The synoptic scale atmosphere-biosphere interaction can cause anomalies of ~10 ppm with length scale of ~1000 km in the monthly averaged surface CO₂ concentration. These anomalies may contribute to the errors and uncertainties of CO₂ inversion estimates.

Regular multi-year measurements of atmospheric CO₂ mixing ratios at a network of sites (Fig. 1) give quantitative spatial and temporal information on surface sources and sinks [e.g., Conway et al., 1994]. Using a global atmospheric tracer transport model in a high-resolution (daily, 4x5 degree pixels) inversion setup, we estimate surface-atmosphere CO₂ fluxes that give the best match between modelled and observed CO₂ concentrations. Building on an earlier study [Rödenbeck et al., 2003], this contribution (1) presents new CO₂ flux estimates using methodological developments, and (2) provides an update on interannual fluxes over the most recent anomalous time period 2002-2003.

The effect of rainfall on mass transfer across the air-water interface was investigated through the CO₂ absorption experiments in a turbulent open-channel flow with the free surface. The results show that the rainfall enhances both the turbulent mixing near the free surface on the liquid side and the CO₂ transfer across the interface. The mass transfer coefficient on the liquid side is well correlated by both the mean vertical momentum flux of rainfall, M, and the mean kinetic energy of rain droplets impinging on the unit area of the air-water interface, KEF. However, it was not concluded which of M and KEF is a better parameter for expressing the rainfall effects on the mass transfer. The comparison between the mass transfer coefficient obtained in this study and that obtained in wind-driven turbulence suggests that it is of great importance to consider the rainfall effect on the CO₂ exchange rate between the atmosphere and ocean in precisely estimating the global carbon cycle in a climate model.

We use the theoretically ideal tracer ¹⁴CO₂ to estimate the fossil fuel CO₂ enhancement in boundary layer air at two sites in New England and Colorado. Improved D¹⁴C measurement precision of 1.6-2.6‰ provides fossil fuel CO₂detection capability of 0.8-1.5 ppm. Using the tracers CO and SF₆, we obtain two additional independent estimates of the fossil fuel CO₂ component, and we assess the biases in these methods by comparison with the ¹⁴CO₂-based estimates. Large differences are observed between the SF₆-based estimates and those from the ¹⁴CO₂ and CO methods. The CO-based estimates show seasonally coherent biases, underestimating fossil fuel CO₂ in winter and overestimating in summer.

The Orbiting Carbon Observatory (OCO) mission will deliver space-based observations of atmospheric CO₂ with the potential to resolve many of the uncertainties in the spatial and temporal variability of carbon sources and sinks.  Our assessments of the measurement requirements for space-based remote sensing of atmospheric CO₂ conclude that the data must support retrievals of the column-averaged CO₂ dry air mole fraction, X_CO2, with precisions of 3 to 4 ppm to resolve the annually averaged gradients between the Northern and Southern hemispheres, but higher precision (1 to 2 ppm) will be needed to resolve East-West gradients and questions like the location and spatial extent of the Northern Hemisphere terrestrial carbon sink.  These conclusions are derived from the results of observational system simulation experiments (OSSEs) and synthesis inversion models [Rayner and O’Brien, 2001; O’Brien and Rayner, 2002; Rayner et al., 2002]. The X_CO2 precision requirements also considered the OCO mission design, the amplitude of X_CO2 spatial and temporal gradients, and the relationship between X_CO2 data precision and regional scale surface CO₂ flux uncertainties inferred from X_CO2 data.

Measurements of the radiocarbon content of atmospheric carbon dioxide are a potentially powerful, yet relatively unexplored method of improving the understanding of natural carbon dynamics and verifying fossil fuel emissions. Development of ¹⁴CO₂ as a tracer has been limited by measurement capabilities given that seasonal and spatial variation in D¹⁴C is currently of the same order as traditional instrument precision: 3-5 per mil. We have demonstrated 1-2 per mil reproducible measurement precision at the Center for Accelerator Mass Spectrometry of Lawrence Livermore National Laboratory. Here we present preliminary measurements of the natural variability of ¹⁴CO₂ from the SIO network of background air sampling stations.

A time series transect has been established in subantarctic surface water off the south east coast of New Zealand.  The 60 km long transect extends from the coast (45-46.20^oS 170-43.20^oE) to a station at 45-50.00^oS 171-30.00^oE. and sea surface temperature, salinity and pCO₂ have been measured bi-monthly since 1998 . SST, pCO₂ and pH of the subantarctic surface water show seasonal cycles that can be fitted with simple harmonic curves.  Temperature has a mean value of 10.4^oC, with an amplitude of 2.1^oC, the maximum occurring in late summer.  pCO₂ has a mean value of 360 matm, an amplitude of 10 matm, the maximum occurring in early spring.  The phase of the pCO₂ and temperature curves are offset by 158 days, indicating that change in sea water temperature is not the major factor affecting pCO₂ in this area.  The relative effects of temperature, biological utilization and air-sea gas exchange on the seasonal change in pCO₂ are determined using a simple model.  The model results reproduce the timing of the observed pCO₂, however the amplitude of the changes is not well reproduced.

We address an ongoing debate regarding the geographic distribution of interannual variability in ocean - atmosphere carbon exchange. We find that, for 1983-1998, both novel high-resolution atmospheric inversion calculations and global ocean biogeochemical models place the primary source of global CO₂ air-sea flux variability in the Pacific Ocean. In ocean biogeochemical models, this variability is clearly associated with the El Niño / Southern Oscillation cycle. Both inversion and models indicate that the Southern Ocean is the second-largest source of air-sea CO₂ flux variability, and that variability is small throughout the Atlantic, including the North Atlantic, in contrast to previous studies.