the toxicity of the drugs currently used in human treatments for CVL, add urgency to the search for new therapeutic agents. This study aimed to evaluate the activity against Leishmania (L.) infantum of 12 amides that are chemically inspired by gibbilimbol B, a bioactive natural product that was initially obtained from Piper malacophyllum. Three of these compounds-N-(2-ethylhexyl)-4-chlorobenzamide (9), N-(2-ethylhexyl)-4-nitrobenzamide (10), and N-(2-ethylhexyl)-4-(tert-butyl)benzamide (12) -demonstrated activity against the intracellular amastigotes without toxicity to mammalian host cells (CC50 > 200 μM); compounds 9, 10, and 12 resulted in EC50 values of 12.7, 12.2, and 5.1 μM, respectively. In silico drug-likeness studies predicted that these compounds would show high levels of gastrointestinal absorption, would be able to penetrate the blood-brain barrier, would show moderate solubility, and would not show unwanted molecular interactions. Due to their promising pharmacological profiles, compounds 9 and 10 were selected for mechanism of action studies (MoA). The MoA studies in L. (L.) infantum revealed that neither of the compounds affected the permeabilization of the plasma membrane. Nevertheless, compound 9 induced strong alkalinization of acidocalcisomes, which resulted in a significant and rapid increase in intracellular Ca2+ levels, thereby causing the depolarization of the mitochondrial membrane potential and a reduction in the levels of reactive oxygen species (ROS). In contrast, compound 10 induced a gradual increase in intracellular Ca2+ levels and a similarly gradual reduction in ROS levels, but it caused neither acidocalcisome alkalinization nor mitochondrial membrane potential depolarization. Finally, the MALDI-TOF/MS assessment of protein alterations in L. (L.) infantum treated separately with compounds 9 and 10 revealed changes in mass spectral profiles from both treatments. These results highlight the anti-L. (L.) infantum potential of these amides-especially for compounds 9 and 10-and they suggest that these compounds could be promising candidates for future in vivo studies in VL-models.

Molecular Characterization of Gaseous Organic Acids and Nitrogen‐Containing Compounds From Crop Straw and Wood Burning

AbstractBiomass burning serves as important sources of volatile organic compounds (VOCs), yet our understanding of the molecular characteristics of oxygenated volatile organic compounds (OVOCs) from fresh emissions remains limited. In this study, gaseous organic compounds in fresh smokes from burning typical Chinese crop straws and woods are measured using an iodide time‐of‐flight chemical ionization mass spectrometer. Approximately 750 molecular formulas are identified, with CHO compounds containing carbon, hydrogen and oxygen atoms accounting for 77%–95% of the total. C1–C3 organic acids and dicarboxylic acids dominate the total CHO signal intensities by 27%–48%, while well‐known molecular markers of biomass burning, such as monosaccharide, guaiacol and syringol derivatives, contribute 7%–17%. Notably, crop straw and wood burning emit a higher abundance of guaiacol than syringol derivatives by a factor of 5. Additionally, a variety of nitrogen‐containing compounds (mainly in the CHON group) is identified, including isocyanate, amide, amino acids, and pyridine. The mass spectral profiles of organic compounds are largely similar between crop straw and wood burning fuels, although wood burning produces higher contributions of compounds with carbon atoms numbers >10. The saturation concentrations of organic compounds are estimated using molecular formula‐based volatility parameterization, revealing that semi‐volatile and intermediate VOCs (S/intermediate volatility organic compounds (IVOCs)) predominate smoke releases by 35%–60% and 20%–43%, respectively, with only a small fraction of low‐volatility compounds. Given the widespread nature of biomass burning in winter China, our results may have significant implications for interpreting secondary organic aerosol formation through gas‐particle partitioning or aqueous‐phase reactions.

