Direct Injection Mass Spectrometry Research Articles

Emerging evidence on the potential of PTR‐MS as rapid, direct and high‐sensitivity sensors to promote innovation in the fermented beverages sector

SummaryIn food technology, the term ‘fermentation’ encompasses a spectrum of microbial‐driven bioprocesses that preserve and improve the quality of raw materials, transforming them into new fermented products with minimal resource consumption. Furthermore, fermentation plays a crucial role in driving the eco‐friendly transformation of the agricultural industry. Within this domain, the fermented beverage sector stands out due to its consumer‐friendly appeal. To promote innovation in this field, there is a need for cost‐effective, versatile and sustainable techniques that can accelerate research and development activities. In the bioprocess sector, innovation management requires consideration of an array of variables, including diverse raw materials, various microorganisms and different fermentation parameters. Direct injection mass spectrometry (DIMS) technologies offer solutions for bioprocess monitoring, particularly in the analysis of volatile organic compounds (VOCs) and are constantly improving their performance in terms of sensitivity and specificity. Among the DIMS methods, proton transfer reaction‐mass spectrometry (PTR‐MS), when coupled with autosampling and customised data handling and analysis, has demonstrated its efficiency in studying VOCs associated with fermentation. This approach brings automation to data production and management, offers exceptional versatility akin to a sensor and aligns closely with the principles of green chemistry. In this perspective paper, after reviewing key aspects of modern fermentation practice, we showcase the application of PTR‐MS as a model to demonstrate its potential as sensor‐like approach to drive innovation within the fermented beverage sector. This approach enables swift, large‐scale assessments of multiple variables while providing comprehensive insights into the quality and safety of the final products.

Spectral averaging with outlier rejection algorithms to increase identifications in top-down proteomics.

The identification of proteoforms by top-down proteomics requires both high quality fragmentation spectra and the neutral mass of the proteoform from which the fragments derive. Intact proteoform spectra can be highly complex and may include multiple overlapping proteoforms, as well as many isotopic peaks and charge states. The resulting lower signal-to-noise ratios for intact proteins complicates downstream analyses such as deconvolution. Averaging multiple scans is a common way to improve signal-to-noise, but mass spectrometry data contains artifacts unique to it that can degrade the quality of an averaged spectra. To overcome these limitations and increase signal-to-noise, we have implemented outlier rejection algorithms to remove outlier measurements efficiently and robustly in a set of MS1 scans prior to averaging. We have implemented averaging with rejection algorithms in the open-source, freely available, proteomics search engine MetaMorpheus. Herein, we report the application of the averaging with rejection algorithms to direct injection and online liquid chromatography mass spectrometry data. Averaging with rejection algorithms demonstrated a 45% increase in the number of proteoforms detected in Jurkat T cell lysate. We show that the increase is due to improved spectral quality, particularly in regions surrounding isotopic envelopes.

Quantitation of glyphosate, glufosinate, and AMPA in drinking water and surface waters using direct injection and charged-surface ultra-high performance liquid chromatography-tandem mass spectrometry

Herbicides glyphosate (N-(phosphonomethyl)glycine) and glufosinate (2-amino-4-(hydroxymethylphosphinyl)butanoic acid) and the main transformation product of glyphosate, aminomethanephosphonic acid (AMPA), are challenging to analyze for in environmental samples. The quantitative method developed by this study adapts previously standardized dechlorination procedures coupled to a novel charged surface C18 column, ultra-high performance liquid chromatography-tandem mass spectrometry, polarity switching, and direct injection. The method was applied to chlorinated tap water, as well as river samples, collected in the City of Winnipeg and rural Manitoba, Canada. Using only syringe filtration without derivatization, the validated method resulted in good accuracies in both tap and surface water, at both 2 and 20 μg L−1. Method limits of detection (MLD) and quantification (MLQ) ranged from 0.022/0.074 to 0.11/0.36 μg L−1, with precisions of 0.46–2.2% (intraday) and 1.3–7.3% (interday). The mean (SEM) of the pesticides in μg L−1 for tap water were 0.11 (0.007) (AMPA), glufosinate and glyphosate < MLDs; and for Red River water were 0.56 (0.045) (AMPA), glufosinate < MLQ, and glyphosate 0.40 (0.072). For the smaller tributaries, glufosinate was >MLD but < MLQ once and that was for Shannon Creek at 0.2 μg L−1. For the remaining rivers, the mean concentrations ranged from 0.31 to 3.1 μg L−1 for AMPA, and 0.087–0.53 μg L−1 for glyphosate. The method will be ideal for supporting monitoring and risk assessment programs that require high throughput sampling and quantitative methods capable of producing robust results that leverages chromatographic and mass spectrometric paradigms instead of being extraction technology focused.

