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.

Carbon dioxide concentrations for the Last Millennium, Antarctica

The most direct method of investigating past variations of the atmospheric CO2 concentration before 1958, when continuous direct atmospheric CO2 measurements started, is the analysis of air extracted from suitable ice cores. Here we present a new detailed CO2 record from the Dronning Maud Land (DML) ice core, drilled in the framework of the European Project for Ice Coring in Antarctica (EPICA) and some new measurements on a previously drilled ice core from the South Pole. The DML CO2 record shows an increase from about 278 to 282 parts per million by volume (ppmv) between ad 1000 and ad 1200 and a fairly continuous decrease to a mean value of about 277 ppmv around ad 1700. While the new South Pole measurements agree well with DML at the minimum at ad 1700 they are on average about 2 ppmv lower during the period ad 1000-1500. Published measurements from the coastal high-accumulation site Law Dome are considered as very reliable because of the reproducibility of the measurements, high temporal resolution and an accurate time scale. Other Antarctic ice cores could not, or only partly, reproduce the pre-industrial measurements from Law Dome. A comparison of the trends of DML and Law Dome shows a general agreement. However we should be able to rule out co-variations caused by the same artefact. Two possible effects are discussed, first production of CO2 by chemical reactions and second diffusion of dissolved air through the ice matrix into the bubbles. While the first effect cannot be totally excluded, comparison of the Law Dome and DML record shows that dissolved air diffusing to bubbles cannot be responsible for the pre-industrial variation. Therefore, the new record is not a proof of the Law Dome results but the first very strong support from an ice core of the Antarctic plateau.