
Oceanic Uptake of Anthropogenic CO2
The oceans role in moderating the build-up of atmospheric CO2 is clearly important but difficult to accurately determine. Box-diffusion and 3-D ocean general circulation models predict similar rates of CO2 uptake of about 2±0.6 Gt C/yr (Siegenthaler and Sarmiento, 1993). The error in the model predicted uptake rates depends primarily on the uncertainty in the model's parameterization of upper ocean mixing, which can be significant, as illustrated by the 0.4 Gt C/yr difference in ocean uptake rates predicted by the Hamburg and GFDL 3-D circulation models (Maier-Reimer and Hasselman, 1987; Sarmiento et al, 1992). Both of these 3-D models have problems accurately simulating the penetration of bomb 14C into the oceans (Toggweiler et al., 1989), the tracer often used to calibrate ocean mixing rates in carbon models.
The low estimates of oceanic CO2 uptake (<1 Gt C/yr) derived from the meridional gradient in atmospheric CO2 and an atmospheric transport model (Tans et al., 1990) shook geochemist's confidence in the ocean models. The low uptake rates derived by Tans et al, however, have been recalculated to higher levels (~1.8 Gt C/yr) by correcting for river input, cooler ocean surface skin temperatures and atmospheric CO oxidation (Siegenthaler and Sarmiento, 1993). The error in the oceanic CO2 uptake rate derived from this approach is "difficult to estimate" (Siegenthaler and Sarmiento, 1993). It is advantageous, therefore, to determine oceanic CO2 uptake using as many approaches as possible in order to narrow the acceptable range.
We determined the oceanic CO2 uptake rates during the last 20 years by constructing atmospheric CO2 and 13CO2 budgets (Quay et al., 1992; Quay et al., submitted). Our approach used the measured changes in the concentration and 13C of atmospheric CO2 and the depth-integrated 13C/12C of the oceanic dissolved inorganic carbon between 1970s and 1990s to directly determine the net oceanic CO2 uptake. This approach, which does not require estimates of rates of ocean mixing or air-sea gas exchange, yielded net CO2 uptake rates of 1.2±1.2 Gt C/yr for the ocean and 1.0±1.0 Gt C/yr for the terrestrial biota. Tans et al (1993) modified our atmospheric CO2 and 13CO2 budget approach by replacing the measured change in the depth-integrated 13C/12C of the ocean with an estimate of the air-sea 13C/12C disequilibrium, i.e., the difference between the measured 13C/12C of the atmospheric CO2 and that expected if the atmosphere was in isotopic equilibrium with the surface ocean. Quay et al. (submitted) calculated an oceanic CO2 uptake rate of 1.2±1.0 Gt C/yr using this approach.
Atmospheric CO2 and 13CO2 budgets, when coupled with an atmospheric transport model, are an important method to estimate oceanic and biospheric uptake of CO2 on shorter temporal and spatial scales, e.g., the "double deconvolution" approach used by Keeling et al. (1989) and others. This method relies on the different isotopic effect that net photosynthesis and air-sea gas exchange have on the 13C/12C of atmospheric CO2 in order to distinguish between oceanic and biospheric CO2 uptake. Recently Battle et al. (2000) determined the oceanic and biospheric CO2 uptake rates of 2.0±0.6 and 1.4±0.8 Gt C yr-1 based on six years of atmospheric CO2, 13C/12C and O2 concentration measurements between 1991 and 1997.
Presently the most uncertainty in the calculated CO2 uptake rates lies primarily in our poor knowledge of the 13C/12C inventory change and air-sea disequilibrium, because of the lack of ocean 13C/12C measurements (Quay et al., 1992; Tans et al., 1993), and secondarily in the isotopic disequilibrium between the atmosphere and land biota. Ciais et al. (submitted) found that the error in the oceanic 13C/12C disequilibrium yielded a ~0.4 Gt C/yr uncertainty in oceanic uptake whereas the error in atmosphere-biota disequilibrium yielded an uncertainty of ~0.1 Gt C/yr when applying the "double deconvolution" approach between 1990 and 1992. These results underscore the need for accurate ocean-wide ocean 13C/12C measurements.
Systematic high quality ocean-wide 13C/12C measurements were made in our laboratory on samples collected during NOAA/OACES cruises and at the WHOI AMS laboratory as part of the WOCE 14C measurement program in the 1990s. In total, approximately 25,000 13C/12C measurements were made during the OACES and WOCE cruises. These oceanic 13C/12C data are necessary to fully utilize the weekly 13C/12C measurements of atmospheric CO2 being made by NOAA at ~25 stations worldwide. These recent 13C/12C data provide better estimates of 13C/12C invitatory changes at -65±33 per mil m decade-1 (Fig. 1), air-sea isotopic disequilibrium at 0.60±0.10 per mil (Fig. 2) and surface ocean 13C/12C change of -0.16±0.02 per mil decade-1 (Fig. 3). Oceanic uptake rates of anthropogenic CO2 of 1.9±0.4 Gt C yr-1 in the 1980s were estimated from an ocean box-diffusion model that was constrained by the measured change in 13C/12C surface and inventory changes.
Fig. 1
Fig. 2
Fig. 3
Papers discussing these results:
Quay, P.D., R. Sonnerup, T. Westby, J. Stutsman and A. McNichol. (submitted). Anthropogenic changes of the 13C/12C of dissolved inorganic carbon in the ocean as a tracer of CO2 uptake. Global Biogeochem. Cycles
Kortzinger, A., P.D. Quay and R.E. Sonnerup. (submitted). The relationship between anthropogenic CO2 and the 13C Suess effect in the North Atlantic Ocean. Global Biogeochem. Cycles
Sonnerup, R.E., P.D. Quay and A.P. McNichol. 2000. The Indian Ocean 13C Suess effect. Global Biogeo. Cycles 14: 903-916.
Sonnerup, R.E., P.D. Quay, A.P. McNichol, J.L. Bullister, T.A. Westby and H.L. Anderson. 1999. Reconstructing the oceanic 13C Suess effect. Global Biogeo. Cycles 13: 857-872.
Zhang, J., P.D. Quay and D.O. Wilbur.1995. Carbon isotope fractionation during gas-water exchange and dissolution of CO2. Geoch. Cosmo. Acta 59: 107-114.
Quay, P.D., B. Tilbrook and C.S. Wong (1992) Oceanic uptake of fossil fuel CO2: Carbon-13 evidence. Science 256: 74-79.
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