Advances in the Application of Direct Injection Mass Spectrometry Techniques to the Analysis of Grape, Wine and Other Alcoholic Beverages.

Direct injection mass spectrometry (DIMS) entails the direct introduction of a gaseous sample into a mass analyser without prior treatment or separation. DIMS techniques offer the opportunity to monitor processes in time, with limits of detection as low as 0.5 parts per trillion in volume (for a 1 s measurement time) while providing results with high informational content. This review provides insight into current and promising future developments of DIMS in the analysis of grape, wine and other alcoholic beverages. Thanks to its unique characteristics, DIMS allows the online monitoring of volatile organic compounds (VOCs) released by grapes during fermentative bioprocesses or by wine directly from the glass headspace or during drinking. A DIMS-based approach can also be adopted to perform quality control and high-throughput analysis, allowing us to characterise the volatile profile of large sample sets rapidly and in a comprehensive fashion. Furthermore, DIMS presents several characteristic elements of green analytical chemistry approaches, catalysing an interest linked to the development of sustainable paths in research and development activities in the field of viticulture and oenology.

Dynamic Instrumental and Sensory Methods Used to Link Aroma Release and Aroma Perception: A Review.

Perception of flavor is a dynamic process during which the concentration of aroma molecules at the olfactory epithelium varies with time as they are released progressively from the food in the mouth during consumption. The release kinetics depends on the food matrix itself but also on food oral processing, such as mastication behavior and food bolus formation with saliva, for which huge inter-individual variations exist due to physiological differences. Sensory methods such as time intensity (TI) or the more-recent methods temporal dominance of sensations (TDS) and temporal check-all-that-apply (TCATA) are used to account for the dynamic and time-related aspects of flavor perception. Direct injection mass spectrometry (DIMS) techniques that measure in real time aroma compounds directly in the nose (nosespace), aimed at obtaining data that reflect the pattern of aroma release in real time during food consumption and supposed to be representative of perception, have been developed over the last 25 years. Examples obtained with MS operated in chemical ionization mode at atmospheric or sub-atmospheric pressure (atmospheric pressure chemical ionization APCI or proton-transfer reaction PTR) are given, with emphases on studies conducted with simultaneous dynamic sensory evaluation. Inter-individual variations in terms of aroma release and their relevance for understanding flavor perception are discussed as well as the evidenced cross-modal interactions.

Evaluation of Solvent Compatibilities for Headspace-SIFT-MS Analysis of Pharmaceutical Products

Procedures for determination of the residual solvent and volatile impurity content in pharmaceutical products usually rely on dissolution in a solvent, followed by headspace-gas chromatography (HS-GC) analysis. Whereas chromatographic systems can utilize a wide variety of solvents, direct-injection mass spectrometry (DIMS) techniques have fewer solvent options, because elimination of the chromatographic column means that the instrument is more susceptible to saturation. Since water has the lowest impact, it has almost always been the default solvent for DIMS. In this study, selected ion flow tube mass spectrometry (SIFT-MS)—a DIMS technique—was applied to the systematic evaluation of the proportion of solvent that can be utilized (with aqueous diluent) without causing instrument saturation and while maintaining satisfactory analytical performance. The solvents evaluated were N,N-dimethylacetamide (DMAC), N,N-dimethylformamide (DMF), 1,3-dimethyl-2-imidazolidinone (DMI), dimethyl sulfoxide (DMSO), methanol, and triacetin. All solvents are compatible with headspace-SIFT-MS analysis at 5% (min) in water, while DMI, DMAC, and DMSO can be used at higher concentrations (50, 100, and 25%, respectively), though suffering substantial diminution of the limit of quantitation for non-polar analytes at higher proportions of non-aqueous solvent. Analytical performance was also evaluated using linearity, repeatability, and recovery measurements. This work demonstrates that organic solvents diluted in water can be utilized with headspace-SIFT-MS and provide an approach for evaluation of additional diluent solvents.

