Isotopomers of CO2 and their use in understanding the global carbon cycle
Contributed by P. Ciais, LSCE, Uniti mixte CEA-CNRS, Gif sur Yvette, France

A Note from the Chair

Science Features
Applications of Stable Isotopes in Atmospheric-Biospheric Chemistry

The Methane Budget

Nitrous Oxide Loss Processes

Aerosol Sulfate Sources

Mass-Independent Isotope Variations

CO2 Isotopers and the Carbon Cycle

It is now clear that fossil fuel combustion and other human activities are perturbing the global carbon cycle [e.g., Heimann, 1997]. Today's patterns of carbon sources and sinks can be downscaled from atmospheric measurements made around the world. Usually, the fluxes are inverted from space and time gradients in carbon dioxide (CO2) using atmospheric transport models. In the case of a passive tracer such as CO2, the transport acts as a linear operator between the sources and the modeled atmospheric concentration field. In addition to CO2 alone, other tracers of the carbon cycle are extremely valuable to improving our estimates of today's carbon sources and sinks.

The 13C/12C ratios in CO2 are strongly modified by plant photosynthesis but negligibly altered during air-sea exchange. As terrestrial plants preferentially fix the lighter isotope 12C, terrestrial uptake of CO2 will impart a fingerprint of slightly increased 13C/12C ratios on the CO2 remaining in the atmosphere. Though small, this signal can be detected by ultraprecise measurements of the 13C isotopic composition of CO2 using mass spectrometry.

The observed meridional gradient of 13C constitutes one of our best clues for understanding the latitudinal distribution of oceanic vs. terrestrial CO2 fluxes. One of the most striking results that 13C data (and now O2/N2 ratio data) unveiled is the existence of a very large repository of anthropogenic CO2 in Northern Hemisphere ecosystems during the early 1990's when the atmospheric CO2 growth rate had diminished to only one third of its normal value. Still, the long term trend and interannual fluctuations of 13C at one given monitoring station is at the limit of detection of mass spectrometers, on the order of 0.01 per mil for 13C in CO2. Thus, even a very slight bias in the isotopic data would translate into different inferred magnitudes of the global land and ocean uptake of anthropogenic CO2.

Variations in the oxygen:nitrogen ratio (O2/N2) with respect to the oxygen:argon ratio in air are due to photosynthesis, respiration, and fossil fuel and biomass burning which are directly linked to the global carbon cycle and its perturbation by man [e.g., Keeling et al., 1996]. These variations can be measured by techniques similar to those used for 13C/12C ratios. Oxygen has a low solubility in water compared to CO2 and lacks a buffering system. Oceanic productivity as well as mixing or upwelling of O2depleted water imprints a distinct signal on the atmosphere, modulated by airsea gas exchange. This leads to relatively large annual O2/N2 variations in both hemispheres. The long term trend as well as interannual fluctuations in O2/N2 can now be resolved with modern techniques like mass spectrometry. In combination with CO2 concentration measurements this gives us much information about the global carbon budget, i.e., the socalled "missing sink".

The 18O/16O ratio in atmospheric CO2 has been identified as a unique tracer to constrain separately the gross uptake (photosynthesis) and release (respiration) of carbon by terrestrial biota. CO2 can exchange an 18O atom with two isotopically distinct water reservoirs: Evaporating leaf water during photosynthesis and soil moisture during respiration. Thus, the 18O/16O isotopic composition of CO2 is controlled indirectly by the 18O/16O ratio of water in the biosphere, and thus is linked to the global water cycle. Atmospheric measurements of 18O/16O in CO2 show a pronounced negative latitudinal gradient, which is interpreted as a fingerprint of respiratory CO2 emissions. The reason 18O in CO2 is useful is that it relates to the gross fluxes of CO2 exchanged by land ecosystems (photosynthesis, respiration), rather than to the net fluxes which are constrained by CO2, 13C and O2/N2.

In pursuing and improving the atmospheric monitoring of CO2 and its isotopic composition, there is a crucial need to augment the coverage of poorly known oceanic and continental areas, thus better improving the diagnostic of carbon fluxes at the continental to regional scale.