Reconstructing past atmospheric CO2 concentration based on ice-core analyses:: open questions due to in situ production of CO2 in the ice

Analysis of air extracted from bubbles of polar ice showed the anthropogenic increase of atmospheric CO2 concentration during the past few hundred years (preindustrial concentration 280 ppmv) and, unexpectedly, that the concentration also increased due to natural causes from 200 to 280 ppmv during the transition from the last glacial epoch to the Holocene. However, more detailed reconstructions based on ice-core analyses suggested that some of the additional observed variations were actually due to the modification of CO2 concentration in the bubbles by chemical reactions between impurities in the ice. Detailed analyses of acidity, the carbonate concentration, the concentration of oxidation agents like hydrogen peroxide (H2O2), and organic compounds (e.g. formaldehyde (HCHO)) along short intervals of ice cores, representing only a few annual layers, allowed us to investigate these chemical reactions. The records are not conclusive but they indicate that the oxidation of organic compounds is at least as important as acid-carbonate reactions. Ice containing a low mean carbonate and a low H2O2 concentration, as well as a small scattering of CO2 results obtained on several adjacent samples representing a few annual layers at most, is at present the best guarantee for reliable results of the atmospheric CO2 concentration.