The application of Selected Ion Flow Tube Mass Spectrometry (SIFT MS) to the analysis of olive oil shows several distinct advantages over more conventional analysis techniques. The two areas described in this thesis examining olive oil quality are the analysis of Volatile Organic Compounds (VOCs) and the assessment of antioxidant activity. VOCs are responsible for the aroma and much of the taste of olive oil, while antioxidants afford some protection from harmful reactions involving radical species inside the body by scavenging radicals when olive oil is ingested. The VOCs of olive oil are used by sensory panel judges to classify oils by their degree of suitability for human consumption. The major parameters used for this evaluation are the strengths of any defects and the degree of fruitiness. A defect is an indication of an undesired process which has occurred in the oil, while fruitiness is a fragile attribute which denotes a good quality oil and is easily masked by defects. SIFT MS was used to measure the strengths of the olive oil defects rancid, winey, musty, fusty and muddy. Great potential was demonstrated for all defects except musty and the concentrations of VOCs in olive oil head space were correlated with the peroxide value, a measure of the degree of oil oxidation. A study aimed at correlating the strength of the fruitiness attribute as determined by a sensory panel with the concentrations of VOCs in olive oil head space was unsuccessful. The SIFT MS Total Oxyradical Scavenging Capacity (TOSC) assay was used to measure olive oil antioxidants. This assay measures all antioxidants in oil, not only those removed by extraction with a solvent, as it is conducted in an emulsion. SIFT MS TOSC assay results were found to correlate well with those of the widely used Folin Ciocalteu assay and the total concentration of phenolic compounds present in olive oil. Discrepancies between the two assays were most likely due to hydrophobic antioxidants which are measured by the SIFT MS TOSC assay but not the other tests.

Data is presented for a range of experiments that have been performed using a selected ion flow tube (SIFT) instrument operated at room temperature (~ 298K) with carrier gas pressures typically in the range of 0.3 – 0.6 Torr. The majority of the experiments discussed are performed on a Voice100 instrument that has not been described in detail previously. The Voice100 is a novel instrument that has been designed particularly for quantitative trace gas analysis using the SIFT-MS technique. A mixture of helium and argon carrier gases are employed in the Voice100 flow tube. By mixing carrier gases, the flow dynamics and diffusion characteristics of a flow tube are altered when compared to classic single carrier gas models. Therefore firstly, optimal flow conditions for the operation of a Voice100 are characterised. The diffusion of an ion in a mixture of carrier gases is then characterised using theoretical models and experimental techniques. This research requires that a new parameter Mp be defined regarding the mass discrimination of an ion in the non-field-free region near the downstream ion sampling orifice. Furthermore, a new method is described for the simultaneous measurement of rate coefficients for the reactions of H₃O⁺.(H₂O)n (n = 1, 2, 3) ions with analytes. Rate coefficients and branching ratios for the reactions of SIFT-MS precursor ions with specific analytes related to four individual applications are presented. For each application, the kinetic parameters are determined so as to facilitate the quantitative detection of the analytes relevant to that application. The GeoVOC application involves the measurement of hydrocarbon concentrations in the headspace of soil and water across a range of humidities. Alkyl esters are investigated to allow for the quantitative detection of each compound in fruits and vegetables. Chemical warfare agents, their surrogates and precursor compounds are studied which allows for the quantitative or semi-quantitative detection of a range of highly toxic compounds. Finally, 17 compounds classified by the US-EPA as hazardous air pollutants are studied that enables SIFT-MS instruments to replicate sections of the TO-14A and TO-15 methods.

Selected Ion Flow Tube-Mass spectrometry (SIFT-MS) is an analytical measurement technology for the real-time quantification of volatile organic compounds in gaseous samples. This technology has current and potential applications in a wide variety of industries, although the focus of this research is in medical science. In this field, SIFT-MS has potential as a diagnostic device, capable of determining the presence of a particular disease or condition. In addition, SIFT-MS can be used to monitor the progression of a disease state, or predict deviations from expected behaviour. Lastly, SIFT-MS can be used for the identification of biomarkers of a particular disease state. All these possibilities are available non-invasively and in real-time, by analysing breath samples. SIFT-MS produces an extensive amount of data, requiring specific mathematical methods to identify biomarker masses that differ significantly between populations or time-points. Two classification methods are presented for the analysis of SIFT-MS mass scan data. The first method is a cross-sectional classification model, intended to differentiate between the diseased and non-diseased state. This model was validated in a simple test case. The second method is a longitudinal classification model, intended to identify key biomarkers that change over time, or in response to treatment. Both of these classification models were validated in 2 clinical trials, investigating renal function in humans and rats. The first clinical trial monitored changes in breath ammonia, TMA and acetone concentrations over the course of dialysis treatment. Correlations with the current gold standard plasma creatinine, and blood urea nitrogen were reported. Finally, biomarkers of renal function were identified that change predictably over the course of treatment. The second trial induced acute renal failure in rats, and monitored the change in renal function observed during recovery. For comparison and validation of the result, a 2-compartment model was developed for estimating renal function via a bolus injection of a radio-labelled inulin tracer, and was compared with the current gold standard plasma creatinine measurement, modified using the Cockcroft-Gault equation for rats. These two methods were compared with SIFT-MS monitoring of breath analytes, to examine the potential for non-invasive biomarkers of kidney function. Results show good promise for the non-invasive, real-time monitoring of breath analytes for diagnosis and monitoring of kidney function, and, potentially, other disease states.

