Measurement of stable carbon isotope ratios of non-methane hydrocarbons and halocarbons

Within the realm of volatile organic compounds, hydrocarbons and halocarbons form a sizable proportion of carbon input to the atmosphere. Within these compound categories, the light non-methane hydrocarbons (NMHC, two to seven carbon atoms) and monocarbon halocarbons have a special place as these have strong, if not exclusive, anthropogenic (human-caused) sources. With common atmospheric molar mixing ratios in the parts-per-trillion (10-12 mole/mole) to parts-per-billion (10-9 mole/mole) range, these trace gases, though decidedly minor constituants of the atmosphere, have diverse consequences due to their atmospheric presence and their removal processes. Effects range from causing ground level air pollution and resulting hazards to health, to contributing to anthropogenic climate change and the destruction of the ozone layer in the stratosphere, among many others. The existance of stable isotopes (otherwise identical atoms with varying amounts of neutrons that do not spontaneously disintegrate) in several elements relevant to atmospheric chemistry and physics is a boon to research. Their presence in molecules is detectable by mass and cause small intra- and intermolecular property changes. These changes range from the physical (e.g. boiling point variation) to the chemical (reaction rate variation) and can influence external interactions as well. The measurement of the ratio of a minor stable isotope of an element to the major one (the stable isotope ratio) can be used to establish source fingerprints, trace the interaction dynamics, and refine the understanding of the relative contribution of sources and sinks to the atmosphere as a whole. The stable minor stable isotope of carbon, 13C, has a natural abundance of approximately 1.1 %. It has a sufficient fractional mass difference from its major isotope as to cause significant effects, making it ideal for measuring the ratios and properties of hydro- and halocarbons. In order to enable a better understanding of the behavior of these compounds in terms of their sources, sinks, inter- and intramolecular processes, it was decided in 2006 to develop an instrument capable of selectively measuring NMHC mixing ratios and stable carbon isotope ratios for use in the laboratory of the Atmospheric Physics and Chemistry Group at Universiteit Utrecht. This thesis documents the successful development, construction, testing and first applications of this stable carbon isotope ratio instrument. It is divided into five chapters, representing the content of three publications and additional material: an introduction; a method section; and applications: analysis of NMHC stable carbon isotopes in urban ambient air, laboratory measurments of the isotope effects in UV degradation of monocarbon chlorofluorocarbons, isotope analysis of diverse gases from firn air samples from Greenland, plus a section on future perspective