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

Vertical fluxes and atmospheric cycling of methanol, acetaldehyde, and acetone in a coastal environment

We present here vertical fluxes of methanol, acetaldehyde, and acetone measured directly with eddy covariance (EC) during March to July 2012 near the southwest coast of the UK. 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. Concentrations and fluxes of these compounds vary significantly with time of day and wind direction. Higher values of acetaldehyde and acetone are usually observed in the daytime and from the direction of a forested park, most likely due to light-driven emissions from terrestrial plants. Methanol concentration and flux do not demonstrate clear 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�) concentration of 0.13 (0.02) ppb at night may be maintained by oceanic emission, while photochemical destruction outpaces production during the day. Air-sea exchange and photochemistry are probably net sinks of methanol and acetone in this region. Their nighttime concentrations of 0.46 (0.20) and 0.39 (0.08) ppb appear to be affected more by terrestrial emissions and long distance transport, respectively

Lagrangian evolution of DMS during the Southern Ocean gas exchange experiment: The effects of vertical mixing and biological community shift

Concentrations of dimethylsulfide (DMS) and its precursor dimethylsulfoniopropionate (DMSP) are highly variable in time and space. What is driving the variability in DMS(P), and can those variability be explained by physical processes and changes in the biological community? During the Southern Ocean Gas Exchange Experiment (SO GasEx) in the austral fall of 2008, two 3He/SF6 labeled patches were created in the surface water. SF6 and DMS were surveyed continuously in a Lagrangian framework, while direct measurements of air-sea exchange further constrained the gas budgets. Turbulent diffusivity at the base of the mixed layer was estimated from SF6 profiles and used to calculate the vertical fluxes of DMS and nutrients. Increasing mixed layer nutrient concentrations due to mixing were associated with a shift in the phytoplankton community structure, which in turned likely affected the sulfur dynamics on timescales of days. DMS concentration as well as air-sea DMS flux appeared to be decoupled from the DMSP concentration, possibly due to grazing and bacterial DMS production. Contrary to expectations, in an environment with high winds and modest productivity, physical processes (air-sea exchange, photochemistry, vertical mixing) only accounted for a small fraction of DMS loss from the surface water. Among the DMS sinks, inferred biological consumption most likely dominated during SO GasEx

Air-sea transfer of gas phase controlled compounds

Gases in the atmosphere/ocean have solubility that spans several orders of magnitude. Resistance in the molecular sublayer on the waterside limits the air-sea exchange of sparingly soluble gases such as SF6 and CO2. In contrast, both aerodynamic and molecular diffusive resistances on the airside limit the exchange of highly soluble gases (as well as heat). Here we present direct measurements of air-sea methanol and acetone transfer from two open cruises: the Atlantic Meridional Transect in 2012 and the High Wind Gas Exchange Study in 2013. The transfer of the highly soluble methanol is essentially completely airside controlled, while the less soluble acetone is subject to both airside and waterside resistances. Both compounds were measured concurrently using a proton-transfer-reaction mass spectrometer, with their fluxes quantified by the eddy covariance method. Up to a wind speed of 15 m s-1, observed air-sea transfer velocities of these two gases are largely consistent with the expected near linear wind speed dependence. Measured acetone transfer velocity is ~30% lower than that of methanol, which is primarily due to the lower solubility of acetone. From this difference we estimate the "zero bubble" waterside transfer velocity, which agrees fairly well with interfacial gas transfer velocities predicted by the COARE model. At wind speeds above 15 m s-1, the transfer velocities of both compounds are lower than expected in the mean. Air-sea transfer of sensible heat (also airside controlled) also appears to be reduced at wind speeds over 20 m s-1. During these conditions, large waves and abundant whitecaps generate large amounts of sea spray, which is predicted to alter heat transfer and could also affect the air-sea exchange of soluble trace gases. We make an order of magnitude estimate for the impacts of sea spray on air-sea methanol transfer