Off-odour Identification from Volatile Organic Compounds (VOCs) of Spirulina

Spirulina platensis is a common cyanobacteria microalga with high nutrition and bioactive compound sources. The addition of spirulina in foods and beverages improves nutrition and bioactive compound content. However, certain species of cyanobacteria are known to produce various compounds causing off-odour. This study investigates the chemical profile and volatile organic compounds (VOCs) in spirulina biomass and determine off-odour potency. The spirulina extract was analysed phytochemical qualitatively and GC-MS (Gas Chromatography-Mass Spectrometry). The Spectra mass was compared to the mass spectral database and profile of chemical compound libraries. The result shows, phytochemical analysis positively contains of alkaloids, flavonoids, tannins, saponins, and terpenoids. A total of 155 volatile compounds consisting of classes acid, alcohol, aldehyde, alkene, benzene, ether, ester, ketone, sulphur-contain, and terpene were identified. The off-odour VOC content such as phytol; cyclopropanebutanoic acid, 2- [[2 - [[2 - [(2- pentylcyclopropyl) methyl) cyclopropyl) methyl) cyclopropyl) methyl]-, methyl ester; 3.7.11.15-tetramethyl-2-hexadecen-1-ol; Imidazole, 2-fluoro-5-(2-carboxyvinyl)-; β-ionone; and N,N-Dimethyl-O-(1-methyl-butyl)-hydroxylamine, were detected in spirulina. The odour descriptions of off-odour VOCs are floral, balsamic, powdery, waxy, rancid, sweaty, woody, alkali, and fish-like. The off-odour content of VOCs might influence food's sensory odour, with spirulina added in excessive quantities.

Real-time chemical characterization of primary and aged biomass burning aerosols derived from sub-Saharan African biomass fuels in smoldering fires.

The influence of biomass burning (BB)-derived organic aerosol (OA) emissions on solar radiation via absorption and scattering is related to their physicochemical properties and can change upon atmospheric aging. We systematically examined the compositionally-resolved mass concentration and production of primary and secondary organic aerosol (POA and SOA, respectively) in the NC A&T University smog chamber facility. Mass spectral profiles of OA measured by the Aerosol Chemical Speciation Monitor (ACSM) revealed the influence of dark- and photo-aging, fuel type, and relative humidity. Unit mass resolution (UMR) mapping, the ratio of the fraction of the OA mass spectrum signal at m/z 55 and 57 (f 55/f 57) vs. the same fraction at m/z 60 (f 60) was used to identify source-specific emission profiles. Furthermore, Positive Matrix Factorization (PMF) analysis was conducted using OA mass spectra, identifying four distinct factors: low-volatility oxygenated OA (LV-OOA), primary biomass-burning OA (BBOA), BB secondary OA (BBSOA), and semi-volatile oxygenated OA (SV-OOA). Data supports a robust four-factor solution, providing insights into the chemical transformations under different experimental conditions, including dark- and photo-aged, humidified, and dark oxidation with NO3 radicals. This work presents the first such laboratory study of African-derived BBOA particles, addressing a gap in global atmospheric chemistry research.

Multidimensional mass profiles increase confidence in bacterial identification when using low-resolution mass spectrometers.

Field-forward analytical technologies, such as portable mass spectrometry (MS), enable essential capabilities for real-time monitoring and point-of-care diagnostic applications. Significant and recent investments improving the features of miniaturized mass spectrometers enable various new applications outside of small molecule detection. Most notably, the addition of tandem mass spectrometry scans (MS/MS) allows the instrument to isolate and fragment ions and increase the analytical specificity by measuring unique chemical signatures for ions of interest. Notwithstanding these technological advancements, low-cost, portable systems still struggle to confidently identify clinically significant organisms of interest, such as bacteria, viruses, and proteinaceous toxins, due to the limitations in resolving power. To overcome these limitations, we developed a novel multidimensional mass fingerprinting technique that uses tandem mass spectrometry to increase the chemical specificity for low-resolution mass spectral profiles. We demonstrated the method's capabilities for differentiating four different bacteria, including attentuated strains of Yersinia pestis. This approach allowed for the accurate (>92%) identification of each organism at the strain level using de-resolved matrix-assisted laser desorption ionization-time of flight (MALDI-TOF) data to mimic the performance characteristics of miniaturized mass spectrometers. This work demonstrates that low-resolution mass spectrometers, equipped with tandem MS acquisition modes, can accurately identify clinically relevant bacteria. These findings support the future application of these technologies for field-forward and point-of-care applications where high-performance mass spectrometers would be cost-prohibitive or otherwise impractical.

