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The depletion of fossil fuel resources, pollution concerns and the challenge of energy security are driving the search for renewable energy sources. The use of lignocellulosic plant biomass as an energy source is increasing in the United Kingdom and worldwide. In the UK, up to 0.35MHa (6% of total arable land) may be planted with perennial bioenergy crops by 2020 in order to meet renewable energy and CO2 reduction targets. Several plant species that produce high biomass from low inputs have been identified. The most promising for the UK climate are the genus Miscanthus, a perennial rhizomatous grass which can grow up to 3.5m in a year, and short rotation coppice (SRC) willow (Salix spp.), plantations of which can remain viable for up to 30 years. Although bioenergy crops are perceived as “carbon neutral”, changes in land use can have a wider impact on atmospheric composition than through CO2 alone. This study compares vegetation fluxes of methyl halides (CH3Br and CH3Cl) and biogenic volatile organic compounds (BVOCs) from perennial bioenergy crops and annual arable crops at three sites in the UK. Methyl halides are the most abundant natural vectors of bromine and chlorine into the stratosphere and play an important role in stratospheric ozone destruction. BVOCs affect atmospheric oxidising capacity and are a major precursor to the formation of ozone and secondary organic aerosols in the troposphere. Although terrestrial vegetation is an important source of these trace gases there are very few previous measurements of these reactive gases from bioenergy crops. This study describes measurements conducted at two SRC willow sites in Scotland, and one site in England planted with adjacent perennial bioenergy crops and annual arable crops, to quantify and characterise natural methyl halide and BVOC fluxes from vegetation. Measurements were conducted with branch chambers, using static enclosure techniques to measure methyl halide fluxes and dynamic enclosures to measure BVOCs such as isoprene and -pinene. Fluxes were calculated from the concentration difference between background/inlet samples and after enclosure/outlet samples. Methyl halide concentrations were determined by sampling gas from static enclosures followed by analysis using an oxygen-doped GC-ECD with a custom-built pre-concentration unit. Samples for BVOC analysis were collected onto adsorbent tubes and a thermal desorption GC-MS was used to determine BVOC concentrations. Potentially influential environmental variables such as photosynthetically active radiation (PAR), total solar radiation, air temperature, soil temperature, internal chamber temperature and soil moisture were recorded in parallel to the enclosures to determine their potential relationships to fluxes. Long-term environmental data was also available from on-site or nearby weather stations. Long-term measurements were carried out for 2 1 2 years at a site in Lincolnshire, England where adjacent fields are planted with Miscanthus, SRC willow and annual arable crops (wheat and oilseed rape crop rotation). Vegetation measurements were made almost every month throughout the period, with more intensive measurements such as full diurnal cycle carried out during the summer. Ten sampling points are sampled in each field and semi-diurnal measurements are taken regularly. Long-term measurements were also carried out at two sites in Scotland planted with SRC willow, one in Arnot, Perth & Kinross which was sampled for a year and one in East Grange, Fife which was sampled for half a year. Up to 30 sampling points were employed in Arnot and another 10 in East Grange. The bioenergy crops and wheat emitted low fluxes of methyl halides in comparison to the oilseed rape. Mean annual net fluxes of CH3Br and CH3Cl from Miscanthus were 1.8 ng g (dry weight)-1 h-1 and 11 ng g-1 h-1, respectively. At the three willow sites, mean annual net fluxes of CH3Br and CH3Cl ranged between 0.6 - 1.7 ng g-1 h-1, and 1.7 - 12 ng g-1 h-1, respectively. Negligible fluxes of methyl halides were measured from wheat but oilseed rape was found to emit large fluxes of methyl halides with mean annual net fluxes of CH3Br and CH3Cl of 20 ng g-1 h-1and 144 ng g-1 h-1, respectively. The largest BVOC fluxes were measured from SRC willow at the Brattleby site, with high mean annual net fluxes of isoprene (77 μ g g-1 h-1), α -pinene (46 g μg-1 h-1), β -pinene (5.5 μ g g-1 h-1), limonene (3.7 μ g g-1 h-1) and δ -3-carene (11 μ g g-1 h-1). However, mean annual net BVOC fluxes measured at Arnot and East Grange were much lower. High fluxes of - pinene were measured from Miscanthus in 2010 (giving a mean annual net flux of 65 μ g g-1 h-1) but no other significant BVOC fluxes were distinguished. Negligible fluxes of isoprene were measured from wheat but fluxes of monoterpenes were high with mean annual net fluxes of 65 μ g g-1 h-1 and 25 μg g-1 h-1 for α -pinene and limonene, respectively. No significant fluxes of BVOCs were measured from the oilseed rape. All fluxes demonstrated a strong seasonal trend with higher emissions during the summer growing season and low to zero emissions over winter. The high spatial variability was captured by sampling from many points in each field. Some diurnal measurements exhibited a clear pattern of higher emissions during the day and low to zero emissions at night. Some positive correlations between fluxes and environmental variables such as PAR and air temperature were observed. An experiment carried out on willow cuttings in the greenhouse found no clear increase or decrease in fluxes of BVOCs in response to N fertiliser treatment, instead fluxes were found to vary significantly with some of the observed environmental variables. UK estimates were derived by extrapolating measured fluxes using the current respective land cover areas for Miscanthus and SRC willow. Estimated UK annual fluxes of CH3Br and CH3Cl from Miscanthus were 0.01Mgy-1 and 0.05Mgy-1, respectively and from SRC willow were 0.06Mgy-1 and 0.4Mgy-1, respectively, accounting for a very small percentage of total global annual turnover of CH3Br and CH3Cl. Estimated UK annual fluxes of the BVOCs isoprene and α -pinene from Miscanthus were 0.01Mgy-1 and 0.4Mgy-1, respectively and from SRC willow were 3Mgy-1 and 1Mgy-1, respectively. Future planting of SRC willow to meet the UKs energy needs could lead to a potential annual isoprene flux of 150 MgMgy-1.

