Advances in Air–Sea \hbox {CO}_2 Flux Measurement by Eddy Correlation

Eddy-correlation measurements of the oceanic \(\hbox {CO}_2\) flux are useful for the development and validation of air–sea gas exchange models and for analysis of the marine carbon cycle. Results from more than a decade of published work and from two recent field programs illustrate the principal interferences from water vapour and motion, demonstrating experimental approaches for improving measurement precision and accuracy. Water vapour cross-sensitivity is the greatest source of error for \(\hbox {CO}_2\) flux measurements using infrared gas analyzers, often leading to a ten-fold bias in the measured \(\hbox {CO}_2\) flux. Much of this error is not related to optical contamination, as previously supposed. While various correction schemes have been demonstrated, the use of an air dryer and closed-path analyzer is the most effective way to eliminate this interference. This approach also obviates density corrections described by Webb et al. (Q J R Meteorol 106:85–100, 1980). Signal lag and frequency response are a concern with closed-path systems, but periodic gas pulses at the inlet tip provide for precise determination of lag time and frequency attenuation. Flux attenuation corrections are shown to be \(<\) 5 % for a cavity ring-down analyzer (CRDS) and dryer with a 60-m inlet line. The estimated flux detection limit for the CRDS analyzer and dryer is a factor of ten better than for IRGAs sampling moist air. While ship-motion interference is apparent with all analyzers tested in this study, decorrelation or regression methods are effective in removing most of this bias from IRGA measurements and may also be applicable to the CRDS.     

The Effect of Breaking Waves on $$\hbox {CO}_2$$ Air–Sea Fluxes in the Coastal Zone

The influence of wave-associated parameters controlling turbulent \(\hbox {CO}_2\) fluxes through the air–sea interface is investigated in a coastal region. A full year of high-quality data of direct estimates of air–sea \(\hbox {CO}_2\) fluxes based on eddy-covariance measurements is presented. The study area located in Todos Santos Bay, Baja California, Mexico, is a net sink of \(\hbox {CO}_2\) with a mean flux of \(-1.3\, \upmu \hbox {mol m}^{-2}\hbox {s}^{-1}\) (\(-41.6\hbox { mol m}^{-2}\hbox {yr}^{-1}\)). The results of a quantile-regression analysis computed between the \(\hbox {CO}_2\) flux and, (1) wind speed, (2) significant wave height, (3) wave steepness, and (4) water temperature, suggest that the significant wave height is the most correlated parameter with the magnitude of the flux but the behaviour of the relation varies along the probability distribution function, with the slopes of the regression lines presenting both positive and negative values. These results imply that the presence of surface waves in coastal areas is the key factor that promotes the increase of the flux from and into the ocean. Further analysis suggests that the local characteristics of the aqueous and atmospheric layers might determine the direction of the flux.     

An Approach to Minimizing Artifacts Caused by Cross-Sensitivity in the Determination of Air–Sea \text{ CO }_{2} Flux Using the Eddy-Covariance Technique

The air–sea $\text{ CO }_{2}$ flux was measured from a research vessel in the North Yellow Sea in October 2007 using an open-path eddy-covariance technique. In 11 out of 64 samples, the normalized spectra of scalars ( $\text{ CO }_{2}$ , water vapour, and temperature) showed similarities. However, in the remaining samples, the normalized $\text{ CO }_{2}$ spectra were observed to be greater than those of water vapour and temperature at low frequencies. In this paper, the noise due to cross-sensitivity was identified through a combination of intercomparisons among the normalized spectra of three scalars and additional analyses. Upon examination, the cross-sensitivity noise appeared to be mainly present at frequencies ${<}0.8\,\text{ Hz }$ . Our analysis also suggested that the high-frequency fluctuations of $\text{ CO }_{2}$ concentration (frequency ${>}0.8\,\text{ Hz }$ ) was probably less affected by the cross-sensitivity. To circumvent the cross-sensitivity issue, the cospectrum in the high-frequency range 0.8–1.5 Hz, instead of the whole range, was used to estimate the $\text{ CO }_{2}$ flux by taking the contribution of the high frequency to the $\text{ CO }_{2}$ flux to be the same as the contribution to the water vapour flux. The estimated air–sea $\text{ CO }_{2}$ flux in the North Yellow Sea was $-0.039\,\pm \,0.048\,\text{ mg } \text{ m }^{-2}\,\text{ s }^{-1},$ a value comparable to the estimates using the inertial dissipation method and Edson’s method (Edson et al., J Geophys Res 116:C00F10, 2011).     

Parameterization and Micrometeorological Measurement of Air–Sea Gas Transfer

Because of the combination of smallconcentrations and/or small fluxes, the determinationof air–sea gas fluxes presents unusual measurementdifficulties. Direct measurements (i.e., eddycorrelation) of the fluxes are rarely attempted. Inthe last decade, there has been an intense scientificeffort to improve measurement techniques and to placebulk parameterizations of gas transfer on firmertheoretical grounds. Oceanic tracer experiments,near-surface mean concentration profiles, eddyaccumulation, and direct eddy covariance methods haveall been used. Theoretical efforts have focusedprimarily in the realm of characterizing the transferproperties of the oceanic molecular sublayer. Recentmajor field efforts organized by the U.S.A. (GASEX-98) andthe European Union (ASGAMAGE) have yielded atmospheric-derivedresults much closer to those from oceanographicmethods. In this paper, we review the physical basisof a bulk-to-bulk gas transfer parameterization thatis generalized for solubility and Schmidt number. Wealso discuss various aspects of recent sensor andtechnique developments used for direct measurementsand demonstrate experimental progress with resultsfrom ASGAMAGE and GASEX-98. It is clear that sensornoise, sensitivity, and cross talk with other speciesand even ship motion corrections still need improvement foraccurate measurements of trace gas exchange over theocean. Significant work remains to resolve issuesassociated with the effects of waves, bubbles, andsurface films.     

