Tedlar™ bags are a promising medium for remote breath collection and later analysis using SIFT-MS for disease diagnosis. It is important to understand the changes in integrity of samples stored in Tedlar™ bags. However, there is little work into this problem completed to date, and thus little known about these issues. Therefore, a study into the integrity of samples stored in Tedlar™ bags and analysed using SIFT-MS was undertaken. The sample integrity of ammonia, acetone, ethanol, isoprene and pentane, all initially at 3ppm in breath and nitrogen substrates, and stored in Tedlar™ bags was investigated. Experiments tested the effect of storage size (0.5, 1, 3L), storage time (6-48 hours), storage temperature (23℃ - 25℃, 37℃), humidity (0.4 - 4.5% absolute) and inter-bag variation using triplicate bags. The SIFT-MS instrument used was LDI2 located at Christchurch Hospital. The repeatability and precision of LDI2 was established using prepared cylinder samples (0.05% absolute humidity) of acetone, pentane and ethanol tested at seven times over a 250 min time period. A generalised Cauchy distribution was used to give a combined distribution from multiple bags for the sample humidity and compound concentration. A combined measure of the repeatability and precision, T s , ranged between 217 - 349 ppb for ethanol, acetone and pentane. The factors affecting the repeatability and precision were both machine and compound dependant. The effect of the factors differed over time, with different precursors and compounds. No obvious effects of bag storage size on the sample integrity of pentane, isoprene, ethanol and acetone were observed. The absolute humidity change within bag samples was linked to the volume to surface area ratio because it was more affected by permeation and condensation. All compounds in the nitrogen substrate (except for 37℃ stored acetone (NO+)) displayed decreases in sample integrity with time. All compounds in the breath substrate displayed regular losses of sample integrity, except for the 37℃ and 23℃ - 25℃ stored ethanol (NO+) and 37℃ stored ethanol (H3O+), pentane (O2+) and ammonia (H3O+, O2+). The average change of sample integrity for pentane, isoprene, ethanol and acetone ranged from 0.2 to 3.6 times the maximum T s , while ammonia ranged from 0.9 - 10 times. All observed behaviour was reproducible. Absolute humidity and storage temperature affected the sample integrity of acetone, ethanol and ammonia. Generally, the intra-bag variance was comparable between all storage temperatures and substrates while the inter-bag variation was affected by the absolute humidity. Only the initial and final concentrations between precursors for the 23℃ - 25℃ stored breath and nitrogen substrates agreed. The breath substrate samples gave erroneous values for ammonia. Permeation of compounds into the bags from the atmosphere was not significant. The overall issues surrounding storing breath in Tedlar™ bags for analysis using SIFTMS is not the loss of sample integrity, but the kinetics, precision and repeatability of the SIFT-MS instrument. The current kinetics are not adequate to accurately monitor acetone, isoprene, pentane, ammonia and ethanol in breath and stored in Tedlar™ bags at breath absolute humidity levels greater than 3%. Generally, the loss of sample integrity was only marginally outside the repeatability and precision of the machine.

The use of breath odours in medical diagnosis dates back to classical times, though in its modern form the technique is only a few decades old. There are several breath tests in common clinical use, though all of them involve administration of a known or labelled exogenous compound. More recently, over the last twenty years, interest has focussed on analysis of endogenous metabolites in breath, but despite a large number of published studies reporting a number of disease markers, there has been little or no impact on clinical practice. Nonetheless, breath analysis offers a number of potential advantages over current biochemical methods. One major advantage of breath analysis is its non-invasive nature, which has led to significant interest in its use at point-of care for monitoring chronic diseases such as diabetes and the chronic infections ubiquitous in cystic fibrosis. However, breath analysis classically involves the use of expensive laboratory based analytical equipment which requires extensively-trained personnel and which cannot readily be miniaturised. Systems based on simple gas sensors might offer a way of overcoming these limitations. In recent years, Cranfield University has developed an instrument called the single metal oxide sensor gas analyser (SMOS-GA, more commonly referred to as the “Breathotron”) as a proof of concept for sensor-based breath analysis. In this project the Breathotron has been used in conjunction with selected ion flow tube mass spectrometry (SIFT-MS) and thermal desorption gas chromatography mass spectrometry (TD-GC-MS) to determine the changes in the concentrations of volatile organic compounds (VOCs) in breath in a number of experimental situations which a relevant to the diagnostic monitoring of diabetes mellitus. Studies conducted on clinically healthy volunteers were: an oral glucose tolerance test (OGTT); a six minute treadmill walking test; and a bicycle ergometer test. Additionally Breathotron and analytical data were also obtained during a hypoglycaemic clamp study carried out on hypoglycaemia-unaware Type I diabetics. The principle breath volatiles determined analytically were: acetone, acetaldehyde, ammonia isoprene though data on a number of others was also available. In general, it proved difficult to establish any reproducible relationship between the concentration of any compound measured and blood glucose concentration any of the experimental interventions. It was notable, though, that statistically significant associations were observed occasionally in data from individual volunteers, but even these were not reproduced in those trials which involved repeated measurements. This remained true even where spirometry data were used to derive VOC clearance rates. This may explain previous reports from smaller studies of an association between glucose and breath acetone concentration. It seems probable that any experimentally-induced changes in breath VOC concentration or clearance were of much smaller magnitude than background variability and was consequently not detectable. These observations were mirrored in the sensor-derived results. Multivariate analysis across all trials where Breathotron data were obtained suggested clustering by individual volunteer rather than glycaemic status. This suggests that that there exists a “background” breath volatile composition, dependent perhaps on such factors as long-term diet, which is independent of our experimental intervention. The Breathotron was also used as a platform to assess the performance of three different types of mixed metal oxide sensor in vitro. Calibration curves were generated for acetone, ammonia and propanol covering the physiological range of concentrations and with a similar water content to breath. Close correlations were obtained between concentration and the amplitude of the sensor response. Sensor response reproducibility was also determined using acetone at a concentration of 10ppm with dry and humidified test gas. There were significant differences between sensor types in overall reproducibility and in response to humidity. These results suggest that had there been substantial changes in breath VOC composition as a result of our experimental interventions, any of the types of sensor used would have been capable of responding to them. In summary, these results do not support the efficacy of breath VOC analysis as a means of non-invasive diagnostic monitoring.

SIFT-MS is a relatively new trace gas analysis technique that has wide application. One particular attribute of the instrument is the ability to detect and quantify volatile organic compounds to the parts per trillion in real-time without the need for sample preparation. However the issue of maintaining accuracy at these low concentrations required attention as it was evident large or polar analytes were being lost by adsorption to the SIFT instrument’s inlet system. The purpose of this research was to evaluate the performance of a passivated inlet in lowering any adsorption in the inlet system compared to the current unpassivated inlet of the SIFT instrument. Volatile concentrations of vanillin (C₈H₈O₃ 152.15 g/mol), ammonia (NH₃ 17.03 g/mol), and hydrogen sulfide (H₂S 34.08 g/mol) were measured. The results determined the passivated inlet provided a significantly better inlet response to these compounds. Consequently improved passivated inlets were installed on current models of SIFT-MS VOICE200®, and also the research laboratory VOICE100™ instrument. Having established a more reliable sampling system for very low concentrations of analyte, attention was paid to SIFT-MS flavour analysis of two foods, cheese and chocolate. The volatile matrix of these foods is highly complex and the compounds of interest are typically difficult to measure. The key aroma compounds for analysis were based on reported literature and earlier SIFT-MS studies which provided a useful framework for the current food flavour research. A significant finding from the SIFT-MS examination of Parmesan cheese is that differences in the relative concentration of some characteristic aroma compounds were a consequence of the milk type used in manufacture. Endogenous enzymes responsible for a multitude of reactions are mostly if not completely inactivated by the pasteurization temperature. A similar analysis approach was attempted for chocolate analysis. Here flavour differences were not as clearly recognised as for the cheese samples. In chocolate there are a greater number of parameters that are involved in its manufacture. Nevertheless, some recognisable differences in chocolate could be attributed to cocoa bean type and flavour additions by the manufacturer.

