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Analysis of volatile organic compounds (VOCs) in water is conventionally conducted using gas chromatography (GC)-based methods, for which sample preparation demands are relatively high and throughput is relatively low due to the time taken to achieve chromatographic separation. Direct mass spectrometry (DMS) techniques such as selected ion flow tube mass spectrometry (SIFT-MS) have potential to analyze water headspace (HS) at high sensitivity with minimal sample preparation, eliminating preconcentration/purging and/or water management steps. However, the dearth of guidance for validation of DMS methods is an impediment to their adoption in routine analysis. This study applies and adapts an internationally recognized pharmaceutical industry guidance document for method validation to a prototypical SIFT-MS headspace analysis method for 17 toxic VOCs in water. The approach to validation is, however, applicable to any routine analysis conducted using SIFT-MS, and very likely to any methods developed using other DMS techniques. For the method developed and validated here, linearities (as measured by the linear regression coefficient, R2) were better than 0.990 for all compounds. Repeatability (measured using relative standard deviation, RSD) was less than 10% for all compounds. Similar method performance was observed for accuracy and recovery. The performance criteria achieved by this HS-SIFT-MS method suggest it has potential application in environmental and pharmaceutical routine analyses, perhaps as a rapid screening tool.

The analysis of volatile organic compounds (VOCs) within breath for noninvasive disease detection and monitoring is an emergent research field that has the potential to reshape current clinical practice. However, adoption of breath testing has been limited by a lack of standardization. This protocol provides a comprehensive workflow for online and offline breath analysis using selected ion flow tube mass spectrometry (SIFT-MS). Following the suggested protocol, 50 human breath samples can be analyzed and interpreted in

Selected ion flow tube mass spectrometry (SIFT‐MS) and ion chromatography (IC) were used to investigate the presence of volatile and nonvolatile compounds in canned tomatoes and in the polymeric lining before and after retorting the cans. This allowed us to observe if these compounds contributed to corrosion and the migration of iron and tin compounds from the cans to the tomatoes. Diced Roma tomatoes and other simulant treatment groups were sealed in two‐piece tinplated cans (controls in glass jars), retorted at 121℃ for 30 min, then stored at 49℃ for 50 days. Results showed that thermal degradation of amino acids in the tomatoes gave rise to volatile methyl sulfides and nonvolatile nitrogenous compounds which were subsequently sorbed by the can lining. SIFT‐MS showed a 20‐fold increase in dimethyl sulfide concentration. Inductively coupled plasma (ICP‐MS) results showed fourfold and 16‐fold increases in iron and tin compounds, respectively, that migrated from the metal to the tomatoes as a result of acid and electrolyte interactions., The process of washing, peeling dicing, canning and retorting of the tomatoes.

Volatile breath metabolites serve as potential disease biomarkers. Online mass spectrometry (MS) presents real-time quantification of breath volatile organic compounds (VOCs). The study aims to assess the relationship between two online analytical mass spectrometry techniques in the quantification of target breath metabolites: selected ion flow tube mass spectrometry (SIFT-MS) and proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS). The two following techniques were employed: (i) direct injection with bag sampling using SIFT-MS and PTR-ToF-MS and (ii) direct injection and thermal desorption (TD) tube comparison using PTR-ToF-MS. The concentration of abundant breath metabolites, acetone and isoprene, demonstrated a strong positive linear correlation between both mass spectrometry techniques (r = 0.97, r = 0.89, respectively; p 0.80, p < 0.001). Analyte concentrations were notably higher with the direct injection of a sampling bag compared to the TD method. All metabolites produced a high degree of agreement in the detection range of VOCs between SIFT-MS and PTR-ToF-MS, with the majority of compounds falling within 95% of the limits of agreement with Bland-Altman analysis. The cross platform analysis of exhaled breath demonstrates strong positive correlation coefficients, linear regression, and agreement in target metabolite detection rates between both breath sampling techniques. The study demonstrates the transferability of using data outputs between SIFT-MS and PTR-ToF-MS. It supports the implementation of a TD platform in multi-site studies for breath biomarker research in order to facilitate sample transport between clinics and the laboratory.

Aims The main aim of this study was to investigate the real-time detection of volatile metabolites for the species-level discrimination of pathogens associated with clinically relevant wound infection, when grown in a collagen wound biofilm model. Methods and Results This work shows that Staphylococcus aureus, Pseudomonas aeruginosa and Streptococcus pyogenes produce a multitude of volatile compounds when grown as biofilms in a collagen-based biofilm model. The real-time detection of these complex volatile profiles using selected ion flow tube mass spectrometry and the use of multivariate statistical analysis on the resulting data can be used to successfully differentiate between the pathogens studied. Conclusions The range of bacterial volatile compounds detected between the species studied vary and are distinct. Discrimination between bacterial species using real-time detection of volatile metabolites and multivariate statistical analysis was successfully demonstrated. Significance and Impact of the Study Development of rapid point-of-care diagnostics for wound infection would improve diagnosis and patient care. Such technological approaches would also facilitate the appropriate use of antimicrobials, minimizing the emergence of antimicrobial resistance. This study further develops the use of volatile metabolite detection as a new diagnostic approach for wound infection.

Garlic releases a strong odor after tissue disruption by chewing or other mechanical effects. This odor is strongly associated with the volatile sulfur compounds that can be used for the characterization of garlic. In this study, different varieties of garlic were examined for their volatile sulfur compound concentration, which may be used for purposes of quality control as well as for authentication and classification of garlic varieties. 2- or 3-vinyl-4H-1, 2- or 3-dithiin, allicin, allyl mercaptan, allyl methyl disulfide, ally' methyl sulfide, allyl methyl tetrasulfide, allyl methyl thiosulfide, allyl methyl trisulfide, diallyl disulfide, diallyl sulfide, diallyl tetrasulfide, diallyl trisulfide, dimethyl disulfide, dimethyl thioether, dimethyl thiosulfide, dimethyl trisulfide, and methyl mercaptan were measured in the headspace of garlic for 30 min by selected ion flow tube mass spectrometry (SIFT-MS). German White was determined to be the garlic variety with the highest volatile sulfur compound concentration. Korean Mountain, Music, and Godfathers Italian varieties were discriminated well based on interclass distance (ICD) values. Also, softneck and hardneck garlic were clearly differentiated with chemometrics.

