Within the context of global climate change and soaring energy prices, people are searching for inexpensive and renewable sources of energy; therefore, burning wood for home heating is increasing. Woodsmoke contains substances known to harm human health and is a major contributor to air pollution in many parts of the world; yet there is limited research into the health effects of woodsmoke and existing research suffers from methodological constraints. As a result, there is interest in producing robust woodsmoke exposure estimates for health research and air quality management purposes. Studying health and the environment is inherently spatial; however, research related to air pollution and health tends to be aspatial. As investigators begin to understand the influence of spatial processes on research findings, the importance of adopting a spatial approach to modelling exposure and health risk is becoming apparent. This thesis describes a spatially explicit model for predicting fine particulate matter (PM2.5) attributable to woodsmoke from residential heating in Victoria, British Columbia, Canada. Spatially resolved measurements of PM2.5 were collected for 32 evenings during the winter heating seasons of 2004/05, 2005/06, 2006/07 using a nephelometer installed in a passenger vehicle. Positional data were collected concurrently using a Global Positioning System (GPS). Levoglucosan, a chemical unique to woodsmoke, was measured to confirm the presence of woodsmoke in the measured PM2.5. The spatial scale for the analysis of woodsmoke data was determined using semivariograms to identify the maximum distance of spatial dependence in the data which typically occurred near 2700m. Different spatial approaches for modelling woodsmoke concentrations were evaluated both qualitatively in terms of transferability, meeting statistical assumptions, and potential for exposure misclassification; and quantitatively to assess the association between the model’s predicted PM2.5 concentrations and observed PM2.5. The baseline model characterized exposure based on the PM2.5 value from the closest fixed monitor (R=0.51, α=0.05). The Krigged model produced a seasonal average surface based on nephelometer measurements and showed the weakest performance (R=0.25, α=0.05). The regression models predicted concentrations of woodsmoke based on predictor variables available from census data, typically used in health research, and spatial property assessment data (SPAD), an underused data source at a finer spatial resolution. Different approaches to regression modelling were investigated. A regression model already developed for Victoria performed the best quantitatively (R=0.84, α=0.05); however, qualitative considerations precluded it from being selected as an appropriate model. A quantitatively (R=0.62, α=0.05) and qualitatively robust regression model was developed using SPAD (M6). SPAD improved the spatial resolution and model performance over census data. Removing spatial and temporal autocorrelation in the data prior to modelling produced the most robust model as opposed to modelling spatial effects post regression. A Bayesian approach to M6 was applied; however, model performance remained unchanged (R=0.62, α=0.05). The spatial distribution of susceptibility to health problems associated with woodsmoke was derived from census data relating to population, age and income. Intersecting the exposure model with population susceptibility in a Geographic Information System (GIS) identified areas at high risk for health effects attributable to woodsmoke.

Background Anthropogenic air pollution is a global health problem estimated to contribute to millions of premature deaths. Exposure to biomass smoke is common due to varying sources, such as wildfires, indoor cooking over open fires, and residential heating from wood stoves. In urban environments transportation and industry rely heavily on the combustion of fossil fuels yet environmental policies increasingly support a shift to renewable fuels such as biodiesel. It has not been investigated how either wood smoke or biodiesel exhaust affect human health in general or the cardiovascular system in particular. We hypothesized that wood smoke exposure would induce acute cardiovascular impairment via similar underlying mechanisms