Relationships between wind speed and gas transfer, combined with knowledge of the partial pressure difference of CO2 across the air-sea interface are frequently used to determine the CO2 flux between the ocean and the atmosphere. Little attention has been paid to the influence of variability in wind speed on the calculated gas transfer velocities and the possibility of chemical enhancement of CO2 exchange at low wind speeds over the ocean. The effect of these parameters is illustrated using a quadratic dependence of gas exchange on wind speed which is fit through gas transfer velocities over the ocean determined by the natural-14C disequilibrium and the bomb-14C inventory methods. Some of the variability between different data sets can be accounted for by the suggested mechanisms, but much of the variation appears due to other causes. Possible causes for the large difference between two frequently used relationships between gas transfer and wind speed are discussed. To determine fluxes of gases other than CO2 across the air-water interface, the relevant expressions for gas transfer, and the temperature and salinity dependence of the Schmidt number and solubility of several gases of environmental interest are included in an appendix.

Relationship between wind speed and gas exchange over the ocean

Numerical assessments of global air quality and potential changes in atmospheric chemical constituents require estimates of the surface fluxes of a variety of trace gas species. We have developed a global model to estimate emissions of volatile organic compounds from natural sources (NVOC). Methane is not considered here and has been reviewed in detail elsewhere. The model has a highly resolved spatial grid (0.5° × 0.5° latitude/longitude) and generates hourly average emission estimates. Chemical species are grouped into four categories: isoprene, monoterpenes, other reactive VOC (ORVOC), and other VOC (OVOC). NVOC emissions from oceans are estimated as a function of geophysical variables from a general circulation model and ocean color satellite data. Emissions from plant foliage are estimated from ecosystem specific biomass and emission factors and algorithms describing light and temperature dependence of NVOC emissions. Foliar density estimates are based on climatic variables and satellite data. Temporal variations in the model are driven by monthly estimates of biomass and temperature and hourly light estimates. The annual global VOC flux is estimated to be 1150 Tg C, composed of 44% isoprene, 11% monoterpenes, 22.5% other reactive VOC, and 22.5% other VOC. Large uncertainties exist for each of these estimates and particularly for compounds other than isoprene and monoterpenes. Tropical woodlands (rain forest, seasonal, drought-deciduous, and savanna) contribute about half of all global natural VOC emissions. Croplands, shrublands and other woodlands contribute 10–20% apiece. Isoprene emissions calculated for temperate regions are as much as a factor of 5 higher than previous estimates.

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A global model of natural volatile organic compound emissions

A climatological mean distribution for the surface water pCO2 over the global oceans in non-El Nino conditions has been constructed with spatial resolution of 4° (latitude) ×5° (longitude) for a reference year 2000 based upon about 3 million measurements of surface water pCO2 obtained from 1970 to 2007. The database used for this study is about 3 times larger than the 0.94 million used for our earlier paper [Takahashi et al., 2002. Global sea–air CO2 flux based on climatological surface ocean pCO2, and seasonal biological and temperature effects. Deep-Sea Res. II, 49, 1601–1622]. A time-trend analysis using deseasonalized surface water pCO2 data in portions of the North Atlantic, North and South Pacific and Southern Oceans (which cover about 27% of the global ocean areas) indicates that the surface water pCO2 over these oceanic areas has increased on average at a mean rate of 1.5 μatm y−1 with basin-specific rates varying between 1.2±0.5 and 2.1±0.4 μatm y−1. A global ocean database for a single reference year 2000 is assembled using this mean rate for correcting observations made in different years to the reference year. The observations made during El Nino periods in the equatorial Pacific and those made in coastal zones are excluded from the database.

Seasonal changes in the surface water pCO2 and the sea-air pCO2 difference over four climatic zones in the Atlantic, Pacific, Indian and Southern Oceans are presented. Over the Southern Ocean seasonal ice zone, the seasonality is complex. Although it cannot be thoroughly documented due to the limited extent of observations, seasonal changes in pCO2 are approximated by using the data for under-ice waters during austral winter and those for the marginal ice and ice-free zones.