Demystifying Sample Preparation for Headspace Analysis Using Direct Injection Mass Spectrometry

Sample preparation for headspace analysis of volatile organic compounds (VOCs) by gas chromatography (GC) is well understood. Newer direct‑injection mass spectrometry (DIMS) techniques have found application in headspace analysis, but with some necessary modifications due to (i) the removal of the chromatographic column, and (ii) the soft chemical ionization that is used in these techniques. These factors place important constraints on the total load of VOCs—whether of solvents, analytes, or other VOCs in the matrix. This article summarizes the basic differences between DIMS and GC approaches, and describes the strategies by which headspace-DIMS can be successfully adopted.

Rapid Determination of Ethyl Carbamate in Chinese Liquor via a Direct Injection Mass Spectrometry with Time-Resolved Flash-Thermal-Vaporization and Acetone-Assisted High-Pressure Photoionization Strategy.

Ethyl carbamate (EC), a carcinogenic compound, is naturally produced in fermented foods and alcoholic beverages. Rapid and accurate measurement of EC is necessary and important for quality control and safety evaluation of Chinese liquor, a traditionally distilled spirit with the highest consumption in China, but it remains a great challenge. In this work, a direct injection mass spectrometry (DIMS) with time-resolved flash-thermal-vaporization (TRFTV) and acetone-assisted high-pressure photoionization (HPPI) strategy has been developed. EC was rapidly separated from the main matrix components, ethyl acetate (EA) and ethanol, by the TRFTV sampling strategy due to the retention time difference of these three compounds with large boiling point differences on the inner wall of a poly(tetrafluoroethylene) (PTFE) tube. Therefore, the matrix effect of EA and ethanol was effectively eliminated. The acetone-assisted HPPI source was developed for efficient ionization of EC through a photoionization-induced proton transfer reaction between EC molecules and protonated acetone ions. The accurate quantitative analysis of EC in liquor was achieved by introducing an internal standard method (ISM) using deuterated EC (d5-EC). As a result, the limit of detection (LOD) for EC was 8.88 μg/L with the analysis time of only 2 min, and the recoveries ranged from 92.3 to 113.1%. Finally, the prominent capability of the developed system was demonstrated by rapid determination of trace EC in Chinese liquors with different flavor types, exhibiting wide potential applications in online quality control and safety evaluation of not only Chinese liquors but also other liquor and alcoholic beverages.

On-Site Detection of Volatile Organic Compounds (VOCs).

Volatile organic compounds (VOCs) are of interest in many different fields. Among them are food and fragrance analysis, environmental and atmospheric research, industrial applications, security or medical and life science. In the past, the characterization of these compounds was mostly performed via sample collection and off-site analysis with gas chromatography coupled to mass spectrometry (GC-MS) as the gold standard. While powerful, this method also has several drawbacks such as being slow, expensive, and demanding on the user. For decades, intense research has been dedicated to find methods for fast VOC analysis on-site with time and spatial resolution. We present the working principles of the most important, utilized, and researched technologies for this purpose and highlight important publications from the last five years. In this overview, non-selective gas sensors, electronic noses, spectroscopic methods, miniaturized gas chromatography, ion mobility spectrometry and direct injection mass spectrometry are covered. The advantages and limitations of the different methods are compared. Finally, we give our outlook into the future progression of this field of research.

Serum metabolomic characterization in pigs in relation to birth weight category and neonatal nutrition.