Convertional methods for the synthesis of biaryl compounds Involve free radicals as intermediates and,in the case where unsymmetrLeal biaryls are desired,give rise to mixtures of products. A more elegant, and certainly more specific, approach would be to define the site oE substitution on the aryl substrate by suitably positioned electron-withdrawing substituents for attack by an aryl anion. Generation of the latter by using aryl lithium compounds, and their use as partners in coupling reactions with aryl halides formed the basis of this study. As the literature on organolithium chemistry is highly controversial and confusing, the present study initially involved a thorough investigation of the reactions of aryl halides with various organolithium reagents. It was found that the aryl halides could couple with themselves after metal - halogen exchange to give rise to biaryl and t n a r y 1 products. The reaction explored most fully was that between 2,4,6-tnbromophenol and methyl1ithium. The effects of varying the nature of the substituents and their position on the aromatic ring were also investigated. When the para substituents on a series of brominated phenol derivatives were varied through -F, -Cl, -Br, -H, am. -CH^, it was found that as the substituent became more electron-withdrawing the yield of biaryl product trom the reaction increased. In a parallel series of reactions, the hydioxyl group of the substrate was replaced by -OCH^, -CHj, -H and -Br. Biaryl products were then obtained only from those brominated aromatic compounds containing substituents capable of metal - hydrogen exchange. These results led to more specific reactions to clarify various points of mechanism and to the proposal that the aryl lithium species resulting from metal - halogen exchange may exist as dimers in solution. Two types of dimers are postulated to occi one type which collapses via an ionic pathway with elimination of lithium halide to form a biaryl product, and a second type of dimer which yields a biaryl product via a radical pathway with the concomitant and transient production of lithium metal. Evidence for the existence of both pathways is presented. Finally, applications of the results of this research were studied. Several avenues to the syntheris of a cannabinol analogue related to the constituents of Cannabis sativa were pursued but this target remained elusive. Other unsymmetrical biaryl compounds were howevei prepared in yields comparable to those quoted in the literature (usually by different methods) and a successful instance of "ionic " steering ot an ionic pathway for such a reaction was realized.

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Thesis (Ph. D.)--Institute of Paper Chemistry, 1965. / Includes bibliographical references (p. 116-119).

published_or_final_version / Chemistry / Master / Master of Philosophy

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