Background Honey has a very important commercial value for producers as a natural product. Honey aroma is formed from the contributions of several volatile compounds, which are influenced by nectar composition, botanical origins, and location. Selected-ion flow-tube mass spectrometry (SIFT-MS) is a technique that quantifies volatile organic compounds simply and rapidly, even in low concentrations. In this study, the headspace concentration of eight monofloral (chestnut, rhododendron, lavender, sage, carob, heather, citrus, and pine) and three multiflower Turkish honeys were analyzed using SIFT-MS. Soft independent modeling of class analogy (SIMCA) was used to differentiate honey samples based on their volatiles. Results This study focused on 78 volatile compounds, which were selected from previous studies of selected honeys. Very clear distinctions were observed between all honeys. Interclass distances greater than 8 indicate that honeys were significantly different. Methanol and ethanol were abundant in the honeys. Chestnut honey collected from the Yalova region had the highest total concentration of volatiles followed by heather honey and chestnut honey collected from the Duzce region. Conclusion Honeys with different botanical and geographical origins showed differences in their volatile profile based on chemometric analysis. Of the honey samples, methanol, ethanol, acetoin, ethyl acetate, and isobutanoic acid had the highest discriminating power. Methanol and ethanol, and then acetic acid, were the volatiles with the highest concentrations in most honeys. © 2020 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

RATIONALE Recycled plastics are increasingly used for packaging of fast-moving consumer goods (FMCG). Compared to packaging made from virgin polymers, there is greater risk of taints entering product due to prior use of the polymers and incomplete cleaning. Increased quality assurance testing of polymer feedstock is required for recycled packaging. Selected ion flow tube mass spectrometry (SIFT-MS) analysis coupled with multivariate statistical data processing can provide high-throughput untargeted screening of recycled polymers at low cost per sample. METHODS SIFT-MS is a direct-injection MS technique that provides high-throughput automated headspace analysis of polymer samples when coupled with a syringe-injection autosampler (12 incubated samples per hour). Full-scan SIFT-MS data were processed using multivariate statistical analysis (specifically, the soft independent modeling by class analogy (SIMCA) algorithm. RESULTS SIFT-MS full-scan data were acquired for ten replicates each of ten recycled and four virgin high-density polyethylene (HDPE) pellet products from multiple manufacturers. The samples varied approximately 20-fold in terms of total volatile residue, while showing very high repeatability across replicates. SIFT-MS scan data were dominated by aliphatic and monoterpene hydrocarbon residues, and - to a lesser extent - alcohols. Application of the SIMCA algorithm to the data resulted in successful classification by both individual samples and manufacturers. CONCLUSIONS Automated, untargeted SIFT-MS analysis coupled with multivariate statistical data analysis has potential to provide rapid, effective screening of recycled polymer products, which would provide increased quality assurance of recycled polymers used for FMCG.

Self-poisoning with professional agricultural pesticide products is responsible for about 20% of global suicide, with most cases occurring in South Asia and China. Treatment of severe poisoning involves long-term intensive clinical care and is often unsuccessful. Solvent co-formulants (such as cyclohexanone) alsocontribute to mortality themselves or via more toxic metabolicproducts (such as cyclohexanol). Faster detection of co-formulantscould aid earlier identification of pesticide poisoning and fasterintervention, reducing mortality. Conventional analysis of volatilesin blood uses headspace (HS)-GC/MS. This paper evaluates SIFTMS, a direct MS technique that provides higher sample throughputthan GC/MS, as a potential tool for cyclohexanone andcyclohexanol analysis in plasma. Both instruments were calibratedusing a conventional approach prior to analysis of each porcineplasma sample on both instruments. Comparative data were evaluated using Bland−Altman plots, demonstrating that the techniqueswere in good agreement. Compared with GC/MS, SIFT-MS provides fourfold higher sample throughput and shows great promise asan alternative analytical tool.

A novel approach for the analysis of volatile organic compounds (VOCs) based on chemical ionization by Au+ ions has been proposed. The ionization is carried out in a commercially available dual sub-atmospheric pressure MALDI/ESI interface without any modifications. The Au+ ions are generated by laser ablation of a gold nanolayer with the MALDI laser, and VOCs are infused via the ESI capillary. The ultrahigh resolving power and sub-ppm mass accuracy of the employed mass spectrometer allow straightforward identification of the formed ion-molecule complexes and other products of Au+ interactions with VOCs in the gas phase. The performance of the technique is demonstrated on the analysis of various classes of organic molecules, namely, alkanes, alkenes, alcohols, aldehydes, ketones, aromatic compounds, carboxylic acids, ethers, or organosulfur compounds, expanding the portfolio of currently available methods for the analysis of VOCs such as secondary electrospray ionization, proton-transfer reaction, and selected ion flow tube mass spectrometry.

Rationale The concentrations of aldehydes and volatile fatty acids have to be controlled because of their potential harmfulness in indoor air or relationship with the organoleptic properties of agri-food products. Although several specific analytical methods are currently used, the simultaneous analysis of these compounds in a complex matrix remains a challenge. The combination of positive and negative ionization selected ion flow tube mass spectrometry (SIFT-MS) allows the accurate, sensitive and high-frequency analysis of complex gas mixtures of these compounds. Methods The ion-molecule reactions of negative precursor ions (OH- , O•- , O2 •- , NO2 - and NO3 - ) with five aldehydes and four carboxylic acids were investigated in order to provide product ions and rate constants for the quantification of these compounds by negative ion SIFT-MS. The results were compared with those obtained by conventional analysis methods and/or with already implemented SIFT-MS positive ionization methods. The modelling of hydroxide ion (OH- )/molecule reaction paths by ab-initio calculation allowed a better understanding of these gas-phase reactions. Results Deprotonation systematically occurs by reaction between negative ions and aldehydes or acids, leading to the formation of [M - H]- primary ions. Ab-initio calculations demonstrated the α-CH deprotonation of aldehydes and the acidic proton abstraction for fatty acids. For aldehydes, the presence of water in the flow tube leads to the formation of hydrated ions, [M - H]- .H2 O. With the NO2 - precursor ion, a second reaction channel results in ion-molecule association with the formation of M.NO2 - ions. Conclusions Except for formaldehyde, all the studied compounds can be quantified by negative ion SIFT-MS with significant rate constants. In addition to positive ion SIFT-MS with H3 O+ , O2 + and NO+ precursor ions, negative ionization with O•- , O2 •- , OH- , NO2 - and NO3 - extends the range of analysis of aldehydes and carboxylic acids in air without a preparation or separation step. This methodology was illustrated by the simultaneous quantification in single-scan experiments of seven aldehydes and six carboxylic acids released by building materials.