The objective of this study was to characterize developmental differences in low birth weight (LBW) and normal birth weight (NBW) piglets with or without pre-weaning nutrient restriction using serum metabolomic profile analysis. At farrowing, 112 piglets were identified as LBW (1.22 ± 0.28 kg) or NBW (1.70 ± 0.27 kg) and were randomly assigned to receive normal nutrition (NN) or restricted nutrition (RN) (6 h/day no suckling) from days 2 to 28 post farrow (n = 8 pigs/group). On day 28, piglets were weaned onto a common diet. Fasted blood samples were obtained on days 28 and 56 (n = 8 pigs/group) and were analyzed using quantitative metabolomics via a combination of direct injection mass spectrometry with a reverse-phase LC-MS/MS custom assay. Data were normalized using logarithmic transformation and auto-scaling. Partial least squares discriminant analysis (PLS-DA) was carried out to further explore the differential metabolites among the groups (metaboanalyst.ca) with an integrated enrichment and pathway topography analysis. On day 28, LBW piglets had lower levels of essential amino acids as well as reduced metabolites associated with fatty acid oxidation, glycolysis, and the tri-carboxylic acid (TCA) cycle compared to the NBW group. The overall reduction of metabolites associated with energy production and regulation suggests that LBW vs. NBW are in an energy-survival state. On day 56, LBW pigs had increased utilization of fatty acids and resultant ketone production, evident by increased carnitines, acetoacetate, β-hydroxybutyrate, and glycerol compared to NBW pigs. In addition, compared to the NBW pigs LBW pigs had a consistent decrease in serum glucose and lactate as well as reduced TCA cycle metabolites: pyruvate, succinate, citrate, and α-ketoglutaric acid similar to day 28. Low reliance on glycolysis and the TCA cycle and higher glycerol production in the LBW pigs may indicate impairments in glucose tolerance at 56 d. In summary, LBW piglets appear to have more metabolic alterations in early life, which is not resolved with adequate nutrition or refeeding and may elucidate physiological and metabolic mechanisms of poor growth and life performance compared to NBW pigs later in life.

Metabolites, elemental profile and chemical activities of Pinus strobus high temperature-derived pyroligneous acid

BackgroundPyroligneous acid (PA) is an aqueous smoky fraction produced during pyrolysis of biomass. The chemical composition of PA from different plant biomass has been studied, but reports on PA metabolites and elemental profiles are rare. In this study, we examined the metabolites, elemental profiles and the associated chemical activities of PA derived from white pine (Pinus strobus) at 1100 °C compared to similar work done elsewhere using different biomass at lower temperatures.ResultsPA from P. strobus biomass exhibited a lower electrical conductivity (2.05 mS/cm), salinity (1.03 g/L) and total dissolved solids (1.42 g/L) but higher oBrix content (9.35 ± 0.06) compared to PA from other feedstock. The P. strobus PA showed a higher antioxidant activity characterized by enhanced radical scavenging activity against 1,1-diphenyl-2-picrylhydrazyl free-radical (78.52%) and accumulation of higher total phenolic (95.81 ± 1.45 gallic acid equivalents (GAE)/mL) and flavonoid content (49.46 µg quercetin/mL). Metabolite profiling by direct injection mass spectrometry with a reverse-phase liquid chromatography–mass spectrometry (DI/LC–MS/MS) identified a total of 156 metabolites. Four (4) main groups including organic acids (90.87%), hexose (8.60%), carnitine (0.3%) and phospholipids (0.24%) were found in the PA. Mineral element analysis revealed that the P. strobus PA contained high concentrations of nitrogen (N), potassium (K), calcium (Ca) and zinc (Zn), while the content of sodium (Na) and trace/heavy metals were present at levels below the reported limit.ConclusionThis study indicates that P. strobus PA is a valuable product that can be used in agriculture to improve plant growth and productivity under normal and environmentally stressful conditions.Graphical

Potential Plasma Metabolite Biomarkers of Diabetic Nephropathy: Untargeted Metabolomics Study.

Diabetic nephropathy (DN) is one of the specific complications of diabetes mellitus and one of the leading kidney-related disorders, often requiring renal replacement therapy. Currently, the tests commonly used for the diagnosis of DN, albuminuria (AU) and glomerular filtration rate (GFR), have limited sensitivity and specificity and can usually be noted when typical morphological changes in the kidney have already been manifested. That is why the extreme urgency of the problem of early diagnosis of this disease exists. The untargeted metabolomics analysis of blood plasma samples from 80 patients with type 1 diabetes and early and late stages of DN according to GFR was performed using direct injection mass spectrometry and bioinformatics analysis for diagnosing signatures construction. Among the dysregulated metabolites, combinations of 15 compounds, including amino acids and derivatives, monosaccharides, organic acids, and uremic toxins were selected for signatures for DN diagnosis. The selected metabolite combinations have shown high performance for diagnosing of DN, especially for the late stage (up to 99%). Despite the metabolite signature determined for the early stage of DN being characterized by a diagnostic performance of 81%, these metabolites as potential biomarkers might be useful in the evaluation of treatment of the disease, especially at early stages that may reduce the risk of kidney failure development.