Bulk and molecular-level composition of primary organic aerosol from wood, straw, cow dung, and plastic burning

Abstract. During the past decades, the source apportionment of organic aerosol (OA) in ambient air has been improving substantially. The database of source retrieval model-resolved mass spectral profiles for different sources has been built with the aerosol mass spectrometer (AMS). However, distinguishing similar sources (such as wildfires and residential wood burning) remains challenging, as the hard ionization of the AMS mostly fragments compounds and therefore cannot capture detailed molecular information. Recent mass spectrometer technologies of soft ionization and high mass resolution have allowed for aerosol characterization at the molecular formula level. In this study, we systematically estimated the emission factors and characterized the primary OA (POA) chemical composition with the AMS and the extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) for the first time from a variety of solid fuels, including beech logs, spruce and pine logs, spruce and pine branches and needles, straw, cow dung, and plastic bags. The emission factors of organic matter estimated by the AMS and hydrocarbon gases estimated by the total hydrocarbon analyzer are 16.2 ± 10.8 g kg−1 and 30.3 ± 8.5 g kg−1 for cow dung burning, which is generally higher than that of wood (beech, spruce, and pine), straw, and plastic bag burning (in the range from 1.1 to 6.2 g kg−1 and 14.1 to 19.3 g kg−1). The POA measured by the AMS shows that the f60 (mass fraction of m/z 60) varies from 0.003 to 0.04 based on fuel types and combustion efficiency for wood (beech, spruce, and pine) and cow dung burning. On a molecular level, the dominant compound of POA from wood, straw, and cow dung is C6H10O5 (mainly levoglucosan), contributing ∼ 7 % to ∼ 30 % of the total intensity, followed by C8H12O6 with fractions of ∼ 2 % to ∼ 9 %. However, as they are prevalent in all burning of biomass material, they cannot act as tracers for the specific sources. By using the Mann–Whitney U test among the studied fuels, we find specific potential new markers for these fuels from the measurement of the AMS and EESI-TOF. Markers from spruce and pine burning are likely related to resin acids (e.g., compounds with 20–21 carbon atoms). The product from the pyrolysis of hardwood lignins is found especially in beech log burning. Nitrogen-containing species are selected markers primarily for cow dung open burning. These markers in the future will provide support for the source apportionment.

The chemistry of gut microbiome-derived lipopolysaccharides impacts on the occurrence of food allergy in the pediatric age.

Introduction: Food allergy (FA) in children is a major health concern. A better definition of the pathogenesis of the disease could facilitate effective preventive and therapeutic measures. Gut microbiome alterations could modulate the occurrence of FA, although the mechanisms involved in this phenomenon are poorly characterized. Gut bacteria release signaling byproducts from their cell wall, such as lipopolysaccharides (LPSs), which can act locally and systemically, modulating the immune system function. Methods: In the current study gut microbiome-derived LPS isolated from fecal samples of FA and healthy children was chemically characterized providing insights into the carbohydrate and lipid composition as well as into the LPS macromolecular nature. In addition, by means of a chemical/MALDI-TOF MS and MS/MS approach we elucidated the gut microbiome-derived lipid A mass spectral profile directly on fecal samples. Finally, we evaluated the pro-allergic and pro-tolerogenic potential of these fecal LPS and lipid A by harnessing peripheral blood mononuclear cells from healthy donors. Results: By analyzing fecal samples, we have identified different gut microbiome-derived LPS chemical features comparing FA children and healthy controls. We also have provided evidence on a different immunoregulatory action elicited by LPS on peripheral blood mononuclear cells collected from healthy donors suggesting that LPS from healthy individuals could be able to protect against the occurrence of FA, while LPS from children affected by FA could promote the allergic response. Discussion: Altogether these data highlight the relevance of gut microbiome-derived LPSs as potential biomarkers for FA and as a target of intervention to limit the disease burden.

Molecular characterization of human peripheral nerves using desorption electrospray ionization mass spectrometry imaging.