Soft chemical ionization mass spectrometry (SCI-MS) techniques can be used to accurately quantify volatile organic compounds (VOCs) in air in real time; however, differentiation of isomers still represents a challenge. A suitable pre-separation technique is thus needed, ideally capable of analyses over a few tens of seconds. To this end, a bespoke fast gas chromatography (GC) instrument with an electrically heated 5 m long metallic capillary column was coupled to selected ion flow tube mass spectrometry (SIFT-MS) measurements. To assess the performance of this combination, a case study of monoterpene isomer (C10H16) analyses was carried out. The monoterpenes were quantified by SIFT-MS using H3O+ reagent ions (analyte ions C10H17+, m∕z 137, and C6H9+, m∕z 81) and NO+ reagent ions (analyte ions C10H16+, m∕z 136, and C7H9+, m∕z 93). The combinations of the fragment ion relative intensities obtained using H3O+ and NO+ were shown to be characteristic of the individual monoterpenes. Two non-polar GC columns (Restek Inc.) were tested: the advantage of MXT-1 was shorter retention, whilst the advantage of MXT-Volatiles was better separation. Thus, it is possible to identify components of a monoterpene mixture in less than 45 s using the MXT-1 column and to separate them in less than 180 s using the MXT-Volatiles column. Quality of the separation and the sensitivity of present technique (limit of detection, LOD, ∼16 ppbv) was found to be inferior compared to commercially available fast GC solutions coupled with proton transfer reaction mass spectrometry (PTR-MS, LOD ∼1 ppbv) due to the limited sample flow through the column. However, using combinations of two reagent ions improved identification of monoterpenes not well resolved by the chromatograms. As an illustrative example, the headspace of needle samples of three conifer species was analysed by both reagent ions and with both columns showing that mainly α-pinene, β-pinene and 3-carene were present. The system can thus be used for direct rapid monitoring of monoterpenes above 20 ppbv, such as applications in laboratory studies of monoterpene standards and leaf headspace analysis. Limitation of the sensitivity due to the total sample flow can be improved using a multi-column pre-separation.

The increasing demand for high-quality biogas and the reduction of reliance on natural gas have driven the need for a well-defined framework to ensure conformity and quality of biogas by the introduction of traceable reference materials and methods across the community. Furthermore, there is a great need to quantify critical trace impurities in biogas. Here, we perform real-time measurements on reference gas standards containing trace hydrocarbons in biogas that are traceable to the international system of units using Selected Ion Flow Tube Mass Spectrometry (SIFT-MS). There are limited data on reaction rate constants in biogas matrices for SIFT-MS, and here we use the traceable gas standards to determine and compare the reaction rate constants of trace hydrocarbons in biogas and nitrogen. Here, we modify SIFT-MS constants for biogas avoiding the current 30 % bias and prevent the overestimation in the concentration of hydrocarbon amount fractions.

Aroma is an essential quality aspect of fresh produce and plays an important role in determining consumer liking and the volatile organic compounds (VOCs) can serve as markers for fermentation and postharvest storage disorders. This study suggests Selected Ion Flow Tube Mass Spectrometry (SIFT-MS) as a candidate technique for the rapid, non-destructive and quantitative measurement of VOCs in postharvest quality research. Strawberry was chosen as a model fruit since its aroma is one of its main quality traits. Combining SIFT-MS in full scan mode with multivariate statistics allowed for inter- and intra-cultivar discrimination of strawberry aroma profiles. Further, by combining SIFT-MS with GC–MS it is possible to tentatively identify volatiles. As compared to GC–MS based approaches total analysis time was reduced by a factor 11.

A new time-integrated thermal desorption technique has been developed that can be used with selected ion flow tube mass spectrometry, TI-TD/SIFT-MS, for off-line quantitative analyses of VOCs accumulated onto sorbents. Using a slow desorption temperature ramp, the absolute amounts of desorbed compounds can be quantified in real time by SIFT-MS and constitutional isomers can be separated. To facilitate application of this technique to environmental atmospheric monitoring, method parameters were optimised for quantification of the three common atmospheric monoterpenes: β-pinene, R-limonene and 3-carene. Three sorbent types, Tenax TA, Tenax GR and Porapak Q, were tested under 26 different desorption conditions determined by the "design of experiment", DOE, systematic approach. The optimal combination of type of sorbent, bed length, sampling flow rate, sample volume and the initial desorption temperature was determined from the experimental results by ANOVA. It was found that Porapak Q exhibited better efficiency of sample collection and further extraction for total monoterpene concentration measurements. On the other hand, Tenax GR or TA enabled separation of all three monoterpenes. The results of this laboratory study were tested with the sample accumulated from a branch of a Pinus nigra tree. Graphical abstract.

Soft chemical ionization mass spectrometry techniques, particularly the well-established proton transfer reaction mass spectrometry, PTR-MS, and selected ion flow tube mass spectrometry, SIFT-MS, are widely used for real-time quantification of volatile organic compounds in ambient air and exhaled breath with applications ranging from environmental science to medicine. The most common reagent ions H3O+, NO+, or O2+• can be selected either by quadrupole mass filtering from a discharge ion source, which is relatively inefficient, or by switching the gas/vapor in the ion source, which is relatively slow. The chosen reagent ions are introduced into a flow tube or flow-drift tube reactor where they react with analyte molecules in sample gas. This article describes a new electrostatic reagent ion switching, ERIS, technique by which H3O+, NO+, and O2+• reagent ions, produced simultaneously in three separate gas discharges, can be purified in post-discharge source drift tubes, switched rapidly, and selected for tr...

Recognized for its nutritional and therapeutic use, extra-virgin Argan Oil (EVAO) is frequently adulterated. Selected-Ion Flow-Tube Mass Spectrometry (SIFT-MS) spectra were applied to quantify adulterants (i.e., Argan oil of lower quality (LQAO), olive oil (OO), and sunflower oil (SO)) in EVAO. Four data sets, i.e., using H3O+, NO+, O2+ reagent ions, and the combined data were considered. Soft independent modelling of class analogy (SIMCA), and partial least squares discriminant analysis (PLS-DA) were assessed to distinguish adulterated- from pure EVAO. The effectiveness of SIFT-MS associated with PLS and support vector machine (SVM) regression to quantify trace adulterants in EVAO was evaluated. Variable Importance in Projection (VIP), and interval-PLS (iPLS) were also investigated to extract useful features. Different models were built to predict the EVAO authenticity and the degree of adulteration. High accuracy was achieved. SIFT-MS spectra handled with the appropriate chemometric tools were found suitable for the quality evaluation of EVAO.

