The isotopic composition of CO in vehicle exhaust

Abstract

We investigated the isotopic composition of CO in the exhaust of individual vehicles. Additionally, the CO2 isotopes, and the CO:CO2, CH4:CO2 and H2:CO gas ratios were measured. This was done under idling and revving conditions, and for three vehicles in a full driving cycle on a testbench. The spread in the results, even for a single vehicle, was large: for δ13C in CO ∼ −60 to 0‰, for δ18O in CO ∼ +10 to +35‰, and for all gas ratios several orders of magnitude. The results show an increase in the spread of isotopic values for CO compared to previous studies, suggesting that increasing complexity of emission control in vehicles might be reflected in the isotopic composition. When including all samples, we find a weighted mean for the δ13C and δ18O in CO of −28.7 ± 0.5‰ and +24.8 ± 0.3‰ respectively. This result is dominated by cold petrol vehicles. Diesel vehicles behaved as a distinct group, with CO enriched in 13C and depleted in 18O, compared to petrol vehicles. For the H2:CO ratio of all vehicles, we found a value of 0.71 ± 0.31 ppb:ppb. The CO:CO2 ratio, with a mean of 19.4 ± 6.8 ppb:ppm, and the CH4:CO2 ratio, with a mean of 0.26 ± 0.05 ppb:ppm, are both higher than recent literature indicates. This is likely because our sampling distribution was biased towards cold vehicles, and therefore towards higher emission situations. The CH4:CO2 ratio was found to behave similarly to the CO:CO2 ratio, suggesting that the processes affecting CO and CH4 are similar. The δ13C values in CO2 were close to the expected δ13C in fuel, with no significant difference between petrol and diesel vehicles. The δ18O values in CO2 for petrol vehicles covered a range of 20–35‰, similar to the δ18O of CO. The δ18O values in CO2 for diesel vehicles were close to the δ18O in atmospheric oxygen. A set of polluted atmospheric samples, taken near a highway and inside parking garages, showed an isotopic signature of CO and a H2:CO ratio that were similar the high emitters in the individual vehicle measurements, with no significant differences between parking garage and highway samples. This suggests that in both environments, which are dominated by different driving conditions, the CO emissions from high emitters (either a few high emission vehicles, or many vehicles with brief bursts of high emissions) dominate the total traffic emissions.