The H2/CO ratio of emissions from combustion sources: comparison of top-down with bottom-up measurements in southwest Germany

The hydrogen-to-carbon monoxide (H₂/CO) emission ratio of anthropogenic combustion sources was determined from more than two years of quasi-continuous atmospheric observations in Heidelberg (49°24' N, 8°42' E), located in the polluted Rhein-Neckar region. Evaluating concurrent mixing ratio changes of H₂ and CO during morning rush hours yielded mean molar H₂/CO ratios of 0.40 ± 0.06, while respective results inferred from synoptic pollution events gave a mean value of 0.31 ± 0.05 mole H₂/mole CO. After correction for the influence of the H₂ soil sink on the measured ratios, mean values of 0.46 ± 0.07 resp. 0.48 ± 0.07 mole H₂/mole CO were obtained, which are in excellent agreement with direct source studies of traffic emissions in the Heidelberg/Mannheim region (0.448 ± 0.003 mole H₂/mole CO). Including results from other European studies, our best estimate of the mean H₂/CO emission ratio from anthropogenic combustion sources (mainly traffic) ranges from 0.45 to 0.48 mole H₂/mole CO, which is about 20% smaller than the value of 0.59 mole H₂/mole CO which is frequently used as the basis to calculate global H₂ emissions from anthropogenic combustion sources.