Selected-Ion Flow-Tube Mass Spectrometry (SIFT-MS) has been applied in a clinical context as diagnostic tool for breath samples using target biomarkers. Exhaled breath sampling is non-invasive and therefore much more patient friendly compared to bronchoscopy, which is the golden standard for evaluating airway inflammation. In the actual pilot study, 55 exhaled breath samples of children with asthma, cystic-fibrosis and healthy individuals were included. Rather than focusing on the analysis of target biomarkers or on the identification of biomarkers, different data analysis strategies, including a variety of pretreatment, classification and discrimination techniques, are evaluated regarding their capacity to distinguish the three classes based on subtle differences in their full scan SIFT-MS spectra. Proper data-analysis strategies are required because these full scan spectra contain much external, i.e. unwanted, variation. Each SIFT-MS analysis generates three spectra resulting from ionmolecule reactions of analyte molecules with H3O+, NO+ and O-2(+). Models were built with Linear Discriminant Analysis, Quadratic Discriminant Analysis, Soft Independent Modelling by Class Analogy, Partial Least Squares - Discriminant Analysis, K-Nearest Neighbours, and Classification and Regression Trees. Perfect models, concerning overall sensitivity and specificity (100% for both) were found using Direct Orthogonal Signal Correction (DOSC) pretreatment. Given the uncertainty related to the classification models associated with DOSC pretreatments (i.e. good classification found also for random classes), other models are built applying other preprocessing approaches. A Partial Least Squares - Discriminant Analysis model with a combined pre-processing method considering single value imputation results in 100% sensitivity and specificity for calibration, but was less good predictive. Pareto scaling prior to Quadratic Discriminant Analysis resulted in 41/55 correctly classified samples for calibration and 34/55 for cross-validation. In future, the uncertainty with DOSC and the applicability of the promising preprocessing methods and models must be further studied applying a larger representative data set with a more extensive number of samples for each class. Nevertheless, this pilot study showed already some potential for the untargeted SIFT-MS application as a rapid pattern-recognition technique, useful in the diagnosis of clinical breath samples.

Rationale Selected ion flow tube mass spectrometry (SIFT-MS) is versatile, rapidly provides result output and determines a wide range of volatiles, making it suitable for biomedical applications. When direct sampling into the SIFT-MS instrument is impractical, combining thermal desorption (TD) and SIFT-MS might offer a solution as it allows sample storage on sorbent tubes for later analysis. This work compares off-line TD SIFT-MS and real-time SIFT-MS for the quantification of selected breath volatiles. Methods Ten healthy non-smoking individuals provided 60 breath samples per method. For off-line analysis, breath was collected onto sorbent tubes via a breath sampler provided with filtered inspiratory air. After TD, samples were re-collected in Tedlar bags which were then connected to the SIFT-MS instrument. For real-time analysis, breath was sampled directly into the instrument. In both cases the analytical method included a total of 155 product ions, and 14 selected volatiles were quantified. The agreement between the methods was assessed using Pearson correlation coefficients and Bland-Altman plots. Results Overall, correlations between real-time and off-line analysis were moderate to very strong (r = 0.43-0.92) depending on the volatile of interest, except for 2,3-butanedione and styrene. The difference between real-time and off-line measured breath concentrations (average bias) ranged between -14.57 and 20.48 ppbv. For acetone and isoprene, it was 251.53 and 31.9 ppbv, respectively. Conclusions Real-time SIFT-MS and off-line TD SIFT-MS for quantification of selected breath volatiles did not show optimal agreement. Analyzing a multitude of analytes in breath via direct exhalation into a SIFT-MS instrument for real-time analysis is challenging. On the other hand, off-line analysis using a breath collection device also has its issues such as possible sample losses due to selective absorption depending on the sorbent used or during desorption and transfer to the instrument. Despite these drawbacks, both methods were moderately well correlated.

Virgin olive oil (VOO) is a highly valued vegetable oil often subjected to fraud practices such as adulteration with lower prized oils such as seed oils and refined olive oil. Thus, there is a need to provide rapid tools that allow high-throughput authentication and quality control of VOO as well as other valued edible oils. The characterization of the chemical composition of edible oils is challenging due to the complexity of the matrix. Different methods have been used for both edible oil quality control and authentication purposes including Raman and infrared spectroscopy, molecular fluorescence, nuclear magnetic resonance as well as chromatographic methods. One of the key features is whether the analyses are performed directly in the oil matrix without further treatment or, sample preparation and processing is mandatory including dilution steps or dedicated sample preparation stages. Given the complexity of the matrix, the first approach is difficult to tackle with. Another feature is the scope of the analysis, whether the entire fat composition (eg. saponifiable fraction) is analyzed or, on the contrary, specific fractions that may contain useful information for quality control and authentication purposes are targeted. Mass spectrometry offers unique features -such as specificity, sensitivity and speed of analysis- that map well against this challenge, either those based on atmospheric pressure ionization methods such as electrospray and atmospheric pressure chemical ionization, or those occurring under vacuum environment such as matrix assisted laser desorption ionization (MALDI) for nonvolatile species or headspace sampling-mass spectrometry using electron impact ionization (HS-MS) or chemical ionization (proton transfer reaction mass spectrometry (PTR-MS) and selected ion flow tube mass spectrometry (SIFT-MS)) for volatile fraction analysis. In addition, more recent atmospheric pressure methods (Ambient MS) enable direct analysis with minor or even no sample manipulation. The aim of this article is to provide a critical overview on all these methods and their potential use for edible oil characterization, highlighting the strengths and weaknesses of the different approaches

A system to differentiate and quantify liquid and headspace vapor leaks from closed system drug-transfer devices (CSTDs) is presented. CSTDs are designed to reduce or eliminate hazardous drug (HD) exposure risk when compounding and administering HDs. CSTDs may leak liquid, headspace, or a mixture of the two. The amount of HD contained in liquid and headspace leaks may be substantially different. Use of a test solution containing two VOCs with differences in ratios of VOC concentrations in the headspace and liquid enables source apportionment of leaked material. SIFT-MS was used to detect VOCs from liquid and headspace leaks in the vapor phase. Included in this report is a novel method to determine the origin and magnitude of leaks from CSTDs. A limit of leak detection of 24 μL of headspace vapor and 0.14 μL of test liquid were found using Selected Ion Flow Tube Mass Spectrometry (SIFT-MS).