Desorption electrospray ionization mass spectrometry imaging (DESI-MSI) is a molecular imaging method that can be used to elucidate the small-molecule composition of tissues and map their spatial information using two-dimensional ion images. This technique has been used to investigate the molecular profiles of variety of tissues, including within the central nervous system, specifically the brain and spinal cord. To our knowledge, this technique has yet to be applied to tissues of the peripheral nervous system (PNS). Data generated from such analyses are expected to advance the characterization of these structures. The study aimed to: (i) establish whether DESI-MSI can discriminate the molecular characteristics of peripheral nerves and distinguish them from surrounding tissues and (ii) assess whether different peripheral nerve subtypes are characterized by unique molecular profiles. Four different nerves for which are known to carry various nerve fiber types were harvested from a fresh cadaveric donor: mixed, motor and sensory (sciatic and femoral); cutaneous, sensory (sural); and autonomic (vagus). Tissue samples were harvested to include the nerve bundles in addition to surrounding connective tissue. Samples were flash-frozen, embedded in optimal cutting temperature compound in cross-section, and sectioned at 14 μm. Following DESI-MSI analysis, identical tissue sections were stained with hematoxylin and eosin. In this proof-of-concept study, a combination of multivariate and univariate statistical methods was used to evaluate molecular differences between the nerve and adjacent tissue and between nerve subtypes. The acquired mass spectral profiles of the peripheral nerve samples presented trends in ion abundances that seemed to be characteristic of nerve tissue and spatially corresponded to the associated histology of the tissue sections. Principal component analysis (PCA) supported the separation of the samples into distinct nerve and adjacent tissue classes. This classification was further supported by the K-means clustering analysis, which showed separation of the nerve and background ions. Differences in ion expression were confirmed using ANOVA which identified statistically significant differences in ion expression between the nerve subtypes. The PCA plot suggested some separation of the nerve subtypes into four classes which corresponded with the nerve types. This was supported by the K-means clustering. Some overlap in classes was noted in these two clustering analyses. This study provides emerging evidence that DESI-MSI is an effective tool for metabolomic profiling of peripheral nerves. Our results suggest that peripheral nerves have molecular profiles that are distinct from the surrounding connective tissues and that DESI-MSI may be able to discriminate between nerve subtypes. DESI-MSI of peripheral nerves may be a valuable technique that could be used to improve our understanding of peripheral nerve anatomy and physiology. The ability to utilize ambient mass spectrometry techniques in real time could also provide an unprecedented advantage for surgical decision making, including in nerve-sparing procedures in the future.

Metabolically Active Zones Involving Fatty Acid Elongation Delineated by DESI-MSI Correlate with Pathological and Prognostic Features of Colorectal Cancer.

Colorectal cancer (CRC) is the second leading cause of cancer deaths. Despite recent advances, five-year survival rates remain largely unchanged. Desorption electrospray ionization mass spectrometry imaging (DESI) is an emerging nondestructive metabolomics-based method that retains the spatial orientation of small-molecule profiles on tissue sections, which may be validated by 'gold standard' histopathology. In this study, CRC samples were analyzed by DESI from 10 patients undergoing surgery at Kingston Health Sciences Center. The spatial correlation of the mass spectral profiles was compared with histopathological annotations and prognostic biomarkers. Fresh frozen sections of representative colorectal cross sections and simulated endoscopic biopsy samples containing tumour and non-neoplastic mucosa for each patient were generated and analyzed by DESI in a blinded fashion. Sections were then hematoxylin and eosin (H and E) stained, annotated by two independent pathologists, and analyzed. Using PCA/LDA-based models, DESI profiles of the cross sections and biopsies achieved 97% and 75% accuracies in identifying the presence of adenocarcinoma, using leave-one-patient-out cross validation. Among the m/z ratios exhibiting the greatest differential abundance in adenocarcinoma were a series of eight long-chain or very-long-chain fatty acids, consistent with molecular and targeted metabolomics indicators of de novo lipogenesis in CRC tissue. Sample stratification based on the presence of lympovascular invasion (LVI), a poor CRC prognostic indicator, revealed the abundance of oxidized phospholipids, suggestive of pro-apoptotic mechanisms, was increased in LVI-negative compared to LVI-positive patients. This study provides evidence of the potential clinical utility of spatially-resolved DESI profiles to enhance the information available to clinicians for CRC diagnosis and prognosis.

A MALDI-TOF MS library for rapid identification of human commensal gut bacteria from the class Clostridia.

