Columnar aerosol properties in a northeastern atlantic site (plymouth united kingdom) by means of ground based skyradiometer data during years 2000-2008.

Between 2000 and 2008, columnar optical and radiative properties were measured at the Plymouth Marine Laboratory (PML), UK (50° 21.95′N, 4° 8.85′W) using an automatic Prede POM01L sun–sky photometer. The database was analyzed for aerosol optical properties using the SKYRAD radiative inversion algorithm and calibrated using the in situ SKYIL calibration method. Retrievals include aerosol optical depth, Ångström wavelength exponent, aerosol volume distribution, refractive index and single scattering albedo. The results show that the Plymouth site is characterized by low values of aerosol optical depth with low variability (0.18 ± 0.08 at 500 nm) and a mean annual Ångström exponent of 1.03 ± 0.21. The annual mean of the single scattering albedo is 0.97, indicative of non-absorbing aerosols. The aerosol properties were classified in terms of air mass back trajectories: the area is mainly affected by Atlantic air masses and the dominant aerosol type is a mixture of maritime particles, present in low burdens with variable size. The maritime air masses were defined by annual mean values for the AOD (at 500 nm) of 0.13–0.14 and a wavelength exponent of 0.96–1.03. Episodic anthropogenic and mineral dust intrusions occasionally occur, but they are sporadic and dilute (AOD at 500 nm about 0.20). Tropical continental air masses were characterized by the highest AOD at 500 nm (0.34) and the lowest wavelength exponent (0.83), although they were the least represented in the analysis.

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.

Air-sea exchange of methanol and acetone during HiWinGS: Estimation of air phase, water phase gas transfer velocities

The air-sea fluxes of methanol and acetone were measured concurrently using a proton-transfer-reaction mass spectrometer (PTR-MS) with the eddy covariance (EC) technique during the High Wind Gas Exchange Study (HiWinGS) in 2013. The seawater concentrations of these compounds were also measured twice daily with the same PTR-MS coupled to a membrane inlet. Dissolved concentrations near the surface ranged from 7 to 28 nM for methanol and from 3 to 9 nM for acetone. Both gases were consistently transported from the atmosphere to the ocean as a result of their low sea surface saturations. The largest influxes were observed in regions of high atmospheric concentrations and strong winds (up to 25 m s(-1)). Comparison of the total air-sea transfer velocity of these two gases (K-a), along with the in situ sensible heat transfer rate, allows us to constrain the individual gas transfer velocity in the air phase (k(a)) and water phase (k(w)). Among existing parameterizations, the scaling of k(a) from the COARE model is the most consistent with our observations. The k(w) we estimated is comparable to the tangential (shear driven) transfer velocity previously determined from measurements of dimethyl sulfide. Lastly, we estimate the wet deposition of methanol and acetone in our study region and evaluate the lifetimes of these compounds in the surface ocean and lower atmosphere with respect to total (dry plus wet) atmospheric deposition.

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 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.