Atmospheric and seawater carbon dioxide at time series station DYFAMED

A time series of fCO2, SST, and fluorescence data was collected between 1995 and 1997 by a CARIOCA buoy moored at the DyFAMed station (Dynamique des Flux Atmospheriques en Mediterranée) located in the northwestern Mediterranean Sea. On seasonal timescales, the spring phytoplankton bloom decreases the surface water fCO2 to approximately 290 µatm, followed by summer heating and a strong increase in fCO2 to a maximum of approximately 510 µatm. While the DELTA fCO2 shows strong variations on seasonal timescales, the annual average air-sea disequilibrium is only 2 µatm. Temperature-normalized fCO2 shows a continued decrease in dissolved CO2 throughout the summer and fall at a rate of approximately 0.6 µatm/d. The calculated annual air-sea CO2 transfer rate is -0.10 to -0.15 moles CO2 m-2 y-1, with these low values reflecting the relatively weak wind speed regime and small annual air-sea fCO2 disequilibrium. Extrapolating this rate over the whole Mediterranean Sea would lead to a flux of approximately -3 * 10**12 to -4.5 * 10**12 grams C/y, in good agreement with other estimates. An analysis of the effects of sampling frequency on annual air-sea CO2 flux estimates showed that monthly sampling is adequate to resolve the annual CO2 flux to within approximately ±10 - 18% at this site. Annual flux estimates made using temperature-derived fCO2 based on the measured fCO2-SST correlations are in agreement with measurement-based calculations to within ± 7-10% (depending on the gas transfer parameterization used), and suggest that annual CO2 flux estimates may be reasonably well predicted in this region from satellite or model-derived SST and wind speed information.

Calibration and application of B/Ca, Cd/Ca, and d11B in Neogloboquadrina pachyderma (sinistral)

The North Atlantic and Norwegian Sea are prominent sinks of atmospheric CO2 today, but their roles in the past remain poorly constrained. In this study, we attempt to use B/Ca and d11B ratios in the planktonic foraminifera Neogloboquadrina pachyderma (sinistral variety) to reconstruct subsurface water pH and pCO2 changes in the polar North Atlantic during the last deglaciation. Comparison of core-top results with nearby hydrographic data shows that B/Ca in N. pachyderma (s) is mainly controlled by seawater [B(OH)4]?/[HCO3]? with a roughly constant partition coefficient (KD =([B/Ca]of CaCO3)/([B(OH)4]-/[HCO3]-)of seawater) of 1.48 ± 0.15 * 10**-3 (2sigma), and d11B in this species is offset below d11B of the borate in seawater by 3.38 ± 0.71 per mil (2sigma). These values represent our best estimates with the sparse available hydrographic data close to our core-tops. More culturing and sediment trap work is needed to improve our understanding of boron incorporation into N. pachyderma (s). Application of a constant KD of 1.48 * 10**-3 to high resolution N. pachyderma (s) B/Ca records from two adjacent cores off Iceland shows that subsurface pCO2 at the habitat depth of N. pachyderma (s) (~50 m) generally followed the atmospheric CO2 trend but with negative offsets of ~10-50 ppmv during 19-10 ka. These B/Ca-based reconstructions are supported by independent estimates from low-resolution d11B measurements in the same cores. We also calibrate and apply Cd/Ca in N. pachyderma (s) to reconstruct nutrient levels for the same down cores. Like today's North Atlantic, past subsurface pCO2 variability off Iceland was significantly correlated with nutrient changes that might be linked to surface nutrient utilization and mixing within the upper water column. Because surface pCO2 (at 0 m water depth) is always lower than at deeper depths and if the application of a constant KD is valid, our results suggest that the polar North Atlantic has remained a CO2 sink during the calcification seasons of N. pachyderma (s) over the last deglaciation.

Radium concentration in water samples from the Northeast Atlantic

We present field measurements of air-sea gas exchange by the radon deficit method that were carried out during JASIN 1978 (NE Atlantic) and FGGE 1979 (Equatorial Atlantic). Both experiments comprised repeated deficit measurements at fixed position over periods of days or longer, using a previously descibed precise and fast-acquiaition, automatic radon measuring system. The deficit time series exhibit variations that only partly reflect the expected changes in gas transfer. By evaluating averages over each time series we deduce the following gas transfer velocities (average wind velocity and water temperature in parentheses): JASIN phase 1: 1.6 ± 0.8 m/d (at ~6 m/s, 13°C) JASIN phase 2: 4.3 ± 1.2 m/d (at ~8 m/s, 13°C) FGGE: 1.2 ± 0.4 m/d (at ~5 m/s, 28°C) 0.9 ± 0.4 m/d (at ~7 m/s, 28°C) 1.5 ± 0.4 m/d (at ~7 m/s, 28°C) The large difference betwen the JASIN phase 2 and FGGE values despite quite similare average wind velocity becomes even larger when the values are, however, fully compatible with the range of gas transfer velocities observed in laboratory experiments and the conclusion is suggested that their difference is caused by the highly different wind variability in JASIN and FGGE. We conclude that in gas exchange parameterization it is not sufficinent to consider wind velocity only. A comparison of our observations with laboratory results outlines the range of variations of air-sea gas transfer velocities with wind velocity and sea state. We also reformulate the radon deficit method, in the light of our observed deficit variations, to account explicitely for non-stationary and horizontal inhomogeneity in previous radon work introduces considerable uncertainty in deduced gas transfere velocity. We furthermore discuss the observational rewuirements that have to be met for an adequate exploitation of the radon deficit method, of which an observation area of minimum horizontal inhomogeneity and monitoring of the remaining inhomogeneities are thought to be the most stringent ones.