Real time detection of Volatile Organic Compounds (VOCs) using Selected Ion Flow Tube – Mass Spectrometry (SIFT-MS) provides a unique opportunity for research into breath testing for clinical diagnosis. However, before engaging in research into breath analytes as markers of disease, appropriate breath collection methods are required. Collection of breath for SIFT-MS instruments fall into two categories, direct breath collection into the instrument and the remote breath collection onto a storage medium. This thesis describes the development and validation of both methods of breath collection equipment for SIFT-MS analysis. Development of the direct breath collection device involved standardising and optimising the way in which breath is sampled by SIFT-MS. Design considerations include ergonomics, patient safety, breathing resistance, materials, and appropriate operating conditions of the device. Results from materials testing showed that all materials emit VOCs and the best approach is to minimise VOC emission by careful material selection. To minimise flow resistance experienced by the patient, the capillary from which the SIFT-MS instrument samples, is placed as close as possible to the users mouth. The optimal operating temperature of the device was found to be 100°C - 120°C, which ensures that water vapour will not condense inside the capillary causing blockage. In order to ensure patient safety the device is adequately insulated using stagnant air which also minimises VOC emission from insulation materials. Because a SIFT-MS instrument is large and cannot be easily shifted around a hospital, a system of remote sample collection is required. It is also important to separately collect and analyse breath from the respiratory alveolar region. For this reason the remote breath collection device designed also fractionates collected breath samples into the breath from the upper airways and alveolar breath. The storage medium chosen for the collected breath samples is a gas sampling bag made from Tedlar™. Collection of breath into Tedlar™ bags allows breath to be stored as a whole air sample, the ideal form for analysis with the SIFT-MS technique. Alveolar breath is fractionated from deadspace gasses by measuring a subject's exhalation and collecting the portion of interest. The breath exhalation is measured by an averaging Pitot tube and pressure transducer. Signal processing and automation of the remote breath collection device is controlled by a Cypress Microsystems PSoC microcontroller. To validate the device isoprene and acetone concentrations in fractionated breath samples were compared with a whole breath sample. Results showed that the alveolar breath fraction had a higher concentration of acetone than the upper airway fraction, indicating that the breath was successfully fractioned. However, isoprene concentrations were lower in both fractions due to hyperventilation of the subject causing a dilution effect of alveolar VOCs. Therefore, a higher sample collection volume is required per exhalation, and regulating subjects' breathing rate will avoid the dilution effect observed in collected breath samples. Overall, this thesis had designed, developed and validated two forms of breath collection systems for use with SIFT-MS technology.

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Dans le procédé de production d’engrais à base de superphosphate, l’attaque de la roche phosphatée par l’acide sulfurique génère des sous-produits gazeux odorants. Bien que leurs émissions se situent dans les limites réglementaires, les usines d’engrais à base de superphosphate sont susceptibles de causer des nuisances olfactives pour les riverains. Cette thèse propose d’étudier la faisabilité d’un procédé de traitement des odeurs par l’ozonation en phase gazeuse homogène. Une première étape de priorisation des composés chimiques ayant le potentiel odorant le plus important a été réalisée. Ce classement a été effectué à partir d’un rapport technique fourni par notre partenaire industriel basé sur une campagne de mesure olfactométrique et de caractérisation chimique des gaz émis par la cheminée d’une usine de production des engrais superphosphate. À partir du calcul de la valeur d’activité odorante (OAV), deux familles de composés ont été ciblées : les composés soufrés – représentés par le sulfure d’hydrogène (H2S), le sulfure d’éthylméthyle (MES) et le disulfure de diméthyle (DMDS) – et les aldéhydes (représentés par le propanal et le butanal). Deux techniques analytiques (GC/FID et SIFT/MS) ont été mises en œuvre afin d’évaluer les performances d’élimination de ces composés, la difficulté d'analyser une matrice gazeuse contenant de l'ozone ayant été mise en évidence. Ainsi, une interférence de l'ozone sur l'analyse des aldéhydes par GC/FID a été identifiée. La technique SIFT/MS a, quant à elle, nécessité un développement important. L’ozonation d’effluents gazeux modèles a été réalisée en suivant l’élimination des composés cibles dans différentes conditions de fonctionnement (temps de résidence, température du réacteur, concentration en ozone et taux d’humidité) dans un domaine expérimental compatible avec les contraintes industrielles. Les composés soufrés ont présenté des taux d’élimination élevés, particulièrement dans le cas de H2S, dont les conversions ont atteint environ 80%. Les monosulfures (MES) et disulfures organiques (DMDS) se sont montrés moins réactifs à l’ozone, puisque les conversions sont restées assez faibles (de l’ordre de 30% pour un ratio O3/soufrés similaire). Dans la gamme de conditions opératoires utilisées, ni l'humidité, ni le temps de résidence dans le réacteur n’ont montré d'influence considérable. La concentration d'ozone s’avère être le paramètre du procédé le plus influant, ayant un effet positif sur les taux de conversion des