A major challenge for breath research is the lack of standardization in sampling and analysis. To address this, a test that utilizes a standardized intervention and a defined study protocol has been proposed to explore disparities in breath research across different analytical platforms and to provide benchmark values for comparison. Specifically, the Peppermint Experiment involves the targeted analysis in exhaled breath of volatile constituents of peppermint oil after ingestion of the encapsulated oil. Data from the Peppermint Experiment performed by proton transfer reaction mass spectrometry (PTR-MS) and selected ion flow tube mass spectrometry (SIFT-MS) are presented and discussed herein, including the product ions associated with the key peppermint volatiles, namely limonene, alpha- and beta-pinene, 1,8-cineole, menthol, menthone and menthofuran. The breath washout profiles of these compounds from 65 individuals were collected, comprising datasets from five PTR-MS and two SIFT-MS instruments. The washout profiles of these volatiles were evaluated by comparing the log-fold change over time of the product ion intensities associated with each volatile. Benchmark values were calculated from the lower 95% confidence interval of the linear time-to-washout regression analysis for all datasets combined. Benchmark washout values from PTR-MS analysis were 353 min for the sum of monoterpenes and 1,8-cineole (identical product ions), 173 min for menthol, 330 min for menthofuran, and 218 min for menthone; from SIFT-MS analysis values were 228 min for the sum of monoterpenes, 281 min for the sum of monoterpenes and 1,8-cineole, and 370 min for menthone plus 1,8-cineole. Large inter- and intra-dataset variations were observed, whereby the latter suggests that biological variability plays a key role in how the compounds are absorbed, metabolized and excreted from the body via breath. This variability seems large compared to the influence of sampling and analytical procedures, but further investigations are recommended to clarify the effects of these factors. Marie Skodowska-Curie Actions Innovative Training Network: Ion-Molecule Processes for Analytical Chemistry Technologies (IMPACT) through the European Commission's HORIZON 2020 Programme [674911]; UK's National Physical Laboratory

35 p.-4 fig.-2 tab., There is an ever-growing interest in metabolomic profiling using noninvasive, real-time techniques that avoid sample manipulation and are painless for the patients. In this context, breath analysis is gaining much attention, and several ionization techniques have been developed to get insights in real-time into metabolic status by analyzing breath through mass spectrometry, such as Proton transfer reaction mass spectrometry (PTR-MS), Selected ion flow tube mass spectrometry (SIFT-MS), and Secondary electrospray ionization mass spectrometry (SESI-MS). SESI-MS is the most recently developed analytical platform displaying particular adequate characteristics for breath analysis, such as the low detection limits, and the detection of low volatility species, which tend to present a higher biological significance. Here, we review the SESI technology development, the different SESI configurations developed, and the standardization procedures described to translate SESI into the clinical environment. Finally, SESI main applications described in the literature with prompt translation into the clinical environment, namely, biomarker discovery or pharmacokinetics and drug monitoring are revised.

The need for rapid and accurate measurement of trace concentrations of compounds present in ambient humid air has led to construction of specialised mass spectrometers based on the Selected Ion Flow Tube Mass Spectrometry, SIFT-MS, its drift-tube variant, SIFDT-MS, and Proton Transfer Mass Spectrometry, PTR-MS. It is currently possible to analyse vapours of volatile organic compounds, VOC, and other gases including ammonia, hydrogen sulphide and hydrogen cyanide present in concentrations even below a part per billion by volume, ppbv. The reagent ions are formed in electrical discharges and their ion-molecule reactions with sampled analyte molecules take place at pressures of 1–2 mbar. As an example of analytical use, SIFT-MS coupled with the Laser Induced Breakdown, LIB, technique was used to analyse stable gaseous products from the decomposition of pure explosive compounds HMX, RDX, PETN and TNT and from 38 types of commercial explosive and propellant mixtures. Decomposition products analysed included NH3, HCN, HCHO, NO, NO2, HONO, HNO3, C2H5OH, CH3CN, DMNB, C2H6CO, C2H2 and nitroglycerine. For four selected explosives, it was found that the end products of the microscopic LIB laboratory tests correspond well to the composition of fumes from realistic explosions of 0.5 kg charges.

International audience; Selected ion flow tube – mass spectrometry (SIFT-MS) is based on chemical reactivity of analytes with reactant ions. The complete understanding of all the ion–molecule reactions is the key to the deployment of this technology for the direct and rapid analysis of VOCs in the gas phase. In the present work, we focused on direct analysis of carboxylic acids and esters, compounds involved in many biochemical processes.The ion–molecule reactions of negative precursor ions (OH–, O●−, O2●−, NO2– and NO3–) with 9 carboxylic acids and 21 esters were investigated in order to provide product ions and rate constants for these compounds analysis by SIFT-MS. The modelling of ion–molecule reaction paths by ab-initio calculations supported the experimental results and provided a better understanding of these gas phase ion–molecule reactions.The most common reaction mechanism with all the tested molecules is deprotonation. However, other specific reactivities, leading to the formation of anion-molecule complexes with NO2– and O2●− in particular, are observed. Furthermore, specific fragmentations of chemical families are also noticed and confirmed with O2●− and O●−. Finally, we demonstrated that the composition of the matrix (H2O, CO2) participates in the formation of secondary ions.In this work, we determined the kinetic rate constants in the nitrogen carrier gas and the detection limits of all the compounds with the eight precursor ions used by SIFT-MS, allowing accurate quantification in the gas phase at the ppb level. These results contribute to enlarge the negative ionization SIFT-MS measurements to applications where quantification of organic acids and esters are required.

Aim\ud To assess in a laboratory setting using extracted teeth the formation of volatile compounds (VOCs) and disinfection by‐products (DBPs) in effluent aliquots, during chemomechanical preparation of artificially infected root canal specimens, and determine the role of silver‐impregnated activated carbon (Ag‐AC) in their removal.\ud \ud Methodology\ud Single‐rooted human teeth were decoronated to obtain 15mm‐long root specimens and a nutrient‐stressed multispecies biofilm was grown in the root canals. Specimens were randomly assigned into three groups [Group 1; instrumentation with rotary files and irrigation with sterile saline, Groups 2 and 3; instrumentation with rotary files and irrigation with 2.5% NaOCl and 17% EDTA]. A portable medical suction device was used to collect the effluent aliquots during root canal irrigation. In Groups 1 and 2, the reaction products of the collected effluents were analysed by selected ion flow tube mass spectrometry (SIFT‐MS). The effluents from Group 3 were treated with Ag‐AC prior to SIFT‐MS analysis, to assess the removal capacity of Ag‐AC against the reaction products. The synthesis of Ag‐AC was characterised with scanning electron microscopy/energy dispersive X‐ray spectroscopy (SEM/EDS). Two‐way analysis of variance (ANOVA) with post hoc Tukey tests were used for data analysis and determination of a significant difference (P\ud \ud Results\ud In Group 1, effluent VOCs and DBPs were detectable at very low levels. In Group 2, the collected effluent aliquots released high concentrations of methanol, propanol, ammonia, chloroform and formaldehyde, which were significantly greater compared to Group 1 (P0.05).\ud \ud Conclusions\ud In this laboratory setting using extracted human teeth, the chemomechanical preparation of artificially infected root canals resulted in the formation of toxic volatile compounds and disinfection by‐products as effluent suspensions. Their release during aspiration with dental suction indicates that potential environmental hazards should be investigated. The use of silver‐impregnated activated carbon had potential for the point‐of‐use treatment of post‐irrigation effluent aliquots.