as have been established for petrodiesel exhaust exposure. We also hypothesized that replacing petrodiesel with biodiesel, as a blend or pure biodiesel, would generate an exhaust profile with a less harmful effect on the cardiovascular system than petrodiesel exhaust. Methods In four separate studies healthy non-smoking subjects were exposed to different air pollutants in controlled exposure chambers followed by clinical investigations of the cardiovascular system. All studies were performed as randomized controlled trials in a crossover fashion with each individual acting as her own control. In study I healthy volunteers were exposed to wood smoke at a target concentration of particulate matter (PM) 300 µg/m3 for three hours followed by measures of blood pressure, heart rate variability and central arterial stiffness. In study II subjects were exposed to wood smoke at a target concentration of PM 1000 µg/m3 for one hour followed by measures of thrombus formation using the Badimon technique and vasomotor function using forearm venous occlusion plethysmography. In study III subjects were exposed to petrodiesel exhaust and a 30% rapeseed methyl ester (RME30) biodiesel blend for one hour at a target concentration of PM 300 µg/m3. Following exposure, thrombus formation and vasomotor function were assessed as in study II. In study IV subjects were exposed to petrodiesel exhaust at a target concentration of PM 300 μg/m3for one hour and pure rapeseed methyl ester (RME100) exhaust generated at identical running conditions of the engine. Following exposure, thrombus formation and vasomotor function were assessed as in study II and III. Results In study I fourteen subjects (8 males) were exposed to wood smoke at P M 294±36 μg/m3. Compared to filtered air exposure, measures of central arterial stiffness were increased and heart rate variability was decreased following wood smoke exposure. No effect was seen on blood pressure. In study II sixteen males were exposed to wood smoke at PM 899±100 μg/m3. We found no evidence of increased thrombus formation or impaired vasomotor function following wood smoke exposure. In study III sixteen subjects (14 males) were exposed to petrodiesel exhaust (PM 314±27 µg/m3) and RME30 exhaust (PM 309±30 µg/m3). Thrombus formation and vasomotor function were equal following either exposure. In study IV nineteen males were exposed to petrodiesel exhaust (PM 310±34 µg/m3, 1.7±0.3 x105 particles/cm3) and RME100 exhaust (PM 165±16 µg/m3, 2.2±0.1 x105 particles/cm3). As in study III, thrombus formation and vasomotor function were identical following both exposures. Conclusions We have for the first time demonstrated that wood smoke exposure can increase central arterial stiffness and decrease heart rate variability in healthy subjects. We did not, however find evidence of increased thrombus formation and impaired vasomotor function following wood smoke exposure at a higher concentration for a shorter time period. We have, for the first time, demonstrated that exhaust from RME biodiesel induced acute adverse cardiovascular effects of increased thrombus formation and impaired vasomotor function in man. These effects are on par with those seen following exposure to petrodiesel exhaust, despite marked physicochemical differences of the exhaust characteristics.

Women living in rural Kenya rely on wood for cooking and are exposed to elevated amounts of wood smoke. The objective of this thesis was to assess the health and quality of life benefits of installing biogas digesters on rural Kenyan dairy farms. Thirty-one farms with biogas digesters and 31 farms without digesters (referent group) were assessed for wood utilization practices, basic respiratory and self-reported health, and exposure to volatile organic compounds (VOCs). Women with biogas digesters spent less time and money acquiring wood, and less time exposed to wood smoke (p<0.01). Multivariable linear regression showed associations between daily wood consumption and having a biogas digester, family size, and number of cows. Individual VOCs were lower in cookhouses on biogas farms (p<0.001) and women with biogas digesters reported fewer respiratory symptoms. Biogas digesters are one technology that can reduce reliance on wood fuel and reduce exposures to harmful wood smoke.

