Molecular composition of biogenic secondary organic aerosols using ultrahigh resolution mass spectrometry: comparing laboratory and field studies

Numerous laboratory experiments have been performed in an attempt to mimic atmospheric secondary organic aerosol (SOA) formation. However, it is still unclear how close the aerosol particles generated in laboratory experiments resemble atmospheric SOA with respect to their detailed chemical composition. In this study, we generated SOA in a simulation chamber from the ozonolysis of α-pinene and a biogenic volatile organic compound (BVOC) mixture containing α- and β-pinene, Δ3-carene, and isoprene. The detailed molecular composition of laboratory-generated SOA was compared with that of background ambient aerosol collected at a boreal forest site (Hyytiälä, Finland) and an urban location (Cork, Ireland) using direct infusion nanoelectrospray ultrahigh resolution mass spectrometry. Kendrick Mass Defect and Van Krevelen approaches were used to identify and compare compound classes and distributions of the detected species. The laboratory-generated SOA contained a distinguishable group of dimers that was not observed in the ambient samples. The presence of dimers was found to be less pronounced in the SOA from the VOC mixtures when compared to the one component precursor system. The elemental composition of the compounds identified in the monomeric region from the ozonolysis of both α-pinene and VOC mixtures represented the ambient organic composition of particles collected at the boreal forest site reasonably well, with about 70% of common molecular formulae. In contrast, large differences were found between the laboratory-generated BVOC samples and the ambient urban sample. To our knowledge this is the first direct comparison of molecular composition of laboratory-generated SOA from BVOC mixtures and ambient samples.

Health care and neoliberalism in Ireland: withholding the gift and corrupting the social contract

The health of a nation tells much about the nature of a social contract between citizen and state. The way that health care is organised, and the degree to which it is equitably accessible, constitutes a manifestation of the effects of moments and events in that country's history. Using four case studies, this thesis uses a historical genealogical approach to explain the evolution of Ireland's particular version of health care provision. The total social fact of the gift relationship, central to all human relations, will be used to form a theoretical and conceptual framework on which to build an analysis of Ireland's health and welfare conditions. Additionally, social contract theory will enable an examination of the role of solidarity in relation to social expectations around health care provision. Through the analysis of these cases, the complex matrix of the influential forces that have shaped current conditions are exposed and revealed, enabling a critical understanding of the extent of acquiescence to the inequitable system that arguably exists. The vulnerability of citizens in need of care to the external and global effects of market forces and neoliberalism, therefore, becomes central to any argument for state-provided health and welfare. The hegemony of such forces can be seen to influence the manner in which the idea of individual self-reliance, in place of collective solidarity, is conceptualised and subsequently infiltrated into a range of aspects of the social world. For example, the particular discourse of the market and of economic concerns succeeds in shaping understandings of responsibilities around central areas of health and welfare. Similarly the 'possessor principle' can be seen to be misplaced within the context of health and social care, but yet has become normalised within this discourse. Within this matrix of complex influencing factors, the welfare state struggles to impose a balance between market values and social values. Responsibilities of the state to support and compensate its citizens for the ills of the market have become devalued, as the core values of classical liberalism have become distorted beyond recognition, leaving instead bare neoliberal concerns. This thesis traces the genealogical origins of this transition within the recent history of Irish health care and thereby reveals the embedding of individualism in place of solidarity, the on going reneging of the social contract and the corruption of the gift relationship.