[link|http://www2.glos.ac.uk/gdn/origins/life/carbon.htm|Carbon] has 3 common isotopes that differ in the number of neutrons in the nucleus of the atom. Carbon 14 is radioactive - it decays into lighter elements over time, with an accurately known rate. By comparing the ratio of isotopes of carbon in a formerly living material, you can get information about how long ago it died - that's the basis of "carbon dating".
Carbon 12 and Carbon 13 are both stable isotopes of carbon. Since Carbon 13 is heavier than Carbon 12, it behaves slightly differently in plants. And one can get information about the [link|http://www.jhu.edu/news_info/news/home00/feb00/fossil.html|CO2 in the atmosphere] during the time the plants were alive.
CO2 from burning ancient coal or oil is going to have carbon isotope ratios different from CO2 from forest fires or from other natural sources.
That's my understanding of the issue. Corrections welcome.
HTH a bit.
[edit:] RealClimate has an article that addresses [link|http://www.realclimate.org/index.php?p=87|how we know that the rise in CO2 in the atmosphere is due to man].
Cheers,
Scott.