Thesis (M. Sc.)--York University, 2001. Graduate Programme in Chemistry. / Typescript. Includes bibliographical references (leaves 131-143). Also available on the Internet. MODE OF ACCESS via web browser by entering the following URL: http://wwwlib.umi.com/cr/yorku/fullcit?pMQ67748.

The deposition of atmospheric nitrogen is now recognized as a major driver of biodiversity changes at mid to high latitudes. It has previously been shown that regional variations in wet nitrogen deposition in the British Isles are reflected in broad targeted chemical parameters in the common heathland lichen Cladonia portentosa. A more detail analysis of alterations in the metabolic pathways in Cladonia portentosa collected from different locations within the UK was undertaken by applying the environmental metabolomics approach. Fourier transform infrared spectroscopy (FTIR) and liquid chromatography mass spectrometry (LC-MS) were applied in combination with principal component analysis (PCA) and partial least squares regression analysis (PLSR). The latter statistical method was used to correlate measured variables with modelled atmospheric data including wet nitrogen deposition, nitrogen concentration and precipitation. While FTIR in combination with PCA and PLSR revealed signatures of broad metabolic classes, LC-MS in combination with PCA and PLSR allowed the identification of betaine lipids (BL) as potential biomarkers of nitrogen enrichment. A compound tentatively identified as monoacylglycerol-(N,N,N trimethyl)-homoserine (MGTS) showed the strongest positive relation to increasing wet nitrogen deposition regimes and consequent phosphorus deficiency. In contrast, the structurally related phosphatidylcholine containing a C18:2 ester showed the opposite trend in natural populations of C. portentosa. Results obtained for C. portentosa collected from the N manipulation site Whim Moss indicated that ammonium is causal for the increase of two of the identified betaine lipids in natural populations in C. portentosa. Betaine lipids as well as the phosphatidylcholine biomarker could potentially be used to monitor nitrogen regimes and resulting phosphorus limitation on the lichen C. portentosa. The approach used for this study represented an effective integration of the complementary analytical techniques of FTIR and LC-MS in combination with multivariate statistical tools for environmental metabolomic studies.

Most undisturbed peatlands sequester carbon, and rising levels of atmospheric nitrogen deposition may have the potential to destabilize this function, possibly resulting in an increased release of carbon dioxide into the atmosphere.  It is therefore of vital importance to investigate further the link between atmospheric nitrogen deposition and carbon dynamics in exposed ecosystems such as peatlands. The work described in this thesis aimed to elucidate the impact of increasing nitrogen on aspects of carbon turnover in peatlands.  Using a long-term field-based experiment, I tested the effects of 4 years of ammonium and nitrate addition (8, 24 and 56 kg N ha^-1 y^-1) on the fate of newly photosynthesised carbon by plants and the turnover of labile and recalcitrant carbon.  A second set of experiments undertaken in the laboratory assessed the use of plant wax analysis as potential biomarkers of past changes in vegetation and carbon status in peat. Overall, this work has shown that the form of nitrogen (ammonium versus nitrate) is a crucial component of atmospheric pollution and must be taken into consideration when investigating or predicting effects of reactive nitrogen on peatlands.  In addition, nitrogen addition affected the fate of newly synthesised carbon differently in <i>Eriophorum vaginatum </i>and <i>Calluna vulgaris, </i>revealing the importance of considering plant traits when investigating environmental changes in terrestrial ecosystems.  Furthermore, it has led to the development of an investigative tool for further exploration of the historical effects of atmospheric nitrogen deposition on vegetation an carbon content in peatlands.

