Air-sea gas exchange

This chapter contains sections titled: Introduction Air-Sea Gas Exchange Models and Theory Laboratory Studies of Air-Water Gas Exchange Large-Scale Estimates of Air-Sea Gas Transfer Local Techniques and Measurements Micrometeorological Techniques and Measurements Parameterizations of Air-Sea Gas Transfer Future Work

Emissions of CH3Br, organochlorines, and organoiodines from temperate macroalgae

The production rates of a range of low molecular weight halogenated organics have been determined in cultures of five temperate species of macroalgae collected from the north coast of Norfolk, England. Compounds studied included CH3Br, the chlorinated organics CH3Cl, CH2Cl2 and CHCl3, and the iodinated organics CH3I, C2H5I, and CH2ClI. Measurements of a wider range of halocarbon concentrations in an isolated rockpool and in air over the seaweed bed were also conducted to evaluate the local impact of the seaweeds on halocarbon concentrations in the natural environment. Estimates for the global emissions of some of the key halogenated compounds from macroalgae have been derived. In general macrophytes appear not to be globally significant producers of the particular halocarbons studied. In coastal regions, however, the impact on local atmospheric composition and chemistry could be greater.

Living in warmer, more acidic oceans retards physiological recovery from tidal emersion in the velvet swimming crab, Necora puber

The distribution patterns of many species in the intertidal zone are partly determined by their ability to survive and recover from tidal emersion. During emersion, most crustaceans experience gill collapse, impairing gas exchange. Such collapse generates a state of hypoxemia and a hypercapnia-induced respiratory acidosis, leading to hyperlactaemia and metabolic acidosis. However, how such physiological responses to emersion are modified by prior exposure to elevated CO2 and temperature combinations, indicative of future climate change scenarios, is not known. We therefore investigated key physiological responses of velvet swimming crabs, Necora puber, kept for 14 days at one of four pCO(2)/temperature treatments (400 mu atm/10 degrees C, 1000 mu atm/10 degrees C, 400 mu atm/15 degrees C or 1000 mu atm/15 degrees C) to experimental emersion and recovery. Pre-exposure to elevated pCO(2) and temperature increased pre-emersion bicarbonate ion concentrations [HCO3-], increasing resistance to short periods of emersion (90 min). However, there was still a significant acidosis following 180 min emersion in all treatments. The recovery of extracellular acid-base via the removal of extracellular pCO(2) and lactate after emersion was significantly retarded by exposure to both elevated temperature and pCO(2). If elevated environmental pCO(2) and temperature lead to slower recovery after emersion, then some predominantly subtidal species that also inhabit the low to mid shore, such as N. puber, may have a reduced physiological capacity to retain their presence in the low intertidal zone, ultimately affecting their bathymetric range of distribution, as well as the structure and diversity of intertidal assemblages.

Air–sea fluxes of oxygenated volatile organic compounds across the Atlantic Ocean

We present air-sea fluxes of oxygenated volatile organics compounds (OVOCs) quantified by eddy covariance (EC) during the Atlantic Meridional Transect cruise in 2012. Measurements of acetone, acetaldehyde, and methanol in air as well as in water were made in several different oceanic provinces and over a wide range of wind speeds (1-18 m s(-1)). The ocean appears to be a net sink for acetone in the higher latitudes of the North Atlantic but a source in the subtropics. In the South Atlantic, seawater acetone was near saturation relative to the atmosphere, resulting in essentially zero net flux. For acetaldehyde, the two-layer model predicts a small oceanic emission, which was not well resolved by the EC method. Chemical enhancement of air-sea acetaldehyde exchange due to aqueous hydration appears to be minor. The deposition velocity of methanol correlates linearly with the transfer velocity of sensible heat, confirming predominant airside control. We examine the relationships between the OVOC concentrations in air as well as in water, and quantify the gross emission and deposition fluxes of these gases.