Air-Sea Exchange of Biogenic Volatile Organic Compounds and the Impact on Aerosol Particle Size Distributions

We report simultaneous, underway eddy covariance measurements of the vertical flux of isoprene, total monoterpenes, and dimethyl sulfide (DMS) over the Northern Atlantic Ocean during fall. Mean isoprene and monoterpene sea-to-air vertical fluxes were significantly lower than mean DMS fluxes. While rare, intense monoterpene sea-to-air fluxes were observed, coincident with elevated monoterpene mixing ratios. A statistically significant correlation between isoprene vertical flux and short wave radiation was not observed, suggesting that photochemical processes in the surface microlayer did not enhance isoprene emissions in this study region. Calculations of secondary organic aerosol production rates (PSOA) for mean isoprene and monoterpene emission rates sampled here indicate that PSOA is on average <0.1 μg m−3 d−1. Despite modest PSOA, low particle number concentrations permit a sizable role for condensational growth of monoterpene oxidation products in altering particle size distributions and the concentration of cloud condensation nuclei during episodic monoterpene emission events from the ocean

Atmospheric deposition of methanol over the Atlantic Ocean

In the troposphere, methanol (CH3OH) is present ubiquitously and second in abundance among organic gases after methane. In the surface ocean, methanol represents a supply of energy and carbon for marine microbes. Here we report direct measurements of air-sea methanol transfer along a similar to 10,000-km north-south transect of the Atlantic. The flux of methanol was consistently from the atmosphere to the ocean. Constrained by the aerodynamic limit and measured rate of air-sea sensible heat exchange, methanol transfer resembles a one-way depositional process, which suggests dissolved methanol concentrations near the water surface that are lower than what were measured at similar to 5 m depth, for reasons currently unknown. We estimate the global oceanic uptake of methanol and examine the lifetimes of this compound in the lower atmosphere and upper ocean with respect to gas exchange. We also constrain the molecular diffusional resistance above the ocean surface-an important term for improving air-sea gas exchange models

Whitecap coverage dependence on wind and wave statistics as observed during SO GasEx and HiWinGS

Concurrent wavefield and turbulent flux measurements acquired during the Southern Ocean (SO) Gas Exchange (GasEx) and the High Wind Speed Gas Exchange Study (HiWinGS) projects permit evaluation of the dependence of the whitecap coverage W on wind speed, wave age, wave steepness, mean square slope, and wind-wave and breaking Reynolds numbers. The W was determined from over 600 high-frequency visible imagery recordings of 20 min each. Wave statistics were computed from in situ and remotely sensed data as well as from a WAVEWATCH III hindcast. The first shipborne estimates of W under sustained 10-m neutral wind speeds U10N of 25 m s−1 were obtained during HiWinGS. These measurements suggest that W levels off at high wind speed, not exceeding 10% when averaged over 20 min. Combining wind speed and wave height in the form of the wind-wave Reynolds number resulted in closely agreeing models for both datasets, individually and combined. These are also in good agreement with two previous studies. When expressing W in terms of wavefield statistics only or wave age, larger scatter is observed and/or there is little agreement between SO GasEx, HiWinGS, and previously published data. The wind speed–only parameterizations deduced from the SO GasEx and HiWinGS datasets agree closely and capture more of the observed W variability than Reynolds number parameterizations. However, these wind speed–only models do not agree as well with previous studies than the wind-wave Reynolds numbers

Wave‐Related Reynolds Number Parameterizations of CO₂ and DMS Transfer Velocities