Catfish fillets that were enhanced with salt and various phosphate treatments through vacuum tumbling or multi-needle injection were evaluated for yield, protein exudate (only tumbling), surface color, pH, cooking loss, tenderness, purge loss and shelf-life. An agglomerated sodium phosphate blend (AGSP) was the optimum treatment for both vacuum tumbling and multi-needle injection and was further utilized in conjunction with potassium lactate (PL) and/or potassium acetate (PA) through vacuum tumbling to determine their effect on the quality, shelf-life and sensory characteristics of enhanced catfish fillets. In addition, the combination of AGSP and PA+PL that maximized shelf-life was further utilized in conjunction with liquid or wood smoking to evaluate the quality and inhibition of L. monocytogenes growth in ready-to-eat (RTE) smoked catfish fillets. All phosphate treatments increased (P<0.05) tenderness, but AGSP that contained mono-, tri-, and polyphosphates increased (P<0.05) pH and yield and decreased (P<0.05) yellowness in both tumbling and injection systems when compared to the control treatment. In addition, AGSP decreased (P<0.05) protein exudate when fillets were tumbled and increased (P<0.05) solution pick-up when injected. Psychrotrophic plate counts (PPC) for all phosphate treatments were similar to the control at each storage time and reached 7 log CFU/g by day 7 of storage; however, when AGSP was used in conjunction with PA+PL, PPC and sensory spoilage scores of raw catfish fillets were lower (P<0.05) than the control at each storage time. Marinating with a combination of 0.25% PA and 0.58% PL increased shelf-life (P<0.05) to between 10 and 14 days when compared to the control which had a shelf-life between 7 and 10 days. In addition, consumers preferred (P<0.05) fried catfish fillets that were treated with AGSP with and without PA+PL when compared to non-marinated controls with respect to appearance, flavor and overall acceptability. In conclusion, AGSP optimized yield and improved the quality of refrigerated catfish fillets, and extended shelf-life three days over other treatments when combined with PA+PL. This combined treatment also enhanced sensory properties of fried catfish fillets and had a synergistic effect with wood smoke constituents that inhibited the growth of L. monocytogenes on RTE smoked catfish fillets.

Exposomics applies metabolomics methods and technologies to the comprehensive analysis of all low molecular weight molecules (< 1.5 kDa) in complex biological samples to characterize the interaction between cellular metabolism and exogenous lifestyle exposures that determine health and quality of life. To fully access the diverse classes of biological molecules related to an individual’s metabolic profile, metabolomics frequently requires the use of complementary analytical platforms, and employs targeted and untargeted molecular profiling strategies to identify biomarkers that are clinically relevant to an individual’s health status. Chapter 2 describes a quinoline-based boronic acid biosensor for N-acetylneuraminic acid that undergoes a striking binding enhancement under strongly acidic conditions. For the first time, this work allows for direct analysis of acidic sugars with high selectivity when using UV absorbance or fluorescence detection based on formation of a highly stable boronate ester complex with metabolites containing an α-hydroxycarboxylate moiety. Chapter 3 describes a targeted analysis of 24 different organic contaminants using GC-MS that can serve as biomarkers of recent smoke exposure following search-and-rescue training exercises by firefighters located at three different sites across the province of Ontario. Importantly, skin and possible respiratory uptake of various polycyclic aromatic hydrocarbons, methoxyphenols, and resin acids was confirmed by peak excretion of several wood smoke biomarkers in urine within 6 h following acute exposure. Chapter 4 applied a cross-platform metabolomics strategy based on CE-MS and GC-MS in order to identify and validate dietary biomarkers in matching plasma and urine samples collected from healthy participants in the pilot Diet and Gene Interaction Study (DIGEST). For the first time, we demonstrate that a panel of metabolites can serve as reliable biomarkers following contrasting Prudent and Western diets over 2 weeks of food provisions, which correlated well with self-reported diet records. This work paves the way for the development of objective biomarkers for accurate assessment of wood smoke exposures, as well as complex dietary patterns as required for new advances in occupational health and nutritional epidemiology. / Dissertation / Doctor of Philosophy (PhD) / Exposomics is an emerging multidisciplinary science aimed at deciphering the complex interactions that impact human health and gene expression, such as lifestyle choices (i.e., habitual diet) and lifelong environmental exposures. There is growing interest in identifying biomarkers that can be readily measured for chronic disease prevention given an alarming global prevalence of obesity and cardiometabolic disorders, including heart disease, type 2 diabetes and cancer. The research in this thesis focuses on developing new analytical methods for identifying and quantifying metabolites that may allow for better assessments of human health, and has contributed to the development of novel biosensors for the targeted analysis of N-acetylneuraminic (sialic) acid and related acidic sugars, as well as high resolution methods for broad spectrum analysis of biotransformed organic contaminants from smoke exposure by GC-MS, and plasma and urinary metabolites that differentiate contrasting Prudent and Western diets and correlate well with self-reported diet records.