Application of Headspace-SIFT-MS to Direct Analysis of Hazardous Volatiles in Drinking Water

Harmful volatile organic compounds (VOCs) are present in drinking water due to anthropogenic activities, such as oil refining (e.g., benzene) and disinfection (e.g., the so-called trihalomethanes, THMs). Gas chromatography (GC)-based techniques are widely applied for analysis of these compounds in the laboratory but have some throughput drawbacks due to sample preparation and the extended analysis time (due to chromatographic separation). Selected ion flow tube mass spectrometry (SIFT-MS) is a direct-injection mass spectrometry (DIMS) technique that has potential to reduce sample preparation and analysis times through direct analysis of aqueous headspace with no preconcentration, drying, or other water management. This study applies headspace-SIFT-MS to the analysis of benzene, related petroleum aromatics, and THMs to evaluate the potential for enhanced sample throughput for drinking water analysis (10 samples per hour). Headspace-SIFT-MS achieved a limit of quantitation (LOQ) of 0.1 to 0.2 μg L−1 for benzene, toluene, ethylbenzene and xylenes (BTEX), and 1 to 2 μg L−1 for the THMs. These LOQs achieve the current European Union and United States regulatory limits but are higher than modern GC methods. Therefore, the potential application of SIFT-MS is envisaged to lie in rapid screening in the laboratory, or field-based real-time monitoring.

Volatile fingerprinting by solid-phase microextraction mass spectrometry for rapid classification of honey botanical source

Volatile fingerprinting by Headspace-Solid-Phase Microextraction followed by Direct Injection Mass Spectrometry (HS-SPME DIMS) has been assessed for the first time as an alternative approach to gas chromatographic methods (HS-SPME GC-MS) for the rapid classification of honey botanical origin. In order to fully evaluate the potential of SPME for honey authentication, samples from different botanical sources (eucalyptus, citrus, acacia, rosemary and honeydew) were analyzed by both approaches using either carboxen/polydimethylsiloxane (C/PDMS) or polyacrylate SPME fibers. These datasets were further subjected to different supervised and unsupervised chemometric techniques, including powerful machine learning methods such as FreeViz, not previously applied for this purpose. The best overall classification rate (99% success), outperforming that provided by GC-MS data (98.25% success), was obtained when partial least squares-linear discriminant analysis was applied to mass spectral fingerprints gathered by C/PDMS fiber. The HS-SPME DIMS approach here optimized is shown as an advantageous alternative in terms of analysis time over chromatographic methods (2 vs 50 min), as well as a reliable and cost-efficient approach for honey source authentication issues both in research and food industry fields.

PSVI-4 Serum Metabolomic Characterization of Birth Weight and Neonatal Nutrient Restriction on Piglet Growth and Development

Abstract The objective was to characterize developmental differences in low birth weight (LBW) and normal birth weight (NBW) piglets with or without nutrient restriction using serum metabolomic profile analysis. After farrowing, 112 piglets were selected as LBW (1.22 ± 0.28 kg) or NBW (1.70 ± 0.27 kg) and were categorized to receive normal nutrition (NN) or restricted nutrition (RN - 6 h/day no suckling) until d 28 when the pigs were weaned onto a common diet until d 56. Blood samples were taken on d 28 and d 56 (n=8 pigs/treatment) and were analyzed using quantitative metabolomics via a combination of direct injection mass spectrometry with a reverse-phase LC-MS/MS custom assay (TMIC prime). Data were normalized using logarithmic transformation and auto-scaling. Partial least squares discriminant analysis (PLS-DA) was carried out to further explore the differential metabolites among the treatments (metaboanalyst.ca) with an integrated enrichment and pathway topography analysis. The results suggest that at d 28, LBW piglets had decreased metabolites associated with fatty acid oxidation, glycolysis and TCA cycle metabolites, and essential amino acids such as valine, leucine, arginine. These indicate a decrease utilization of gluconeogenic, and TCA cycle pathways compared with the NBW group. On d 56, LBW piglets had increased utilization of fatty acids, exhibited by increased production of serum acetoacetate, B-hydroxybutyrate, glycerol, compared with NBW. Additionally, the LBW piglets had decreased glucose utilization, pyruvate, succinate, citrate, a-ketoglutaric acid, and lactate compared with the NBW piglets. Due to low utilization of glycolysis and the TCA cycle, associated amino acids were less in LBW piglets, except for a increased glycerol which may indicate impairments in glucose tolerance. In summary, LBW piglets appear to have more metabolic deficiencies in early life, which is not resolved with nutrition in early life, but may be responsive to a tailored nutritional intervention post-weaning.