Microbial isolates from culture can be identified using 16S or whole-genome sequencing which generates substantial costs and requires time and expertise. Protein fingerprinting via Matrix-assisted Laser Desorption Ionization-time of flight mass spectrometry (MALDI-TOF MS) is widely used for rapid bacterial identification in routine diagnostics but shows a poor performance and resolution on commensal bacteria due to currently limited database entries. The aim of this study was to develop a MALDI-TOF MS plugin database (CLOSTRI-TOF) allowing for rapid identification of non-pathogenic human commensal gastrointestinal bacteria. We constructed a database containing mass spectral profiles (MSP) from 142 bacterial strains representing 47 species and 21 genera within the class Clostridia. Each strain-specific MSP was constructed using >20 raw spectra measured on a microflex Biotyper system (Bruker-Daltonics) from two independent cultures. For validation, we used 58 sequence-confirmed strains and the CLOSTRI-TOF database successfully identified 98 and 93% of the strains, respectively, in two independent laboratories. Next, we applied the database to 326 isolates from stool of healthy Swiss volunteers and identified 264 (82%) of all isolates (compared to 170 (52.1%) with the Bruker-Daltonics library alone), thus classifying 60% of the formerly unknown isolates. We describe a new open-source MSP database for fast and accurate identification of the Clostridia class from the human gut microbiota. CLOSTRI-TOF expands the number of species which can be rapidly identified by MALDI-TOF MS.

Aerosol Mass Spectral Profiles from NAMaSTE Field-Sampled South Asian Combustion Sources.

Unit mass resolution mass spectral profiles of nonrefractory submicron aerosol were retrieved from undersampled atmospheric emission sources common to South Asia using a "mini" aerosol mass spectrometer. Emission sources including wood- and dung-fueled cookstoves, agricultural residue burning, garbage burning, engine exhaust, and coal-fired brick kilns were sampled during the 2015 Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE) campaign. High-resolution peak fitting estimates of the mass spectra were used to characterize ions found within each source profile and help identify mass spectral signatures unique to aerosol emissions from the investigated source types. The first aerosol mass spectral profiles of dung burning, charcoal burning, garbage burning, and brick kilns are provided in this work. The online aerosol mass spectra show that organics were generally the dominant component of the nonrefractory aerosol. However, inorganic aerosol components including ammonium and chloride were significant in dung- and charcoal-fired cookstove emissions and sulfate compounds were major components of the coal-fired brick kiln emissions. Organic mass spectra from both the charcoal burning and zigzag brick kiln were dominated by nitrogen-containing ions thought to be from the electron ionization of amines and amides contained in the emissions. The mixed garbage burning emissions profiles were dominated by plastic combustion with very low fractions of organic markers associated with biomass burning. The plastic burning emissions were associated with enhanced organic signal at mass-to-charge (m/z) 104 and m/z 166, which could be useful fragment ion indicators for garbage burning in ambient aerosol profiles. Finally, a framework for the identification of emission sources using the unit mass resolution organic mass fractions at m/z 55 (f 55), m/z 57 (f 57), and m/z 60 (f 60) is proposed in this work. Plotting the ratio of f 55 to f 57 versus f 60 is found to be effective for the identification of emissions by the fuel type and even useful in separating emissions of similar source types. Although the sample size was limited, these results give further context to the aerosol and gas-phase emission factors presented in other NAMaSTE works and provide a critical reference for future aerosol composition measurements in South Asia.

