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.

Toward autonomous measurements of photosynthetic electron transport rates: An evaluation of active fluorescence-based measurements of photochemistry

This study presents a methods evaluation and intercalibration of active fluorescence-based measurements of the quantum yield ( inline image) and absorption coefficient ( inline image) of photosystem II (PSII) photochemistry. Measurements of inline image, inline image, and irradiance (E) can be scaled to derive photosynthetic electron transport rates ( inline image), the process that fuels phytoplankton carbon fixation and growth. Bio-optical estimates of inline image and inline image were evaluated using 10 phytoplankton cultures across different pigment groups with varying bio-optical absorption characteristics on six different fast-repetition rate fluorometers that span two different manufacturers and four different models. Culture measurements of inline image and the effective absorption cross section of PSII photochemistry ( inline image, a constituent of inline image) showed a high degree of correspondence across instruments, although some instrument-specific biases are identified. A range of approaches have been used in the literature to estimate inline image and are evaluated here. With the exception of ex situ inline image estimates from paired inline image and PSII reaction center concentration ( inline image) measurements, the accuracy and precision of in situ inline image methodologies are largely determined by the variance of method-specific coefficients. The accuracy and precision of these coefficients are evaluated, compared to literature data, and discussed within a framework of autonomous inline image measurements. This study supports the application of an instrument-specific calibration coefficient ( inline image) that scales minimum fluorescence in the dark ( inline image) to inline image as both the most accurate in situ measurement of inline image, and the methodology best suited for highly resolved autonomous inline image measurements.