Back in 2003, Prosenjit Ghosh and Willi Brand described one of the more clever ways in which the link between fossil fuel combustion and the accumulation of carbon dioxide in the atmosphere has been demonstrated. In their article “Stable isotope ratio mass spectrometry in global climate change research” (PDF), they discuss how the ratio of isotopes of carbon in the atmosphere can be used to identify the sources of atmospheric CO2. Their work was published in 2003, in the International Journal of Mass Spectrometry.
By tracking the ratio of carbon-12 to carbon-13 in the atmosphere, the distinctive imprint of fossil fuel combustion can be identified. This is really just confirmation of the inevitable chemical fact that burning coal, oil, and natural gas produces CO2. Nevertheless, it is nice to have an independent line of evidence showing that human activities really are the major cause behind observed increases in the atmospheric concentration of CO2.