Ion-molecule reactions (IMR) are at the very core of trace gas analyses in modern chemical ionization (CI) mass spectrometer instruments, which are increasingly being used in diverse areas of research and industry. The focus of this Perspective is on the ion chemistry that underpins gas-phase analytical CI methods. Special attention is given to the soft chemical ionization method known as selected ion flow tube-mass spectrometry (SIFT-MS). The processes involved in the ion chemistry of the reagent cations, H

Pollution from microplastics (MPs) has become one of the most relevant topics in environmental chemistry. The risks related to MPs include their capability to adsorb toxic and harmful molecular species, and to release additives and degradation products into ecosystems. Their role as a primary source of a broad range of harmful volatile organic compounds (VOCs) has also been recently reported. In this work, we applied a non-destructive approach based on selected-ion flow tube mass spectrometry (SIFT-MS) for the characterization of VOCs released from a set of plastic debris collected from a sandy beach in northern Tuscany. The interpretation of the individual SIFT-MS spectra, aided by principal component data analysis, allowed us to relate the aged polymeric materials that make up the plastic debris (polyethylene, polypropylene, and polyethylene terephthalate) to their VOC emission profile, degradation level, and sampling site. The study proves the potential of SIFT-MS application in the field, as a major advance to obtain fast and reliable information on the VOCs emitted from microplastics. The possibility to obtain qualitative and quantitative data on plastic debris in less than 2 min also makes SIFT-MS a useful and innovative tool for future monitoring campaigns involving statistically significant sets of environmental samples.

Current available methods for the clinical diagnosis of urinary tract infection (UTI) rely on a urine dipstick test or culturing of pathogens. The dipstick test is rapid (available in 1–2 min), but has a low positive predictive value, while culturing is time-consuming and delays diagnosis (24–72 h between sample collection and pathogen identification). Due to this delay, broad-spectrum antibiotics are often prescribed immediately. The over-prescription of antibiotics should be limited, in order to prevent the development of antimicrobial resistance. As a result, there is a growing need for alternative diagnostic tools. This paper reviews applications of chemical-analysis instruments, such as gas chromatography–mass spectrometry (GC-MS), selected ion flow tube mass spectrometry (SIFT-MS), ion mobility spectrometry (IMS), field asymmetric ion mobility spectrometry (FAIMS) and electronic noses (eNoses) used for the diagnosis of UTI. These methods analyse volatile organic compounds (VOCs) that emanate from the headspace of collected urine samples to identify the bacterial pathogen and even determine the causative agent’s resistance to different antibiotics. There is great potential for these technologies to gain wide-spread and routine use in clinical settings, since the analysis can be automated, and test results can be available within minutes after sample collection. This could significantly reduce the necessity to prescribe broad-spectrum antibiotics and allow the faster and more effective use of narrow-spectrum antibiotics.

Cervicovaginal mucus is a mixture of mucins, ions, salts, and water, the proportions of which change during the reproductive cycle. It is suspected that this mucus emits an important volatile signal indicative of the reproductive state of the female. The objective of this study was to identify volatile organic compounds (VOC) in bovine cervicovaginal mucus that are modulated during the estrous cycle and could potentially be used as biomarkers of estrus and ovulation. Cervicovaginal mucus was collected from crossbred beef heifers (n = 8), which were synchronized using an 8-d controlled internal drug release (CIDR) protocol and in which onset of estrus and time of ovulation were determined by visual observation and ultrasonography, respectively. Mucus samples were collected between 0 and 96 h after CIDR removal (estrus onset occurred at 49.1 ± 3.3 h after CIDR removal). A validation study was performed on an independent group of 15 heifers from which cervicovaginal mucus samples were collected every 8 h from 40 to 80 h after CIDR removal. The VOC in mucus were identified using gas chromatography-mass spectrometry and selected compounds were quantified using selected-ion flow-tube mass spectrometry. The presence of 47 VOC was detected in mucus samples by gas chromatography-mass spectrometry with those exhibiting highest abundance including 2-butanone, acetone, 2-pentanone, 4-methyl-2-pentanone, 1-(1-methylethoxy)-2-propanone, ethanol, 2-methyl-2-propanol, and 2-butanol. All VOC peaked between 24 to 47 h after the onset of estrus (ovulation occurred 26.6 ± 5.6 h after estrus onset). Two VOC, 2-pentanone and 4-methyl-2-pentanone, exhibited a significant increase at the onset of estrus, whereas concentration of 2-butanone increased significantly just after estrus onset, indicating that these VOC may be used as putative biomarkers of estrus. The results of our study may contribute to the development of a sensor device based on VOC to aid the detection of estrus and ovulation in cattle, with particular relevance for the dairy industry where the majority of females are bred by artificial insemination.

RATIONALE The volatile compounds generated by the electrochemical reduction of atmospheric carbon dioxide and nitrogen include isobaric methanol (CH3 OH) and, potentially, hydrazine (N2 H4 ). To achieve quantification of hydrazine molecules by selected ion flow tube mass spectrometry (SIFT-MS), its reactions with H3 O+ , NO+ and O2+ reagent ions must be understood. METHODS A SIFT study (using a SIFT-MS instrument) was carried out to obtain rate coefficients and product ions for the reactions of H3 O+ , NO+ and O2+ reagent ions with N2 H4 and CH3 OH molecules present in the humid headspace of their aqueous solutions. Using the kinetics data obtained, solution headspace concentrations were determined for both compounds as a function of their liquid-phase concentrations at 10, 20 and 35°C. RESULTS Both compounds react with H3 O+ ions via rapid proton transfer to produce CH3 OH2+ and H5 N2+ ions with the common m/z value of 33. It is revealed that NO+ rapidly transfers charge to N2 H4 (rate coefficient k = 2.3 × 10-9 cm3 s-1 ) but only slowly associates with CH3 OH (k2eff = 7.1 × 10-11 cm3 s-1 ). Thus, selective analysis can be achieved using both H3 O+ and NO+ reagent ions. The headspace methanol vapour concentration was found to increase with increasing solution temperature, but that of hydrazine decreased with an associated increase of ammonia (NH3 ) as measured with O2+ reagent ions. CONCLUSIONS The isobaric compounds methanol and hydrazine can be separately analysed in real time by SIFT-MS using H3 O+ and NO+ reagent ions, even when they co-occur in humid air. The evolution of hydrazine from aqueous solutions can be quantitatively monitored together with its decomposition at elevated temperatures.

