Combining Thermal Desorption with Selected Ion Flow Tube Mass Spectrometry for Analyses of Breath Volatile Organic Compounds.

An instrument integrating thermal desorption (TD) to selected ion flow tube mass spectrometry (SIFT-MS) is presented, and its application to analyze volatile organic compounds (VOCs) in human breath is demonstrated for the first time. The rationale behind this development is the need to analyze breath samples in large-scale multicenter clinical projects involving thousands of patients recruited in different hospitals. Following adapted guidelines for validating analytical techniques, we developed and validated a targeted analytical method for 21 compounds of diverse chemical class, chosen for their clinical and biological relevance. Validation has been carried out by two independent laboratories, using calibration standards and real breath samples from healthy volunteers. The merging of SIFT-MS and TD integrates the rapid analytical capabilities of SIFT-MS with the capacity to collect breath samples across multiple hospitals. Thanks to these features, the novel instrument has the potential to be easily employed in clinical practice.

Robust Automated SIFT-MS Quantitation of Volatile Compounds in Air Using a Multicomponent Gas Standard.

Selected ion flow tube mass spectrometry, SIFT-MS, has been widely used in industry and research since its introduction in the mid-1990s. Previously described quantitation methods have been advanced to include a gas standard for a more robust and repeatable analytical performance. The details of this approach to calculate the concentrations from ion-molecule reaction kinetics based on reaction times and instrument calibration functions determined from known concentrations in the standard mix are discussed. Important practical issues such as the overlap of product ions are outlined, and best-practice approaches are presented to enable them to be addressed during method development. This review provides a fundamental basis for a plethora of studies in broad application areas that are possible with SIFT-MS instruments.

Accurate selected ion flow tube mass spectrometry quantification of ethylene oxide contamination in the presence of acetaldehyde.

In September 2020, traces of ethylene oxide (a toxic substance used as a pesticide in developing countries but banned for use on food items within the European Union) were found in foodstuffs containing ingredients derived from imported sesame seed products. Vast numbers of foodstuffs were recalled across Europe due to this contamination, leading to expensive market losses and extensive trace exposure of ethylene oxide to consumers. Therefore, a rapid analysis method is needed to ensure food safety by high-throughput screening for ethylene oxide contamination. Selected ion flow tube mass spectrometry (SIFT-MS) is a suitable method for rapid quantification of trace amounts of vapours in the headspace of food samples. It turns out, however, that the presence of acetaldehyde complicates SIFT-MS analyses of its isomer ethylene oxide. It was proposed that a combination of the H3O+ and NO+ reagent ions can be used to analyse ethylene oxide in the presence of acetaldehyde. This method is, however, not robust because of the product ion overlaps and potential interferences from other matrix species. Thus, we studied the kinetics of the reactions of the H3O+, NO+, OH- and O-˙ ions with these two compounds and obtained their rate coefficients and product ion branching ratios. Interpretation of these experimental data revealed that the OH- anions are the most suitable SIFT-MS reagents because the product ions of their reactions with acetaldehyde (CH2CHO- at m/z 43) and ethylene oxide (C2H3O2- at m/z 59) do not overlap.

Recent developments and applications of selected ion flow tube mass spectrometry (SIFT-MS).

Selected ion flow tube mass spectrometry (SIFT-MS) is now recognized as the most versatile analytical technique for the identification and quantification of trace gases down to the parts-per-trillion by volume, pptv, range. This statement is supported by the wide reach of its applications, from real-time analysis, obviating sample collection of very humid exhaled breath, to its adoption in industrial scenarios for air quality monitoring. This review touches on the recent extensions to the underpinning ion chemistry kinetics library and the alternative challenge of using nitrogen carrier gas instead of helium. The addition of reagent anions in the Voice200 series of SIFT-MS instruments has enhanced the analytical capability, thus allowing analyses of volatile trace compounds in humid air that cannot be analyzed using reagent cations alone, as clarified by outlining the anion chemistry involved. Case studies are reviewed of breath analysis and bacterial culture volatile organic compound (VOC), emissions, environmental applications such as air, water, and soil analysis, workplace safety such as transport container fumigants, airborne contamination in semiconductor fabrication, food flavor and spoilage, drugs contamination and VOC emissions from packaging to demonstrate the stated qualities and uniqueness of the new generation SIFT-MS instrumentation. Finally, some advancements that can be made to improve the analytical capability and reach of SIFT-MS are mentioned.

Untargeted selected ion flow tube mass spectrometry headspace analysis: High-throughput differentiation of virgin and recycled polyethylene pellets.

RATIONALE: Recycled plastics are increasingly used for packaging of fast-moving consumer goods (FMCG). Compared with packaging made from virgin polymers, there is greater risk of taints entering products 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 the potential to provide rapid, effective screening of recycled polymer products, which would provide increased quality assurance of recycled polymers used for FMCG.