Contributions of primary sources to submicron organic aerosols in Delhi, India

Abstract. Delhi, India, experiences extremely high concentrations of primary organic aerosol (POA). Few prior source apportionment studies on Delhi have captured the influence of biomass burning organic aerosol (BBOA) and cooking organic aerosol (COA) on POA. In a companion paper, we develop a new method to conduct source apportionment resolved by time of day using the underlying approach of positive matrix factorization (PMF). We call this approach “time-of-day PMF” and statistically demonstrate the improvements of this approach over traditional PMF. Here, we quantify the contributions of BBOA, COA, and hydrocarbon-like organic aerosol (HOA) by applying positive matrix factorization (PMF) resolved by time of day on two seasons (winter and monsoon seasons of 2017) using organic aerosol measurements from an aerosol chemical speciation monitor (ACSM). We deploy the EPA PMF tool with the underlying Multilinear Engine (ME-2) as the PMF solver. We also conduct detailed uncertainty analysis for statistical validation of our results. HOA is a major constituent of POA in both winter and the monsoon. In addition to HOA, COA is found to be a major constituent of POA in the monsoon, and BBOA is found to be a major constituent of POA in the winter. Neither COA nor the different types of BBOA were resolved in the seasonal (not time-resolved) analysis. The COA mass spectra (MS) profiles are consistent with mass spectral profiles from Delhi and around the world, particularly resembling MS of heated cooking oils with a high m/z 41. The BBOA MS have a very prominent m/z 29 in addition to the characteristic peak at m/z 60, consistent with previous MS observed in Delhi and from wood burning sources. In addition to separating the POA, our technique also captures changes in MS profiles with the time of day, a unique feature among source apportionment approaches available. In addition to the primary factors, we separate two to three oxygenated organic aerosol (OOA) components. When all factors are recombined to total POA and OOA, our results are consistent with seasonal PMF analysis conducted using EPA PMF. Results from this work can be used to better design policies that target relevant primary sources of organic aerosols in Delhi.

New Insights into Human Biotransformation of BDE-209: Unique Occurrence of Metabolites of Ortho-Substituted Hydroxylated Higher Brominated Diphenyl Ethers in the Serum of e-Waste Dismantlers

Extremely high levels of decabromodiphenyl ether (BDE-209) are frequently found in the serum of occupationally exposed groups, such as e-waste dismantlers and firefighters. However, the metabolism of BDE-209 in the human body is not adequately studied. In this study, 24 serum samples were collected from workers at a typical e-waste recycling workshop in Taizhou, Eastern China, and the occurrence and fate of these higher brominated diphenyl ethers (PBDEs) were investigated. The median concentration of the total PBDEs in the serum was 199 ng/g lipid weight (lw), ranging from 125 to 622 ng/g lw. Higher brominated octa- to deca-BDEs accounted for more than 80% of the total PBDEs. Three ortho-hydroxylated metabolites of PBDEs─6-OH-BDE196, 6-OH-BDE199, and 6'-OH-BDE206─were widely detected with a total concentration (median) of 92.7 ng/g lw. The concentrations of the three OH-PBDEs were significantly higher than their octa- and nona-PBDE homologues, even exceeding those of the total PBDEs in several samples, indicating that the formation of OH-PBDEs was a major metabolic pathway of the higher brominated PBDEs in occupationally exposed workers. An almost linear correlation between 6-OH-BDE196 and 6-OH-BDE199 (R = 0.971, P < 0.001) indicates that they might undergo a similar biotransformation pathway in the human body or may be derived from the same precursor. In addition, the occurrence of a series of penta- to hepta- ortho-substituted OH-PBDEs was preliminarily identified according to their unique "predioxin" mass spectral profiles by GC-ECNI-MS. Taken together, the tentative metabolic pathway for BDE-209 in e-waste dismantlers was proposed. The oxidative metabolism of BDE-209 was mainly observed at the ortho positions to form 6'-OH-BDE-206, which later underwent a consecutive loss of bromine atoms at the meta or para positions to generate other ortho-OH-PBDEs. Further studies are urgently needed to identify the chemical structures of these ortho-OH-PBDE metabolites, and perhaps more importantly to clarify the potentially toxic effects, along with their underlying molecular mechanisms.

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 10m × 0.25mm ID × 0.25µm df and medium polarity with dimensions 2m × 0.10mm ID × 0.10µm 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.

