Temporal patterns, sources, and sinks of C₈-C₁₆ hydrocarbons in the atmosphere of Mace Head, Ireland

During the 1999 New Particle Formation and Fate in the Coastal Environment (PARFORCE) field campaign, 16 C₈-C₁₆ volatile organic compounds (VOCs) were identified in the coastal atmosphere of Mace Head, Ireland. Sampling took place over 24 days, with 12 VOCs routinely quantified. Concentrations were observed in the low <10-150 parts per trillion by volume range, with levels typically in the order of aldehydes > ketones ≥ n-alkanes. Concentrations of these compounds were also measured in shoreline surface seawater. No relationship was observed between atmospheric concentrations and high/low tide events. Many VOCs revealed a temporal pattern in the atmosphere, with highest concentrations measured during the early morning and lowest concentrations in the afternoon. The strongest pattern was observed for the n-alkanes. However, this was dependent on the prevailing air mass direction and the local meteorology. A Lagrangian box model was applied to assess this diurnal cycle, using seawater emissions as a source (based on the seawater concentrations and observed wind speeds), and depletion via OH radicals and dilution by entrainment as sinks (using measured [OH] and boundary layer height data). The model gave good agreement to the observed concentrations for selected air mass types, predicting the daytime decrease in VOC concentrations due to OH radical chemistry and boundary layer growth, and the subsequent increase in VOC concentrations toward evening as both oxidation chemistry diminished and the mixing layer height fell.