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.     

Model analysis of the influence of gas diffusivity in soil on CO and H2 uptake

CO and H₂ uptake by soil was studied as a diffusion process. A diffusion model was used to determine how the surface fluxes (net deposition velocities) were controlled by in‐situ microbial uptake rates and soil gas diffusivity calculated from the 3‐phase system (solid, liquid, gas) in the soil. Analytical solutions of the diffusion model assuming vertical uniformity of soil properties showed that physical properties such as air‐filled porosity and soil gas diffusivity were more important in the uptake process than in the emission process. To incorporate the distribution of in‐situ microbial uptake, we used a 2‐layer model incorporating "a microbiologically inactive layer and an active layer" as suggested from experimental results. By numerical simulation using the 2‐layer model, we estimated the effect of several factors on deposition velocities. The variations in soil gas diffusivity due to physical properties, i.e., soil moisture and air‐filled porosity, as well as to the depth of the inactive layer and in‐situ microbial uptake, were found to be important in controlling deposition velocities. This result shows that the diffusion process in soil is critically important for CO and H₂ uptake by soil, at least in soils with higher in‐situ uptake rates and/or with large variation in soil moisture. Similar uptake rates and the difference in deposition velocity between CO and H₂ may be attributable to differences in CO and H₂ molecular diffusivity. The inactive layer is resistant to diffusion and creates uptake limits in CO and H₂ by soil. The coupling of high temperature and a thick inactive layer, common in arid soils, markedly lowers net CO deposition velocity. The temperature for maximum uptake of CO changes with depth of the inactive layer.