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.

Technical Note: Ensuring consistent, global measurements of short-lived halocarbon gases in the ocean and atmosphere

Very short-lived halocarbons are significant sources of reactive halogen in the marine boundary layer, and likely in the upper troposphere and lower stratosphere. Quantifying ambient concentrations in the surface ocean and atmosphere is essential for understanding the atmospheric impact of these trace gas fluxes. Despite the body of literature increasing substantially over recent years, calibration issues complicate the comparison of results and limit the utility of building larger-scale databases that would enable further development of the science (e.g. sea-air flux quantification, model validation, etc.). With this in mind, thirty-one scientists from both atmospheric and oceanic halocarbon communities in eight nations gathered in London in February 2008 to discuss the scientific issues and plan an international effort toward developing common calibration scales (http://tinyurl.com/c9cg58). Here, we discuss the outputs from this meeting, suggest the compounds that should be targeted initially, identify opportunities for beginning calibration and comparison efforts, and make recommendations for ways to improve the comparability of previous and future measurements.

Space-based lidar measurements of global ocean carbon stocks

Global ocean phytoplankton biomass (C-phyto) and total particulate organic carbon (POC) stocks have largely been characterized from space using passive ocean color measurements. A space-based light detection and ranging (lidar) system can provide valuable complementary observations for C-phyto and POC assessments, with benefits including day-night sampling, observations through absorbing aerosols and thin cloud layers, and capabilities for vertical profiling through the water column. Here we use measurements from the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) to quantify global C-phyto and POC from retrievals of subsurface particulate backscatter coefficients (b(bp)). CALIOP b(bp) data compare favorably with airborne, ship-based, and passive ocean data and yield global average mixed-layer standing stocks of 0.44 Pg C for C-phyto and 1.9 Pg for POC. CALIOP-based C-phyto and POC data exhibit global distributions and seasonal variations consistent with ocean plankton ecology. Our findings support the use of spaceborne lidar measurements for advancing understanding of global plankton systems.