The application of Selected Ion Flow Tube Mass Spectrometry (SIFT MS) to the analysis of olive oil shows several distinct advantages over more conventional analysis techniques. The two areas described in this thesis examining olive oil quality are the analysis of Volatile Organic Compounds (VOCs) and the assessment of antioxidant activity. VOCs are responsible for the aroma and much of the taste of olive oil, while antioxidants afford some protection from harmful reactions involving radical species inside the body by scavenging radicals when olive oil is ingested. The VOCs of olive oil are used by sensory panel judges to classify oils by their degree of suitability for human consumption. The major parameters used for this evaluation are the strengths of any defects and the degree of fruitiness. A defect is an indication of an undesired process which has occurred in the oil, while fruitiness is a fragile attribute which denotes a good quality oil and is easily masked by defects. SIFT MS was used to measure the strengths of the olive oil defects rancid, winey, musty, fusty and muddy. Great potential was demonstrated for all defects except musty and the concentrations of VOCs in olive oil head space were correlated with the peroxide value, a measure of the degree of oil oxidation. A study aimed at correlating the strength of the fruitiness attribute as determined by a sensory panel with the concentrations of VOCs in olive oil head space was unsuccessful. The SIFT MS Total Oxyradical Scavenging Capacity (TOSC) assay was used to measure olive oil antioxidants. This assay measures all antioxidants in oil, not only those removed by extraction with a solvent, as it is conducted in an emulsion. SIFT MS TOSC assay results were found to correlate well with those of the widely used Folin Ciocalteu assay and the total concentration of phenolic compounds present in olive oil. Discrepancies between the two assays were most likely due to hydrophobic antioxidants which are measured by the SIFT MS TOSC assay but not the other tests.

Data is presented for a range of experiments that have been performed using a selected ion flow tube (SIFT) instrument operated at room temperature (~ 298K) with carrier gas pressures typically in the range of 0.3 – 0.6 Torr. The majority of the experiments discussed are performed on a Voice100 instrument that has not been described in detail previously. The Voice100 is a novel instrument that has been designed particularly for quantitative trace gas analysis using the SIFT-MS technique. A mixture of helium and argon carrier gases are employed in the Voice100 flow tube. By mixing carrier gases, the flow dynamics and diffusion characteristics of a flow tube are altered when compared to classic single carrier gas models. Therefore firstly, optimal flow conditions for the operation of a Voice100 are characterised. The diffusion of an ion in a mixture of carrier gases is then characterised using theoretical models and experimental techniques. This research requires that a new parameter Mp be defined regarding the mass discrimination of an ion in the non-field-free region near the downstream ion sampling orifice. Furthermore, a new method is described for the simultaneous measurement of rate coefficients for the reactions of H₃O⁺.(H₂O)n (n = 1, 2, 3) ions with analytes. Rate coefficients and branching ratios for the reactions of SIFT-MS precursor ions with specific analytes related to four individual applications are presented. For each application, the kinetic parameters are determined so as to facilitate the quantitative detection of the analytes relevant to that application. The GeoVOC application involves the measurement of hydrocarbon concentrations in the headspace of soil and water across a range of humidities. Alkyl esters are investigated to allow for the quantitative detection of each compound in fruits and vegetables. Chemical warfare agents, their surrogates and precursor compounds are studied which allows for the quantitative or semi-quantitative detection of a range of highly toxic compounds. Finally, 17 compounds classified by the US-EPA as hazardous air pollutants are studied that enables SIFT-MS instruments to replicate sections of the TO-14A and TO-15 methods.

6 Abstract This thesis focuses on the identification and quantification of volatile metabolites in the exhaled breath that might be used as possible biomarkers of Gastroesophageal Reflux Disease. Animal tissue samples were exposed to conditions simulating the gastric environment to identify specific volatile compounds that would be chosen for real-time quantification in exhaled breath of GERD patients and healthy controls using selected ion flow tube mass spectrometry. Solid phase microextraction, was used in combination with gas chromatography mass spectrometry, for qualitative analyses of the headspace of these samples. Only acetic acid was significantly elevated and so it has been elected for the quantitative analysis in the breath of the patients. The median concentration of acetic acid measured by SIFT-MS in the exhaled breath of twenty-two GERD patients was found to be higher (85 ppbv) in comparison to the control group (31 ppbv). The results show that breath acetic acid could be valuable marker for GERD diagnosis and monitoring.

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