Long-term study of VOCs measured with PTR-MS at a rural site in New Hampshire with urban influences

Abstract. A long-term, high time-resolution volatile organic compound (VOC) data set from a ground site that experiences urban, rural, and marine influences in the Northeastern United States is presented. A proton-transfer-reaction mass spectrometer (PTR-MS) was used to quantify 15 VOCs: a marine tracer dimethyl sulfide (DMS), a biomass burning tracer acetonitrile, biogenic compounds (monoterpenes, isoprene), oxygenated VOCs (OVOCs: methyl vinyl ketone (MVK) plus methacrolein (MACR), methanol, acetone, methyl ethyl ketone (MEK), acetaldehyde, and acetic acid), and aromatic compounds (benzene, toluene, C₈ and C₉ aromatics). Time series, overall and seasonal medians, with 10th and 90th percentiles, seasonal mean diurnal profiles, and inter-annual comparisons of mean summer and winter diurnal profiles are shown. Methanol and acetone exhibit the highest overall median mixing ratios 1.44 and 1.02 ppbv, respectively. Comparing the mean diurnal profiles of less well understood compounds (e.g., MEK) with better known compounds (e.g., isoprene, monoterpenes, and MVK + MACR) that undergo various controls on their atmospheric mixing ratios provides insight into possible sources of the lesser known compounds. The constant diurnal value of ~0.7 for the toluene:benzene ratio in winter, may possibly indicate the influence of wood-based heating systems in this region. Methanol exhibits an initial early morning release in summer unlike any other OVOC (or isoprene) and a dramatic late afternoon mixing ratio increase in spring. Although several of the OVOCs appear to have biogenic sources, differences in features observed between isoprene, methanol, acetone, acetaldehyde, and MEK suggest they are produced or emitted in unique ways.