Selected Ion Flow Tube-Mass Spectrometry (SIFT-MS) as an Alternative to Gas Chromatography/Mass Spectrometry (GC/MS) for the Analysis of Cyclohexanone and Cyclohexanol in Plasma.

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) also contribute to mortality themselves or via more toxic metabolic products (such as cyclohexanol). Faster detection of co-formulants could aid earlier identification of pesticide poisoning and faster intervention, reducing mortality. Conventional analysis of volatiles in blood uses headspace (HS)-GC/MS. This paper evaluates SIFT-MS, a direct MS technique that provides higher sample throughput than GC/MS, as a potential tool for cyclohexanone and cyclohexanol analysis in plasma. Both instruments were calibrated using a conventional approach prior to analysis of each porcine plasma sample on both instruments. Comparative data were evaluated using Bland-Altman plots, demonstrating that the techniques were in good agreement. Compared with GC/MS, SIFT-MS provides fourfold higher sample throughput and shows great promise as an alternative analytical tool.

Standard Validation Protocol for Selected Ion Flow Tube Mass Spectrometry Methods Applied to Direct Headspace Analysis of Aqueous Volatile Organic Compounds.

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.

Rapid monitoring of volatile organic compounds: a comparison between gas chromatography/mass spectrometry and selected ion flow tube mass spectrometry.

RATIONALE: The gold standard for monitoring volatile organic compounds (VOCs) is gas chromatography/mass spectrometry (GC/MS). However, in many situations, when VOC concentrations are at the ppmv level, there are complicating factors for GC/MS. Selected ion flow tube mass spectrometry (SIFT-MS) is an emerging technique for monitoring VOCs in air. It is simpler to use and provides results in real time. METHODS: Three different experiments were used for the comparison. First SIFT-MS was applied to monitor the concentrations of 25 VOCs in a mixture at concentrations up to 1 ppmv using only a generic database for known kinetic data of three reagent ions (H3O(+), NO(+) and O2(+)) with each VOC. In experiment 2, a side-by-side comparison was made of 17 VOCs at concentrations between 1 ppmv and 5 ppbv after small corrections had been made to the SIFT-MS kinetic data. In a third experiment, a side-by-side comparison examined two groups of samples received for commercial analysis. RESULTS: In experiment 1, 85% of the VOC concentrations were within 35% of their stated values without any calibration of the SIFT-MS instrument. In experiment 2, the two techniques yielded good correspondence between the measured VOC concentrations. In experiment 3, good correlation was found for VOCs from three of the samples. However, interferences from some product ions gave over-reported values in one sample from the SIFT-MS instrument. CONCLUSIONS: These three experiments showed that GC/MS was better suited to monitoring samples containing large numbers of VOCs at high concentrations. In all other applications, SIFT-MS proved simpler to use, was linear with concentration over a much wider concentration range than GC/MS and provided faster results.

Selected ion flow tube studies of several siloxanes.

RATIONALE: People are using increasing amounts of siloxanes that ultimately end up in landfills and then in landfill gas and biogas digesters. Their presence poses difficulties for industries seeking to utilize the energy content of landfill and biogas, as the combustion process oxidises silicon to silicon dioxide that in turn damages engine parts. Rapid, efficient and accurate methods are needed to quantify their presence. METHODS: Selected ion flow tube mass spectrometry (SIFTMS) is an emerging real-time technique that has found application for monitoring trace volatiles in air. Samples containing the trace volatiles are simply drawn into the flow tube and convected in a stream of helium. Chemical ionization reactions from mass-selected reagent ions with the volatiles ensue. To quantify the volatiles in the sample, the ion chemistry of the reagent ion with each volatile must be known. RESULTS: Rate coefficients and product ion branching ratios were found for the compounds dodecamethylpentasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, octamethylcyclotetrasiloxane, triethylsilanol, tetramethylsilane and hexamethyldisilazane. CONCLUSIONS: The ion-molecule reactions of the seven silicon-containing compounds examined here were fast, occurring at or near the collision rate, thus allowing for detection at low levels. The very simple reaction chemistry found of proton transfer, electron transfer and methyl loss will enable easy quantitation of the siloxanes in landfill gas and biogas using the SIFTMS technique.

Application of selected ion flow tube-mass spectrometry to the characterization of monofloral New Zealand honeys.

