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).     

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.