Predicting future climate hinges on our understanding of and ability to quantify air‐sea gas transfer. The latter relies on parameterizations of the gas transfer velocity k, which represents physical mass transfer mechanisms and is usually parameterized as a nonlinear function of wind forcing. In an attempt to reduce uncertainties in k, this study explores empirical parameterizations that incorporate both wind speed and sea state dependence via wave‐wind and breaking Reynolds numbers, RH and RB. Analysis of concurrent eddy covariance gas transfer and measured wavefield statistics supplemented by wave model hindcasts shows for the first time that wave‐related Reynolds numbers collapse four open ocean data sets that have a wind speed dependence of CO₂ transfer velocity ranging from lower than quadratic to cubic. Wave‐related Reynolds number and wind speed show comparable performance for parametrizing dimethyl sulfide (DMS) which, because of its higher solubility, is less affected by bubble‐mediated exchange associated with wave breaking

Global Synthesis of Air-Sea CO2 Transfer Velocity Estimates From Ship-Based Eddy Covariance Measurements

The air-sea gas transfer velocity (K660) is typically assessed as a function of the 10-m neutral wind speed (U10n), but there remains substantial uncertainty in this relationship. Here K660 of CO2 derived with the eddy covariance (EC) technique from eight datasets (11 research cruises) are reevaluated with consistent consideration of solubility and Schmidt number and inclusion of the ocean cool skin effect. K660 shows an approximately linear dependence with the friction velocity (u*) in moderate winds, with an overall relative standard deviation (relative standard error) of about 20% (7%). The largest relative uncertainty in K660 occurs at low wind speeds, while the largest absolute uncertainty in K660 occurs at high wind speeds. There is an apparent regional variation in the steepness of the K660-u* relationships: North Atlantic ≥ Southern Ocean > other regions (Arctic, Tropics). Accounting for sea state helps to collapse some of this regional variability in K660 using the wave Reynolds number in very large seas and the mean squared slope of the waves in small to moderate seas. The grand average of EC-derived K660 ( − 1:47 + 76:67u* + 20:48u2 * or 0:36 + 1:203U10n + 0:167U2 10n) is similar at moderate to high winds to widely used dual tracer-based K660 parametrization, but consistently exceeds the dual tracer estimate in low winds, possibly in part due to the chemical enhancement in air-sea CO2 exchange. Combining the grand average of EC-derived K660 with the global distribution of wind speed yields a global average transfer velocity that is comparable with the global radiocarbon (14C) disequilibrium, but is ~20% higher than what is implied by dual tracer parametrizations. This analysis suggests that CO2 fluxes computed using a U2 10n dependence with zero intercept (e.g., dual tracer) are likely underestimated at relatively low wind speeds

Wind Speed and Sea State Dependencies of Air-Sea Gas Transfer: Results From the High Wind Speed Gas Exchange Study (HiWinGS)

A variety of physical mechanisms are jointly responsible for facilitating air-sea gas transfer through turbulent processes at the atmosphere-ocean interface. The nature and relative importance of these mechanisms evolves with increasing wind speed. Theoretical and modeling approaches are advancing, but the limited quantity of observational data at high wind speeds hinders the assessment of these efforts. The HiWinGS project successfully measured gas transfer coefficients (k660) with coincident wave statistics under conditions with hourly mean wind speeds up to 24 m s−1 and significant wave heights to 8 m. Measurements of k660 for carbon dioxide (CO2) and dimethylsulfide (DMS) show an increasing trend with respect to 10-meter neutral wind speed (U10N), following a power-law relationship of the form: math formula and math formula. Among seven high wind speed events, CO2 transfer responded to the intensity of wave breaking, which depended on both wind speed and sea state in a complex manner, with k660 co2 increasing as the wind sea approaches full development. A similar response is not observed for DMS. These results confirm the importance of breaking waves and bubble injection mechanisms in facilitating CO2 transfer. A modified version of the Coupled Ocean-Atmosphere Response Experiment Gas transfer algorithm (COAREG ver. 3.5), incorporating a sea state-dependent calculation of bubble-mediated transfer, successfully reproduces the mean trend in observed k660 with wind speed for both gases. Significant suppression of gas transfer by large waves was not observed during HiWinGS, in contrast to results from two prior field programs