The reactions of five structurally similar unsaturated alcohols, i.e., (Z)-2-penten-1-ol, (E)-2-hexen-1-ol, (E)-3-hexen-1-ol, (Z)-3-hexen-1-ol, and 1-octen-3-ol, with Cl atoms in the gas phase, were investigated at 296 &plusmn, 2 K and 1 atm by the relative-rate kinetic technique using a 600-L Teflon reaction chamber. Selected ion flow tube mass spectrometry (SIFT-MS) was used simultaneously to monitor the decay of the alcohols of interest and selected reference compounds. Tetrahydrofuran (THF), propan-1-ol, and octane were used as reference compounds. Chlorine atoms were produced by the photolysis of molecular chlorine (Cl2) using broadband actinic lamps near 365 nm. The estimated rate constant values (in 10&minus, 10 cm3∙molecule&minus, 1∙s&minus, 1) followed the order 2.99 &plusmn, 0.53 ((Z)-2-penten-1-ol) &lt, 3.05 &plusmn, 0.59 ((E)-3-hexen-1-ol) &lt, 3.15 &plusmn, 0.58 ((Z)-3-hexen-1-ol) &lt, 3.41 &plusmn, 0.65 ((E)-2-hexen-1-ol) &lt, 4.03 &plusmn, 0.77 (1-octen-3-ol). The present work provides the first value of the rate constant for the reaction of 1-octen-3-ol with Cl atoms. The results are discussed and interpreted in relation to other studies where literature data are available. The structure&ndash, activity relationship and the atmospheric implications are discussed as well.

Rationale The analysis of volatile organic compounds (VOCs) within exhaled breath potentially offers a non-invasive method for the detection and surveillance of human disease. Oral contamination of exhaled breath may influence the detection of systemic VOCs relevant to human disease. This study aims to assess the impact of oral cleansing strategies on exhaled VOC levels in order to standardise practice for breath sampling. Methods Ten healthy volunteers consumed a nutrient challenge followed by four oral cleansing methods: (a) water, (b) saltwater, (c) toothbrushing, and (d) alcohol-free mouthwash. Direct breath sampling was performed using selected ion flow tube mass spectrometry after each intervention. Results Proposed reactions suggest that volatile fatty acid and alcohol levels (butanoic, pentanoic acid, ethanol) declined with oral cleansing interventions, predominantly after an initial oral rinse with water. Concentrations of aldehydes and phenols (acetaldehyde, menthone, p-cresol) declined with oral water rinse; however, they increased after toothbrushing and mouthwash use, secondary to flavoured ingredients within these products. No significant reductions were observed with sulphur compounds. Conclusions Findings suggest that oral rinsing with water prior to breath sampling may reduce oral contamination of VOC levels, and further interventions for oral decontamination with flavoured products may compromise results. This intervention may serve as a simple and inexpensive method of standardisation within breath research.

Selected ion flow tube mass spectrometry, SIFT-MS, is a non-separative method for direct quantitative analyses of volatile compounds, VOCs, in air and humid breath based on chemical ionization. Selected reagent ions, either H3O+, NO+ or O2+ (non-reactive with major components of air), ionize analyte molecules during a defined time in a flow tube by ion-molecule reactions thus producing analyte ions that are characteristic of the neutral analyte VOCs. Concentrations can be calculated in real-time from the ion count rates. Direct on-line analysis of single or multiple breath exhalations or off-line analysis of breath samples collected into bags can be performed. Several volatile breath metabolites have been quantified by SIFT-MS, including ammonia, acetone, hydrogen cyanide, alcohols, pentane, acetic acid, methane, and sulphur compounds. Their potential as biomarkers is discussed.

Macadamia has increasing commercial importance in the food, cosmetics, and pharmaceutical industries. However, the toxic compound hydrogen cyanide (HCN) released from the hydrolysis of cyanogenic compounds in Macadamia causes a safety risk. In this study, optimum conditions for the maximum release of HCN from Macadamia were evaluated. Direct headspace analysis of HCN above Macadamia plant parts (flower, leaves, nuts, and husks) was carried out using selected ion flow tube&ndash, mass spectrometry (SIFT-MS). The cyanogenic glycoside dhurrin and total cyanide in the extracts were analyzed using HPLC-MS and UV&ndash, vis spectrophotometer, respectively. HCN released in the headspace was at a maximum when Macadamia samples were treated with pH 7 buffer solution and heated at 50 &deg, C for 60 min. Correspondingly, treatment of Macadamia samples under these conditions resulted in 93%&ndash, 100% removal of dhurrin and 81%&ndash, 91% removal of total cyanide in the sample extracts. Hydrolysis of cyanogenic glucosides followed a first-order reaction with respect to HCN production where cyanogenesis is principally induced by pH changes initiating enzymatic hydrolysis rather than thermally induced reactions. The effective processing of different Macadamia plant parts is important and beneficial for the safe production and utilization of Macadamia-based products.

Background: Breath based non-invasive diagnostics have the potential to provide valuable information about a person's health status. However, it is not yet widely used in clinical practice due to multiple factors causing variability and the lack of standardized procedures. This study focuses on the comparison of oral and nasal breathing and on variability of volatile metabolites over short and long term. Methods: Selected ion flow tube mass spectrometry (SIFT-MS) was used for on-line analysis of selected volatile metabolites in oral and nasal breath of 10 healthy individuals 5 times in one day (short term) and 6 times spread over 3 weeks (long term) resulting in nearly 100 breath samplings. Intra-class correlation coefficients (ICC) were used to assess short and long term biological variability. Additionally, the composition of ambient air was analyzed at different samplings. The selected volatiles common in exhaled breath were propanol, 2,3 butanedione, acetaldehyde, acetone, ammonia, dimethyl sulfide, isoprene, pentane, and propanal. Additionally, environmental compounds benzene and styrene were analyzed as well. Results: Volatile metabolite concentrations in ambient air were not correlated with those in exhaled breath and were significantly lower than in breath samples. All volatiles showed significant correlation between oral and nasal breath. Five were significantly higher in oral breath compared to nasal breath, while for acetone, propanal, dimethyl sulfide and ammonia concentrations were similar in both matrices. Variability depended on the volatile metabolite. Most physiologically relevant volatiles (acetone, isoprene, propanol, acetaldehyde) showed good to very good biological reproducibility (ICC > 0.61) mainly in oral breath and over a short term period of one day. Conclusion: Both breathing routes showed relatively similar patterns, however bigger differences were expected. Therefore, since sampling from the mouth is practically more easy, the latter might be preferred.