Various epidemiological studies have linked exposure to Ultrafine Particles (UFP; diameter< 100 nm) to adverse health impacts. Roadway traffic is one of the major sources of UFPs and heavily influences UFP concentrations in the nearby vicinity of major roadways. Modeling efforts to predict UFPs have been limited due to the scarcity of reliable information on emissions, lack of monitoring data and limited understanding of complex processes affecting UFP concentrations near sources. In this study continuous measurement of ultrafine particle number concentrations (PNC) and mass concentrations of nitric oxide (NO), nitrogen dioxide (NO2) and PM2.5 was conducted near an arterial road and freeway at different seasons and meteorological conditions and integrated with traffic count data. PNC showed high correlation with NO (r=0.64 for arterial; 0.61 for freeway), NO2 (r=0.57 for arterial; 0.53 for freeway) and NOx (NOx=NO+NO2; r=0.63 for arterial; 0.59 for freeway) and moderate to low correlation with traffic volume (r=0.33 for arterial; 0.32 for freeway) and PM2.5 (r=0.28 for arterial; 0.23 for freeway); respectively; for both sites at 15 minute averages. The PNC-NOx relationship prevailed on a shorter term (15 min), hourly, and throughout the day basis. Both PNC and NOx showed comparatively higher correlation with traffic during the morning period but became lower during evening which can be attributed to the higher boundary layer and wind speeds. The variable meteorology in the evening affects both PNC and NOx concentrations in the same way and the correlation between NOx and PNC is maintained high both during morning (r=0.74 for arterial; 0.69 for freeway), and evening (r=0.62 for arterial; 0.59 for freeway) periods. Thus nitrogen oxides can be used as a proxy for traffic-related UFP number concentration reflecting the effect of both traffic intensity and meteorological dilution. The PNC-NOx relation was explored for various meteorological parameters i.e. wind speed and temperature. It is found that NOx emission is temperature independent and can be used to reflect the effect of traffic intensity and meteorological dilution. Once the effect of traffic intensity and dilution is removed, the effect of temperature on PNC-NOx ratio becomes important which can be attributed to the variation in PNC emission factors with temperature. The high morning PNC-NOx ratio found at the arterial road is a result of new particle formation due to lower temperature and low concentration of exhaust gases in the morning air favoring nucleation over condensation. This finding has important implication when calculating emission factors for UFP number concentrations. Thus it can be concluded that roadside concentration of ultrafine particles not only depends on traffic intensity but also on meteorological parameters affecting dilution or new particle formation. High concentrations of ultrafine particle number concentration close to a roadway is expected due to higher traffic intensity , as well as during low wind speed causing low dilution and low temperature conditions favoring new particle formation. Finally a simplified approach of calculating particle number emission factor was developed using existing and easily available emission inventory for traffic related tracer gases. Using NOx emission factors from MOVES emission model, the emission ratio of PNC to NOx was converted to develop particle number emission factors. NOx was selected as the traffic related tracer gas since the number concentration of particles is closely correlated to NOx, NOx and particles are diluted in the same way and NOx emission factors are available for a variety of traffic situations. To ensure contribution of fresh traffic exhaust, the average of the difference of pollutant concentrations at high traffic condition and background condition was used to calculate PNC-NOX ratio. Using nitrogen oxides to define background and high-traffic conditions and MOVES emission factor for NOX to convert corresponding PNC-NOX ratio, an average emission factor of (1.82 ± 0.17) E+ 14 particle/ vehicle-km was obtained, suitable for summertime. When compared to existing particle number emission factors derived from dynamometer tests, it was found that there exits reasonable agreement between the calculated real world particle number emission factors and emission factors from dynamometer tests. The calculated emission factor and R-Line dispersion model was tested in predicting near-road particle number concentrations. Although only 23% of the variability in PNC was explained by the dispersion model, 84.33% of the measurements fell within the factor of two envelope. This suggests that there is potential to effectively use these models and thus warrants more in-depth analysis. Finally, a simple map of PNC gradients from major roads of Portland was developed. The results of this study helped identify proxy-indicators to provide reference values for estimating UFP concentrations and emissions that can be used for simple evaluation of particle concentration near major roadways for environmental and urban planning purposes and to assess expected impact of UFP pollution on population living near roadways exposed to elevated concentrations.

Thesis (Ph. D.)--University of Nevada, Reno, 2008. / "December, 2008." Includes bibliographical references. Online version available on the World Wide Web.