Honeys have a range of physicochemical and organoleptic properties, depending on the nectar source. Selected Ion Flow Tube-Mass Spectrometry (SIFT-MS) is an emerging technology that quantifies volatile organic compounds (VOCs) to low concentrations (usually parts-per-trillion (ppt) levels) and is here applied to monitor the aromas in the headspace of different New Zealand monofloral honeys. Honey aromas arise from VOCs in the honeys that differ according to the flower type from which they were derived. In this exploratory study, the headspaces of nine monofloral New Zealand honeys (beech honeydew, clover, kamahi, manuka, rata, rewarewa, tawari, thyme, and vipers bugloss) were analyzed using SIFT-MS without sample preparation. The purpose of the investigation was to identify the major volatiles in each of the honeys and to test the feasibility of using SIFT-MS to distinguish between New Zealand monofloral honeys. In the nine monofloral honeys sampled, a clear distinction was observed between them based on their aroma signatures.

Headspace analysis of Italian and New Zealand parmesan cheeses.

UNLABELLED: New Zealand is a leader in the global dairy industry. Milk powder is the principal export product, but there is also a prominent cheese manufacturing industry, catering more for the domestic market. The Selected Ion Flow Tube-Mass Spectrometric (SIFT-MS) technique was used to compare 4 New Zealand cheeses marketed as "parmesan" with 4 Italian Parmigiano Reggiano and Grana Padano cheeses. The cheese headspace was analyzed in real time without any sample preconcentration. Total of 38 volatile compounds in the cheese headspace were monitored with headspace concentrations varying between single digit parts per billion (ppb) to tens of parts per million (ppm). When the results were subjected to multivariate statistical analysis, a clear discrimination was found between the New Zealand "parmesan" and Italian cheeses based solely on the measured concentrations of these volatile compounds. If the volatile compounds used in the analyses were restricted to known odor-active compounds in Parmigiano Reggiano cheese, the ability to discriminate between the cheeses was maintained. The analyses also showed that it was possible to clearly differentiate between the different processing plants in individual countries. Important discriminatory volatiles in the samples tested were butanoic acid and phenylacetaldehyde for discriminating between Italian cheeses and ethyl butyrate, acetaldehyde and methylbutanals between New Zealand cheeses. We conclude that the New Zealand "parmesans" do not provide a good representation of the aroma of Italian "parmesans." PRACTICAL APPLICATION: SIFT-MS has been shown to clearly differentiate both country of origin and the manufacturer of "parmesan" cheeses made in Italy and New Zealand based on differences in volatile organic compounds. Thus this method will have benefit for use in the quality control of "parmesan" and other cheese varieties.

Rapid discrimination and characterization of vanilla bean extracts by attenuated total reflection infrared spectroscopy and selected ion flow tube mass spectrometry.

Vanilla beans have been shown to contain over 200 compounds, which can vary in concentration depending on the region where the beans are harvested. Several compounds including vanillin, p-hydroxybenzaldehyde, guaiacol, and anise alcohol have been found to be important for the aroma profile of vanilla. Our objective was to evaluate the performance of selected ion flow tube mass spectrometry (SIFT-MS) and Fourier-transform infrared (FTIR) spectroscopy for rapid discrimination and characterization of vanilla bean extracts. Vanilla extracts were obtained from different countries including Uganda, Indonesia, Papua New Guinea, Madagascar, and India. Multivariate data analysis (soft independent modeling of class analogy, SIMCA) was utilized to determine the clustering patterns between samples. Both methods provided differentiation between samples for all vanilla bean extracts. FTIR differentiated on the basis of functional groups, whereas the SIFT-MS method provided more specific information about the chemical basis of the differentiation. SIMCA's discriminating power showed that the most important compounds responsible for the differentiation between samples by SIFT-MS were vanillin, anise alcohol, 4-methylguaiacol, p-hydroxybenzaldehyde/trimethylpyrazine, p-cresol/anisole, guaiacol, isovaleric acid, and acetic acid. ATR-IR spectroscopy analysis showed that the classification of samples was related to major bands at 1523, 1573, 1516, 1292, 1774, 1670, 1608, and 1431 cm(-1) , associated with vanillin and vanillin derivatives.

Monitoring chloramines and bromamines in a humid environment using selected ion flow tube mass spectrometry.

The selectivity and sensitivity of selected ion flow tube mass spectrometry (SIFT-MS) for individual breath analysis of haloamines has been improved by heating the flow tube in a commercial instrument to around 106 degrees C. Data is presented showing the marked reduction in the number density of water clusters of product ions of common breath metabolites that are isobaric with the product ions from monochloramine and monobromamine that are used to monitor the haloamine concentrations. These results have direct relevance to the real-time monitoring of chloramines in drinking water, swimming pools and food processing plants. However, once the isobaric overlaps from water cluster ions are reduced at the higher temperatures, there is no conclusive evidence showing the presence of haloamines on single breath exhalations in the mid parts per trillion range from examination of the breaths of volunteers.