The net air–sea CO2 flux is estimated using the sea–air pCO2 difference and the air–sea gas transfer rate that is parameterized as a function of (wind speed)2 with a scaling factor of 0.26. This is estimated by inverting the bomb 14C data using Ocean General Circulation models and the 1979–2005 NCEP-DOE AMIP-II Reanalysis (R-2) wind speed data. The equatorial Pacific (14°N–14°S) is the major source for atmospheric CO2, emitting about +0.48 Pg-C y−1, and the temperate oceans between 14° and 50° in the both hemispheres are the major sink zones with an uptake flux of −0.70 Pg-C y−1 for the northern and −1.05 Pg-C y−1 for the southern zone. The high-latitude North Atlantic, including the Nordic Seas and portion of the Arctic Sea, is the most intense CO2 sink area on the basis of per unit area, with a mean of −2.5 tons-C month−1 km−2. This is due to the combination of the low pCO2 in seawater and high gas exchange rates. In the ice-free zone of the Southern Ocean (50°–62°S), the mean annual flux is small (−0.06 Pg-C y−1) because of a cancellation of the summer uptake CO2 flux with the winter release of CO2 caused by deepwater upwelling. The annual mean for the contemporary net CO2 uptake flux over the global oceans is estimated to be −1.6±0.9 Pg-C y−1, which includes an undersampling correction to the direct estimate of −1.4±0.7 Pg-C y−1. Taking the pre-industrial steady-state ocean source of 0.4±0.2 Pg-C y−1 into account, the total ocean uptake flux including the anthropogenic CO2 is estimated to be −2.0±1.0 Pg-C y−1 in 2000.

Climatological mean and decadal change in surface ocean pCO2, and net sea–air CO2 flux over the global oceans

Over the past decade it has become apparent that the atmosphere is a significant pathway for the transport of many natural and pollutant materials from the continents to the ocean. The atmospheric input of many of these species can have an impact (either positive or negative) on biological processes in the sea and on marine chemical cycling. For example, there is now evidence that the atmosphere may be an important transport path for such essential nutrients as iron and nitrogen in some regions. In this report we assess current data in this area, develop global scale estimates of the atmospheric fluxes of trace elements, mineral aerosol, nitrogen species, and synthetic organic compounds to the ocean; and compare the atmospheric input rates of these substances to their input via rivers. Trace elements considered were Pb, Cd, Zn, Cu, Ni, As, Hg, Sn, Al, Fe, Si, and P. Oxidized and reduced forms of nitrogen were considered, including nitrate and ammonium ions and the gaseous species NO, NO2, HNO3, and NH3. Synthetic organic compounds considered included polychlorinated biphenyls (PCBs), hexachlorocyclohexanes (HCHs), DDTs, chlordane, dieldrin, and hexachlorobenzenes (HCBs). Making this assessment was difficult because there are very few actual measurements of deposition rates of these substances to the ocean. However, there are considerably more data on the atmospheric concentrations of these species in aerosol and gaseous form. Mean concentration data for 10° × 10° ocean areas were determined from the available concentration data or from extrapolation of these data into other regions. These concentration distributions were then combined with appropriate exchange coefficients and precipitation fields to obtain the global wet and dry deposition fluxes. Careful consideration was given to atmospheric transport processes as well as to removal mechanisms and the physical and physicochemical properties of aerosols and gases. Only annual values were calculated. On a global scale atmospheric inputs are generally equal to or greater than riverine inputs, and for most species atmospheric input to the ocean is significantly greater in the northern hemisphere than in the southern hemisphere. For dissolved trace metals in seawater, global atmospheric input dominates riverine input for Pb, Cd, and Zn, and the two transport paths are roughly equal for Cu, Ni, As, and Fe. Fluxes and basin-wide deposition of trace metals are generally a factor of 5-10 higher in the North Atlantic and North Pacific regions than in the South Atlantic and South Pacific. Global input of oxidized and reduced nitrogen species are roughly equal to each other, although the major fraction of oxidized nitrogen enters the ocean in the northern hemisphere, primarily as a result of pollution sources. Reduced nitrogen species are much more uniformly distributed, suggesting that the ocean itself may be a significant source. The global atmospheric input of such synthetic organic species as HCH,PCBs, DDT, and HCB completely dominates their input via rivers.

The atmospheric input of trace species to the world ocean

Soil microorganisms as controllers of atmospheric trace gases (H2, CO, CH4, OCS, N2O, and NO).

In this chapter we attempt to present a brief introduction to the subject of air-sea gas exchange First the basic equations governing such exchange are given, then a review of some models proposed to describe the gas transfer process Following this, experimental approaches through both laboratory (principally using wind/water tunnels) and field measurements are summarised Finally, we present what seems to us to be the best current synthesis of the wind tunnel and field results for the prediction of gas exchange rates across the sea surface

Liliane Merlivat

Papers

Air-Sea Gas Exchange Rates: Introduction and Synthesis