trois composés soufrés étudiés. Parallèlement, pour le DMDS, une augmentation de la température du réacteur a aussi amélioré la conversion. De manière globale, les taux de conversion les plus importants ont été obtenus pour les ratio O3/soufrés et la température du réacteur les plus élevés. A l’inverse, même lorsque les conditions de réaction les plus favorables ont été appliquées (température et concentration d’ozone les plus élevées), les aldéhydes se sont montrés non réactifs vis-à-vis de l’ozone. Malgré les faibles conversions obtenues, l’utilisation du SIFT/MS a permis d’identifier les principaux sousproduits de la réaction ozone-composés soufrés en phase gazeuse comme étant le méthyléthylsulfoxyde (MESO), le méthyléthylsulfone (MESO2), le diméthyl thiosulfinate (DMSOS), les isomères de diméthyl thiosulfonate (DMSO2S), le diméthyldisulfoxyde (DM(SO)2) et également le dioxyde (SO2) et le trioxyde de soufre (SO3). Le procédé de traitement des odeurs par ozonation directe des gaz en sortie de cheminée industrielle apparaît donc difficilement envisageable en raison de la faible efficacité d’élimination des composés malodorants démontrée dans nos essais. En revanche, cette technique couplée avec une absorption chimique pourrait s’avérer intéressante pour éliminer les nuisances olfactives avec une bonne efficacité / In the superphosphate-based fertilizers production process, the attack of phosphate rock by sulfuric acid generates odorous gaseous by-products. Although their emissions are within regulatory limits, superphosphate fertilizer plants are likely to cause odor nuisance to residents. This thesis proposes to study the feasibility of a process of odor treatment by ozonation in homogeneous gas phase. A first step of prioritization of the chemical compounds with the most important odorous potential has been realized. This ranking was established from a technical report provided by our industrial partner based on a campaign of olfactometric measurement and chemical characterization of the gases emitted by the chimney of a superphosphate fertilizer production plant. From the calculation of the odor activity value (OAV), two families of compounds were targeted: sulfur compounds - represented by hydrogen sulphide (H2S), ethylmethyl sulphide (MES) and dimethyl disulfide (DMDS) - and aldehydes (represented by propanal and butanal). Two analytical techniques (GC/FID and SIFT/MS) were applied in order to evaluate the elimination performance of these compounds, the difficulty of analyzing a gaseous matrix containing ozone having been demonstrated. Thus, ozone interference on GC/FID analysis of aldehydes has been identified. The SIFT/MS technique, in turn, required significant development. The ozonation of model gaseous effluents was carried out following the elimination of the target compounds under different operating conditions (residence time, reactor temperature, ozone concentration and moisture) in an experimental field compatible with the industrial constraints. The sulfur compounds exhibited high removal rates, particularly in the case of H2S, whose conversions reached about 80%. Organic monosulfides (MES) and disulfides (DMDS) were less reactive to ozone, as conversions remained quite low (around 30% for the same level of O3/sulfur ratio). In the range of operating conditions used, neither the moisture nor the residence time in the reactor showed considerable influence. The ozone concentration is the most influential process parameter, having a positive effect on the conversion rates of the three sulfur compounds studied. Meanwhile, for DMDS, an increase in reactor temperature also improved the conversion. Overall, the highest conversion rates were obtained for the highest O3/sulfur ratios and reactor temperature. Conversely, even when the most favorable reaction conditions have been applied (highest temperature and ozone concentration), the aldehydes have been inert to ozone. Despite the low conversions obtained, the use of SIFT/MS has identified the main by-products of the ozone-sulfur compounds gas phase reaction as methylethylsulfoxide (MESO), methylethylsulfone (MESO2), dimethyl thiosulfinate (DMSOS), isomers of dimethyl thiosulfonate (DMSO2S), dimethyldisulfoxide (DM(SO)2) and also sulfur dioxide (SO2) and trioxide (SO3). The odors treatment process by direct ozonation of the gases at the outlet of industrial chimney thus appears difficult to envisage because of the low efficiency of malodorous compounds elimination demonstrated in our tests. On the other hand, this technique coupled with chemical absorption could be interesting to eliminate the olfactory nuisances with a good efficiency

Whole grain is associated with rougher texture and off-flavours which has decreased consumer acceptance. Pasta drying is also critical during production because of influence on texture and quality. The effects of drying type and whole grain content on physicochemical and qualitative properties of pasta were investigated. Increasing whole grain content lowered paste viscosity and increased cooking loss while low temperature drying improved quality. The impact of these effects on pasta texture and flavour was further explored. While bitterness, branniness, and surface roughness positively correlated with whole grain content, drying type only affected firmness. Phenolic content, headspace, and textural analysis corroborated this data. Change in pasta flavour upon addition of sodium-reduced cheese sauce was also examined. Sodium not only enhances flavour of dishes, it also suppresses bitterness. While flavours were uniquely affected upon sauce addition, sodium content did not affect bitterness. Headspace analysis using SIFT-MS showed volatile concentration to reduce, likely caused by a barrier created from the sauce. / MITACS Accelerate, Kraft Mississauga Mill