International audience; The quantification of hydrogen sulphide (H2S) by Selected Ion Flow Tube coupled with Mass Spectrometry (SIFT/MS) was investigated for application in industrial emission context, usually faced with concentrations of water vapour higher than the saturation at room condition. H2S concentrations measured by SIFT/MS (using nitrogen as carrier gas and flow tube temperature at 119°C) were affected by water content, reducing the sensibility for H2S measurements. Accurate concentrations were obtained when the influence of water was considered on SIFT/MS analysis, requiring although the information about water content in the sample. In addition, the association of low concentration of H2S (around 50 ppbv) and high humidity level (4.0 %vol of water) was highlighted as a critical point for measuring H2S by SIFT/MS, due to the sensibility reduction as function of water content and the measurement uncertainty enhancement at low signal intensity.

Selected ion flow tube mass spectrometry (SIFT-MS) is a chemical ionization technique that offers sensitive, real-time detection of volatile organic compounds (VOCs) down to trace levels. This chapter briefly introduces the technique and summarizes the recent research into SIFT-MS analyses of exhaled breath and the most pertinent results obtained. The search for single-breath VOCs is illustrated by the online quantification by SIFT-MS of ammonia, acetone, hydrogen cyanide, methanol, pentane, and acetic acid. The breathprint approach to the analysis of SIFT-MS spectra is illustrated by several studies of the exhaled breath of patients with several clinical conditions, including heart failure and liver disease. The results of detailed breath SIFT-MS studies in patients with gastroesophageal cancer indicate that VOC profiling may be suitable in identifying those at high risk of this disease. In vitro studies of the VOCs emitted by pulmonary pathogens illustrate the search for exhaled breath biomarkers of airways colonization by such organisms.

Atomization of hydrides and their methylated analogues in a dielectric barrier discharge (DBD) plasma atomizer was investigated. Selected ion flow tube mass spectrometry (SIFT-MS) was chosen as a detector being capable of selective detection of non-atomized original volatile species allowing thus direct quantification of atomization efficiency. Selenium hydride (SeH2) and three volatile arsenic species, namely arsenic hydride (AsH3), monomethylarsane (CH3AsH2) and dimethylarsane ((CH3)2AsH), were selected as model analytes. The mechanistic study performed contributes to understanding of the atomization processes in atomic absorption spectrometry (AAS). The presented results are compatible with a complete atomization of arsenic hydride as well as its methylated analogues and with atomization efficiency of SeH2 below 80%. Using AsH3 as a model analyte and a combination of AAS and SIFT-MS detectors has revealed that the hydride is not atomized, but decomposed in the DBD atomizer in absence of hydrogen fraction in the carrier gas. Apart from investigation of analyte atomization, the SIFT-MS detector is capable of quantitative determination of water vapor content being either transported to, or produced in the atomizer. This information is crucial especially in the case of the low-power/temperature DBD atomizer since its performance is sensitive to the amount of water vapor introduced into the plasma.

This study investigated the effectiveness of SIFT-MS versus chemical profiling, both coupled to multivariate data analysis, to classify 95 Extra Virgin Argan Oils (EVAO), originating from five Moroccan Argan forest locations. The full scan option of SIFT-MS, is suitable to indicate the geographic origin of EVAO based on the fingerprints obtained using the three chemical ionization precursors (H3O+, NO+ and O2+). The chemical profiling (including acidity, peroxide value, spectrophotometric indices, fatty acids, tocopherols- and sterols composition) was also used for classification. Partial least squares discriminant analysis (PLS-DA), soft independent modeling of class analogy (SIMCA), K-nearest neighbors (KNN), and support vector machines (SVM), were compared. The SIFT-MS data were therefore fed to variable-selection methods to find potential biomarkers for classification. The classification models based either on chemical profiling or SIFT-MS data were able to classify the samples with high accuracy. SIFT-MS was found to be advantageous for rapid geographic classification.

Objectives: To assess the release and apical extrusion of toxic volatile compounds and disinfection by-products during instrumentation and irrigation of artificially infected root canal specimens, with sodium hypochlorite and ethylene diamine tetra acetic acid. Methods: Forty-two single-rooted human teeth were decoronated to obtain 15 mm-long root specimens and working length was determined 1 mm short of root apex. All specimens were initially preflared, to create sufficient conical space for the development of a nutrient-stressed multispecies biofilm. The specimens were randomly assigned into three groups [Group 1; no endodontic intervention, Group 2; instrumentation with rotary files and irrigation with sterile saline, Group 3; instrumentation with rotary files and irrigation with 2.5% sodium hypochlorite (NaOCl) and 17% ethylene diamine tetra acetic acid (EDTA)]. A customised experimental model apparatus was fabricated for each specimen. The apical root third was inserted in a glass vial filled with sterile ultrapure water, to simulate high-compliance periradicular space. The reaction products of the aliquots obtained from the glass vials were analysed in real time, by selected ion flow tube mass spectrometry (SIFT-MS) in triplicates. Two-way analysis of variance (ANOVA) with post hoc Tukey tests were used for data analysis. The level of statistical significance was set at P < 0.05. Results: The group of teeth that were not subjected to endodontic intervention did not show any volatile compounds (VOCs) or disinfection by products (DBPs) whilst instrumentation and irrigation of root canals (Groups 2 and 3) resulted in the apical extrusion of VOCs and DBPs. In Group 3, the aliquots obtained from periradicular space released high concentrations of methanol, propanol, ammonia, chloroform, together with unexpected higher levels of formaldehyde, which were statistically significant compared to Group 2 (P < 0.05). Significance: The mechanical preparation and irrigation of artificially infected root canals with rotary files, 2.5% NaOCl and 17% EDTA resulted in the formation of toxic VOCs and DBPs in a water-closed periradicular space. The chemical interaction of NaOCl and EDTA resulted in the generation of high concentrations of formaldehyde. The formation of chloroform and formaldehyde indicate that risk assessment of the potential hazards to health should be carried out.