PSVIII-B-8 Effects of Habituation to Livestock Trailer and Extended Transportation on Plasma Metabolomic Profiles in Goats

Abstract Goats raised for meat production are often transported long distances. Twelve-month-old male Spanish goats were used to determine the effects of habituation to trailers on plasma metabolomic profiles when transported for long periods. In a split-plot design, 168 goats were separated into two treatment (TRT; whole plot) groups and maintained on two different paddocks. Concentrate supplement was fed to one group inside two livestock trailers (habituated group, H), while the other group received the same quantity of concentrate, but not inside the trailers (non-habituated, NH). Goats were subjected to a 10-hour transportation stress in 4 replicates (n = 21 goats/replicate/TRT) after 4 weeks of habituation period. Blood samples were collected prior to loading (Preload), 20 min after loading (0 h), and at 2, 4, 6, 8, and 10 h of transportation (Time; subplot). A targeted quantitative metabolomics approach was employed to analyze the samples using a combination of direct injection mass spectrometry with a reverse-phase LC–MS/MS custom assay. The data were analyzed using R software. Several amino acids (alanine, serine, glycine, histidine, glutamate, trans-hydroxyproline, asparagine, threonine, methylhistidine, ornithine, proline, leucine, tryptophan) were higher (P &amp;lt; 0.05) in the H group compared to the NH group. Five diacylphosphotidyl cholines, 10 lysophosphotidyl cholines, and several other sphingomyelins were higher (P &amp;lt; 0.05) in the NH group compared to the H group. Butyric acid, propionic acid, alpha-ketoglutaric acid, and beta-hydroxybutyric acid concentrations were lower (P &amp;lt; 0.05) in the NH goats compared to the H goats. In general, amino acid concentrations decreased and acylcarnitine levels increased with transportation time (P&amp;lt;0.05). Habituation to trailers can be beneficial in enhancing stress coping abilities in goats due to higher concentrations of metabolites that support energy homeostasis and antioxidant activities. Fatty acid metabolism may be the main energy pathway in goats during long-distance transportation.

The Prevalence of Opioids in US Drinking Water Sources Detected Using Direct-Injection High-Performance Liquid Chromatography-Tandem Mass Spectrometry.

Active pharmaceutical ingredient (API) contamination of water sources, including opioid contamination, has become more common in recent years. Although drinking water-treatment plants help mitigate API infiltration, API contamination remains in some drinking water sources. Therefore, the ability to detect APIs at ultratrace concentrations is vital to ensure safe drinking water. A method for the ultratrace determination of fentanyl, hydrocodone, and codeine in drinking water via direct injection and high-performance liquid-chromatography tandem mass spectrometry (HPLC-MS/MS) was developed and validated. Drinking water samples (10 ml) are simply syringe-filtered and then analyzed by HPLC-MS/MS. A wide linear range (0.25-100 ng/L) and ultratrace limits of detection (80, 150, and 500 pg/L for fentanyl, hydrocodone, and codeine, respectively) were features of the method. The method produced excellent aggregate accuracies of 90%-115% and precisions of ≤11% for the three analytes tested. This method was used to test drinking water samples from 53 US locations, with hydrocodone and codeine detected in approximately 40% of the samples tested at concentrations between 0.3 and 20 ng/L. Codeine was detected at higher concentrations than hydrocodone (up to 7.3 times) for each sample containing these APIs. Fentanyl was not detected in any field drinking water sample. The detection of opioids in a large fraction of the US drinking water samples tested is cause for concern, and these levels should continue to be monitored to ensure that they do not become a threat to human health. Environ Toxicol Chem 2022;41:2658-2666. © 2022 SETAC.

