Measurements of OVOC fluxes by eddy covariance using a proton-transfer-reaction mass spectrometer – method development at a coastal site

We present here vertical fluxes of oxygenated volatile organic compounds (OVOCs) measured with eddy covariance (EC) during the period of March to July 2012 near the southwest coast of the United Kingdom. The performance of the proton-transfer-reaction mass spectrometer (PTR-MS) for flux measurement is characterized, with additional considerations given to the homogeneity and stationarity assumptions required by EC. Observed mixing ratios and fluxes of OVOCs (specifically methanol, acetaldehyde, and acetone) vary significantly with time of day and wind direction. Higher mixing ratios and fluxes of acetaldehyde and acetone are found in the daytime and from the direction of a forested park, most likely due to light-driven emissions from terrestrial plants. Methanol mixing ratio and flux do not demonstrate consistent diel variability, suggesting sources in addition to plants. We estimate air-sea exchange and photochemical rates of these compounds, which are compared to measured vertical fluxes. For acetaldehyde, the mean (1 sigma) mixing ratio of 0.13 (0.02) ppb at night may be maintained by oceanic emission, while photochemical destruction out-paces production during the day. Air-sea exchange and photochemistry are probably net sinks of methanol and acetone in this region. Their nighttime mixing ratios of 0.46 (0.20) and 0.39 (0.08) ppb appear to be affected more by terrestrial emissions and long-distance transport, respectively.

Transfer Across the Air-Sea Interface

The efficiency of transfer of gases and particles across the air-sea interface is controlled by several physical, biological and chemical processes in the atmosphere and water which are described here (including waves, large- and small-scale turbulence, bubbles, sea spray, rain and surface films). For a deeper understanding of relevant transport mechanisms, several models have been developed, ranging from conceptual models to numerical models. Most frequently the transfer is described by various functional dependencies of the wind speed, but more detailed descriptions need additional information. The study of gas transfer mechanisms uses a variety of experimental methods ranging from laboratory studies to carbon budgets, mass balance methods, micrometeorological techniques and thermographic techniques. Different methods resolve the transfer at different scales of time and space; this is important to take into account when comparing different results. Air-sea transfer is relevant in a wide range of applications, for example, local and regional fluxes, global models, remote sensing and computations of global inventories. The sensitivity of global models to the description of transfer velocity is limited; it is however likely that the formulations are more important when the resolution increases and other processes in models are improved. For global flux estimates using inventories or remote sensing products the accuracy of the transfer formulation as well as the accuracy of the wind field is crucial.