Air–Sea Interaction Features in the Baltic Sea and at a Pacific Trade-Wind Site: An Inter-comparison Study

A systematic comparison of wind profiles and momentum exchange at a trade wind site outside Oahu, Hawaii and corresponding data from the Baltic Sea is presented. The trade wind data are to a very high degree swell dominated, whereas the Baltic Sea data include a more varied assortment of wave conditions, ranging from a pure growing sea to swell. In the trade wind region swell waves travel predominantly in the wind direction, while in the Baltic, significant cross-wind swells are also present. Showing the drag coefficient as a function of the 10-m wind speed demonstrates striking differences for unstable conditions with swell for the wind-speed range 2 m s^?1 < U ₁₀ < 7 m s^?1, where the trade-wind site drag values are significantly larger than the corresponding Baltic Sea values. In striking contrast to this disagreement, other features studied are surprisingly similar between the two sites. Thus, exactly as found previously in Baltic Sea studies during unstable conditions and swell, the wind profile in light winds (3 m s^?1) shows a wind maximum at around 7–8 m above the water, with close to constant wind speed above. Also, for slightly higher wind speeds (4 m s^?1 < U ₁₀ < 7 m s^?1), the similarity between wind profiles is striking, with a strong wind-speed increase below a height of about 7–8 m followed by a layer of virtually constant wind speed above. A consequence of these wind-profile features is that Monin–Obukhov similarity is no longer valid. At the trade-wind site this was observed to be the case even for wind speeds as high as 10 m s^?1. The turbulence kinetic energy budget was evaluated for four cases of 8–16 30- min periods at the trade-wind site, giving results that agree very well with corresponding figures from the Baltic Sea.     

A Model Evaluation of Biological Effects on Seasonal Variation of Air–Sea CO2 Flux in the Yellow and East China Seas

Based on a coupled physical-biogeochemical model of the Yellow and East China Seas (YECS), the influence of biological activity on the seasonal variation of the air–sea CO₂ flux is evaluated. The solution of a sensitivity experiment that excludes biological activity is compared with that of a reference experiment that includes the full processes. The comparison reveals that biological activity results in a much stronger seasonal variation of surface dissolved inorganic carbon (DIC) and, hence, the ratio of total alkalinity to DIC in the northern parts of the YECS. The increased ratio resulting from biological DIC consumption contributes to the undersaturated partial pressure of CO₂ at the sea surface with respect to the atmosphere, causing the central Yellow Sea in summer and autumn to shift from being a CO₂ source to a sink; this same shift also occurs over the Changjiang Bank in summer. In the southern YECS, the biological effect is relatively weak. The comparison further reveals that low water temperature, instead of biological activity, is the dominant factor causing the YECS to become a carbon sink in spring. The biological effect on the variation of DIC (both at the surface and in the water column) differs greatly among the three representative regions of the YECS because of differences in primary production and hydrodynamic conditions. Particle-tracking simulations quantify the regional difference in horizontal advection. In the northern region, weaker horizontal advection causes the longer residence time of low DIC water induced by biological consumption. Over the entire YECS, biological activity contributes to about one-third of the total annual absorption of atmospheric CO₂.     

Summertime land–sea thermal contrast and atmospheric circulation over East Asia in a warming climate—Part II: Importance of CO2-induced continental warming

In this the second of a two-part study, we examine the physical mechanisms responsible for the increasing contrast of the land–sea surface air temperature (SAT) in summertime over the Far East, as observed in recent decades and revealed in future climate projections obtained from a series of transient warming and sensitivity experiments conducted under the umbrella of the Coupled Model Intercomparison Project phase 5. On a global perspective, a strengthening of land–sea SAT contrast in the transient warming simulations of coupled atmosphere–ocean general circulation models is attributed to an increase in sea surface temperature (SST). However, in boreal summer, the strengthened contrast over the Far East is reproduced only by increasing atmospheric CO₂ concentration. In response to SST increase alone, the tropospheric warming over the interior of the mid- to high-latitude continents including Eurasia are weaker than those over the surrounding oceans, leading to a weakening of the land–sea SAT contrast over the Far East. Thus, the increasing contrast and associated change in atmospheric circulation over East Asia is explained by CO₂-induced continental warming. The degree of strengthening of the land–sea SAT contrast varies in different transient warming scenarios, but is reproduced through a combination of the CO₂-induced positive and SST-induced negative contributions to the land–sea contrast. These results imply that changes of climate patterns over the land–ocean boundary regions are sensitive to future scenarios of CO₂ concentration pathways including extreme cases.