Chemistry and Release of Gases from the Surface Ocean

The sea-surface layer is the very upper part of the sea surface where reduced mixing leads to strong gradients in physical, chemical and biological properties1. This surface layer is naturally reactive, containing a complex chemistry of inorganic components and dissolved organic matter (DOM), the latter including amino acids, proteins, fatty acids, carbohydrates, and humic-type components,2 with a high proportion of functional groups such as carbonyls, carboxylic acids and aromatic moieties.3 The different physical and chemical properties of the surface of the ocean compared with bulk seawater, and its function as a gateway for molecules to enter the atmosphere or ocean phase, make this an interesting and important region for study. A number of chemical reactions are believed to occur on and in the surface ocean; these may be important or even dominant sources or sinks of climatically-active marine trace gases. However the sea surface, especially the top 1um to 1mm known as the sea surface microlayer (ssm), is critically under-sampled, so to date much of the evidence for such chemistry comes from laboratory and/or modeling studies. This review discusses the chemical and physical structure of the sea surface, mechanisms for gas transfer across it, and explains the current understanding of trace gas formation at this critical interface between the ocean and atmosphere.

Annual study of oxygenated volatile organic compounds in UK shelf waters

We performed an annual study of oxygenated volatile organic compound (OVOC) seawater concentrations at a site off Plymouth, UK in the Western English Channel over the period of February 2011–March 2012. Acetone concentrations ranged from 2–10 nM (nanomole/L) in surface waters with a maximum observed in summer. Concentrations correlated positively with net shortwave radiation and UV light, suggestive of photochemically linked acetone production. We observed a clear decline in acetone concentrations below the mixed layer. Acetaldehyde varied between 4–37 nM in surface waters with higher values observed in autumn and winter. Surface concentrations of methanol ranged from 16–78 nM, but no clear annual cycle was observed. Methanol concentrations exhibited considerable inter-annual variability. We estimate consistent deposition to the sea surface for acetone and methanol but that the direction of the acetaldehyde flux varies during the year.

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.

20 Years of the Atlantic Meridional Transect — AMT

The AMT (www.amt-uk.org) is a multidisciplinary programme which undertakes biological, chemical, and physical oceanographic research during an annual voyage between the UK and a destination in the South Atlantic such as the Falkland Islands,South Africa, or Chile. This transect of >12,000 km crosses a range of ecosystems from subpolar to tropical, from euphotic shelf seas and upwelling systems, to oligotrophic mid-ocean gyres. The year 2015 has seen two milestones in the history of the AMT: the achievement of 20 years of this unique ocean going programme and the departure of the 25th cruise on the 15th of September. Both of these events were celebrated in June this year with an open science conference hosted by the Plymouth Marine Laboratory (PML) and will be further documented in a special issue of Progress in Oceanography which is planned for publication in 2016. Since 1995, the 25 research cruises have involved 242 sea-going scientists from 66 institutes representing 22 countries.

Progress in satellite remote sensing for studying physical processes at the ocean surface and its borders with the atmosphere and sea-ice

Physical oceanography is the study of physical conditions, processes and variables within the ocean, including temperature-salinity distributions, mixing of the water column, waves, tides, currents, and air-sea interaction processes. Here we provide a critical review of how satellite sensors are being used to study physical oceanography processes at the ocean surface and its borders with the atmosphere and sea-ice. The paper begins by describing the main sensor types that are used to observe the oceans (visible, thermal infrared and microwave) and the specific observations that each of these sensor types can provide. We then present a critical review of how these sensors and observations are being used to study i) ocean surface currents, ii) storm surges, iii) sea-ice, iv) atmosphere-ocean gas exchange and v) surface heat fluxes via phytoplankton. Exciting advances include the use of multiple sensors in synergy to observe temporally varying Arctic sea-ice volume, atmosphere- ocean gas fluxes, and the potential for 4 dimensional water circulation observations. For each of these applications we explain their relevance to society, review recent advances and capability, and provide a forward look at future prospects and opportunities. We then more generally discuss future opportunities for oceanography-focussed remote-sensing, which includes the unique European Union Copernicus programme, the potential of the International Space Station and commercial miniature satellites. The increasing availability of global satellite remote-sensing observations means that we are now entering an exciting period for oceanography. The easy access to these high quality data and the continued development of novel platforms is likely to drive further advances in remote sensing of the ocean and atmospheric systems.