Real-time measurement of peroxyacetyl nitrate using selected ion flow tube mass spectrometry.

The on-line detection of gaseous peroxyacetyl nitrate (PAN) using selected ion flow tube mass spectrometry (SIFT-MS) has been investigated using a synthetic sample of PAN in air at a humidity of approximately 30%. Using the H(3)O(+) reagent ion, signals due to PAN at m/z 122, 77 and 95 have been identified. These correspond to protonated PAN, protonated peractetic acid and its water cluster, respectively. These products and their energetics have been probed through quantum mechanical calculations. The rate coefficient of H(3)O(+) has been estimated to be 4.5 x 10(-9) cm(3) s(-1), leading to a PAN sensitivity of 138 cps/ppbv. This gives a limit of detection of 20 pptv in 10 s using the [M+H](+) ion of PAN at m/z 122.

Real-time monitoring of hazardous air pollutants.

Selected ion flow tube mass spectrometry (SIFT-MS) is a technique that offers real-time alternatives to existing methods for monitoring hazardous air pollutants (HAPs) in the environment using chemical ionization. The use of this technique requires knowledge of the kinetic parameters of the reagent ions H(3)O(+), NO(+), and O(2)(+) that are most commonly used. We report here measurements with these reagent ions of kinetic parameters for 17 HAP molecules ranging from 1,1-dichloroethene to nitrobenzene. From these data, limits of quantitation are established for all 17 compounds on a commercial SIFT-MS instrument and are found to be well below the time-weighted averages required by legislating bodies for workplace conditions.

Detection of volatile metabolites produced by bacterial growth in blood culture media by selected ion flow tube mass spectrometry (SIFT-MS).

To achieve faster bacteremia diagnosis, selected ion flow tube mass spectrometry (SIFT-MS) measured metabolic gases in the headspaces of BacT/ALERT blood culture bottles. Pseudomonas aeruginosa, Streptococcus pneumoniae, Escherichia coli, Staphylococcus aureus and Neisseria meningitidis growth and trace gas patterns were detected from 10 colony forming units after 6 h.

Real-time detection of common microbial volatile organic compounds from medically important fungi by Selected Ion Flow Tube-Mass Spectrometry (SIFT-MS).

We describe a new method, Selected Ion Flow Tube-Mass Spectrometry (SIFT-MS) for the rapid and sensitive real-time detection and quantification of volatile organic compounds from medically important fungi, grown on a range of laboratory media. SIFT-MS utilises the chemical ionisation reactions of mass-selected ions to characterise volatile organic compounds (VOCs) that are produced as metabolites from fungi. This technique has the distinct advantage over others in that it readily detects low molecular weight, reactive volatiles, and allows for real-time, quantitative monitoring. The fungi examined in this study were Aspergillus flavus, Aspergillus fumigatus, Candida albicans, Mucor racemosus, Fusarium solani, and Cryptococcus neoformans grown on or in malt extract agar, Columbia agar, Sabouraud's dextrose agar, blood agar, and brain-heart infusion broth. Common metabolites (ethanol, methanol, acetone, acetaldehyde, methanethiol, and crotonaldehyde) were detected and quantified. We found the fingerprint of volatiles, in terms of presence and quantity of volatiles to be strongly dependent on the culture medium, both in terms of variety and quantity of volatiles produced, but may form the basis for species specific identification of medically important fungi.

Infrared identification of matrix isolated H2O.O2.

Theoretical studies of the H2O.O2 complex have been carried out over the past decade, but the complex has not previously been experimentally identified. We have assigned IR vibrations from an H2O.O2 complex in an inert rare gas matrix. This identification is based upon theoretical calculations and concentration dependent behavior of absorption bands observed upon co-deposition of H2O and O2 in argon matrixes at 11.5 +/- 0.5 K. To aid assignment, we have used a harmonically coupled anharmonic oscillator local mode model with an ab initio calculated dipole moment function to calculate the OH-stretching and HOH-bending frequencies and intensities in the complex. The high abundance of H2O and O2 makes the H2O.O2 complex likely to be significant in atmospheric and astrophysical chemistry.

Infrared measurements and calculations on H2O.HO.

We have measured the infrared spectrum of H2O.HO in argon matrices at 11.5 +/- 0.5 K. We have also calculated the vibrational frequencies and intensities of the H2O.HO complex. As a result of these measurements and calculations, we have assigned a previously unassigned absorption band at 3442.1 cm-1 to the OH stretch in the radical complexed to the water molecule. This absorption originates from a complex that is situated in a different site within the argon matrix to those absorptions already assigned to this vibration at 3452.2 and 3428.0 cm-1. We observe a decrease in intensity of the OH radical stretching vibration of the H2O.HO complex upon isotopic substitution of D for H that agrees well with our calculations.