Characterization of Kimchi by Ultra-Performance Liquid Chromatography (UPLC) and High-Resolution Mass Spectrometry (HR-MS) with Principal Component Analysis (PCA) and Partial Least Squares-Discriminant Analysis (PLS-DA)

The geographic origin of kimchi is of interest to both consumers and producers as the prices of these products vary substantially depending on the geographic origin. Therefore, social problems related to the geographic origin of kimchi in Korea are of concern. In this study, nine types of kimchi from Korea and China were analyzed, each of which was fermented for one or four weeks. This is the first report on mass spectral profiling of kimchi using liquid chromatography–high resolution–mass spectrometry (LC-HR-MS), from which 1552 kinds of spectral peaks were obtained. Distinguishing the geographic origins of kimchi was possible by analyzing the mass spectral profiles of the Korean and Chinese kimchi samples using multivariate analyses, irrespective of the fermentation period. Based on the variable importance in projection (VIP) scores from the partial least squares (PLS) and the p-values from the t-test, 25 spectral peaks were selected that exhibited the potential to be biomarkers. Therefore, LC-HR-MS is a powerful tool for clearly distinguishing kimchi samples with different origins. This study forms a basis for mass spectral profiling analyses of other fermented vegetables.

Comparison of Plasma Ionization- and Secondary Electrospray Ionization- High-resolution Mass Spectrometry for Real-time Breath Analysis

Real-time breath analysis by high-resolution mass spectrometry (HRMS) is a promising method to noninvasively retrieve relevant biochemical information. In this work, we conducted a head-to-head comparison of two ionization techniques: Secondary electrospray ionization (SESI) and plasma ionization (PI), for the analysis of exhaled breath. Two commercially available SESI and PI sources were coupled to the same HRMS device to analyze breath of two healthy individuals in a longitudinal study. We analyzed 58 breath specimens in both platforms, leading to 2,209 and 2,296 features detected by SESI-HRMS and by PI-HRMS, respectively. 60% of all the mass spectral features were detected in both platforms. However, remarkable differences were noted in terms of the signal-to-noise ratio (S/N), whereby the median (interquartile range, IQR) S/N ratio for SESI-HRMS was 115 (IQR = 408), whereas for PI-HRMS it was 5 (IQR = 5). Differences in the mass spectral profiles for the same samples make the inter-comparability of both techniques problematic. Overall, we conclude that both techniques are excellent for real-time breath analysis because of the very rich mass spectral fingerprints. However, further work is needed to fully understand the exact metabolic insights one can gather using each of these platforms.

Introducing Nafion for In Situ Desalting and Biofluid Profiling in Spray Mass Spectrometry.

We introduce Nafion into the ambient ionization technique of spray mass spectrometry to serve for in situ desalting and direct analysis of biological fluids. Nafion was coated onto the surface of the triangular spray tip as the cation exchange material. Because the sulfonic group from the Nafion membrane effectively exchanges their carried protons with inorganic salt ions (e.g., Na+ and K+), the analyte’s ionization efficiency can be significantly enhanced by reducing ion suppression. The desalting efficiency can reach 90% and the maximum tolerance of the absolute salt amount reaches 100 μmol. The mass spectral profile can also be simplified by removing the multiple adducted ion types from small-molecule drugs and metabolites ([M + Na]+ and [M + K]+), or multiply charged ions formed by proteins ([M + nNa]n+ and [M + nK]n+). Thus, the Nafion coating makes less ambiguous data interpretation collected from spray mass spectrometry for qualitative profiling or quantitative measurement of a target analyte.

SIMS Analysis of Thin EUV Photoresist Films.

This study reports on the application of secondary ion mass spectrometry (SIMS) for examining thin (20-50 nm) chemically amplified resist films on silicon. SIMS depth profiling was carried out using a gas cluster ion beam to ensure minimal sputter-induced damage to the organic constituents of interest. Specific attention concerned the distribution of the photo acid generator (PAG) molecule within these films, along with the photo-induced fragmentation occurring on extreme ultra-violet photo exposure. Positive secondary ion spectra were collected using a traditional time of flight (ToF)-SIMS and the latest generation IONTOF Hybrid SIMS instrumentation equipped with an OrbitrapTM mass analyzer. Tandem mass spectrometry (MS/MS) capability within the OrbitrapTM secondary ion column was utilized to verify that the C19H17S+ secondary ion did indeed have the molecular structure consistent with the PAG structure. The superior mass resolving power of the OrbitrapTM mass analyzer (∼20× of the ToF mass analyzer) along with improved mass accuracy (a few ppm) proved pivotal in the mass spectral and depth profile analysis of these films. This was not the case for the ToF-SIMS experiments, as the mass spectra, as well as the associated depth profiles, exhibited severe molecular (isobaric) interferences.