Real-Time Monitoring of Volatile Organic Compounds in Ambient Air Using Direct-Injection Mass Spectrometry

Exposure to volatile organic compounds (VOCs) at low parts per billion (ppb) concentrations (by volume, ppbV) in ambient air is increasingly being recognized as a health risk. Furthermore, VOCs contribute to the formation of photochemical smog and particulate matter, which are hazardous and negatively impact the environment. Although most urban VOCs are anthropogenic in origin, some are produced by living organisms, especially trees. Gas chromatography (GC) is conventionally applied to VOC analysis of air, but it generally has a time resolution of tens of minutes and detection at low ppbV levels, frequently requiring sample preconcentration (such as using thermal desorption tubes (TDTs) or canister sampling with cryotrapping prior to analysis). Newer direct-injection mass spectrometry (DIMS) techniques can address the challenge of time resolution (seconds to tens of seconds) and eliminate the need for sampling via TDTs or canisters while still providing sufficient specificity. In this article, the results of a DIMS air monitoring campaign in Auckland, New Zealand, are described. Real-time selected ion flow tube mass spectrometry (SIFT–MS) measurements were obtained at three sites over a period of several weeks each: (i) adjacent to a freeway, (ii) in a residential area, and (iii) at a rural location. There were 13 compounds that were targeted in the study, covering various sources: fugitive emissions and incomplete combustion (benzene, toluene, and ethylbenzene, along with the xylene isomers, styrene, and ethanol), incomplete combustion (1,3-butadiene, formaldehyde, acetaldehyde, acrolein, benzaldehyde, and acetone), and biogenic origin (isoprene and monoterpenes (total of all isomers). At each site, SIFT–MS provided effective on-site analysis to sub-ppbV levels with better than 1-min time resolution.

Multiple Headspace Extraction-Selected Ion Flow Tube Mass Spectrometry (MHE-SIFT-MS). Part 1: A Protocol for Method Development and Transfer to Routine Analysis

The toxicity of many volatile organic compounds (VOCs) means that the safety of polymeric and other materials in contact with, or near, pharmaceutical and food products must be assured through sensitive, quantitative measurement. The multiple headspace extraction (MHE) technique was developed in the 1980s to provide quantitative analysis of VOCs in condensed-phase samples. Selected ion flow tube mass spectrometry (SIFT-MS) is a direct-injection mass spectrometry (DIMS) technique that often significantly reduces the analysis time for routine VOCs in headspace compared to gas chromatography (GC) methods. Using the prototypical polystyrene system, this study represents the first detailed application of MHE to SIFT-MS, describing protocols for method development (including optimization of equilibration temperature and time, plus calibration), data evaluation, and adoption of the technique into routine analysis. MHE-SIFT-MS gives an eight-fold throughput advantage over MHE-GC while being highly repeatable (relative standard deviation, RSD, less than 2%).

Energy Starvation in Daphnia magna from Exposure to a Lithium Cobalt Oxide Nanomaterial.

Growing evidence across organisms points to altered energy metabolism as an adverse outcome of metal oxide nanomaterial toxicity, with a mechanism of toxicity potentially related to the redox chemistry of processes involved in energy production. Despite this evidence, the significance of this mechanism has gone unrecognized in nanotoxicology due to the field's focus on oxidative stress as a universal─but nonspecific─nanotoxicity mechanism. To further explore metabolic impacts, we determined lithium cobalt oxide's (LCO's) effects on these pathways in the model organism Daphnia magna through global gene-expression analysis using RNA-Seq and untargeted metabolomics by direct-injection mass spectrometry. Our results show that a sublethal 1 mg/L 48 h exposure of D. magna to LCO nanosheets causes significant impacts on metabolic pathways versus untreated controls, while exposure to ions released over 48 h does not. Specifically, transcriptomic analysis using DAVID indicated significant enrichment (Benjamini-adjusted p ≤0.0.5) in LCO-exposed animals for changes in pathways involved in the cellular response to starvation (25 genes), mitochondrial function (70 genes), ATP-binding (70 genes), oxidative phosphorylation (53 genes), NADH dehydrogenase activity (12 genes), and protein biosynthesis (40 genes). Metabolomic analysis using MetaboAnalyst indicated significant enrichment (γ-adjusted p <0.1) for changes in amino acid metabolism (19 metabolites) and starch, sucrose, and galactose metabolism (7 metabolites). Overlap of significantly impacted pathways by RNA-Seq and metabolomics suggests amino acid breakdown and increased sugar import for energy production. Results indicate that LCO-exposed Daphnia respond to energy starvation by altering metabolic pathways, both at the gene expression and metabolite levels. These results support altered energy production as a sensitive nanotoxicity adverse outcome for LCO exposure and suggest negative impacts on energy metabolism as an important avenue for future studies of nanotoxicity, including for other biological systems and for metal oxide nanomaterials more broadly.