A photochemical trajectory model containing speciated emissions of 124 non-methane volatile organic compounds (VOC), and a comprehensive description of the chemistry of VOC degradation, has been used to simulate the chemical evolution of boundary layer air masses arriving at a field campaign site in the southern UK during a widespread and prolonged photochemical pollution event in August 2003. The simulated concentrations and distributions of organic compounds at the arrival location are compared with observations of a series of hydrocarbons and carbonyl compounds, which were measured using GC-FID and multidimensional GC methods. The comparison of the simulated and observed distributions of 34 emitted hydrocarbons provides some support for the magnitude and applied emissions speciation of anthropogenic hydrocarbons, but is indicative of an under representation of the input of biogenic hydrocarbons, particularly at elevated temperatures. Simulations of the detailed distribution of ca. 1250 carbonyl compounds, formed primarily from the degradation of the 124 emitted VOC, focus on 61 aldehydes, ketones, dicarbonyls, hydroxycarbonyls and aromatic aldehydes which collectively account for ca. 90% of the simulated total molar concentration of carbonyls. The simulated distributions indicate that the photolysis of formaldehyde and alpha-dicarbonyls make major contributions to free radical production for the arrival conditions of five case study trajectories. The simulated concentrations of hydroxycarbonyls demonstrate preferential formation of the 1,4-substituted isomers (compared with 1,2- and 1,3-isomers of the same carbon number), which are formed during the initial oxidation sequence of longer chain alkanes.