Potential of ¹⁴C-based vs. ΔCO-based ΔffCO₂ observations to estimate urban fossil fuel CO₂ (ffCO₂) emissions

Abstract

Atmospheric transport inversions are a powerful tool for independently estimating surface CO2 fluxes from atmospheric CO2 concentration measurements. However, additional tracers are needed to separate the fossil fuel CO2 (ffCO2) emissions from non-fossil CO2 fluxes. In this study, we focus on radiocarbon (14C), the most direct tracer of ffCO2, and the continuously measured surrogate tracer carbon monoxide (CO), which is co-emitted with ffCO2 during incomplete combustion. In the companion paper by Maier et al. (2024), we determined discrete 14C-based and continuous ΔCO-based estimates of the ffCO2 excess concentration (ΔffCO2) compared with a clean-air reference for the urban Heidelberg observation site in southwestern Germany. The ΔCO-based ΔffCO2 concentration was calculated by dividing the continuously measured ΔCO excess concentration by an average 14C-basedΔCO/ΔffCO2 ratio. Here, we use the CarboScope inversion framework adapted for the urban domain around Heidelberg to assess the potential of both types of ΔffCO2 observations to investigate ffCO2 emissions and their seasonal cycle. We find that, although they are more precise, 14C-based ΔffCO2 observations from almost 100 afternoon flask samples collected in the 2 years of 2019 and 2020 are not well suited for estimating robust ffCO2 emissions in the main footprint of this urban area, which has a very heterogeneous distribution of sources including several point sources. The benefit of the continuous ΔCO-based ΔffCO2 estimates is that they can be averaged to reduce the impact of individual hours with an inadequate model performance. We show that the weekly averaged ΔCO-based ΔffCO2 observations allow for a robust reconstruction of the seasonal cycle of the area source ffCO2 emissions from temporally flat a priori emissions. In particular, the distinct COVID-19 signal – with a steep drop in emissions in spring 2020 – is clearly present in these data-driven a posteriori results. Moreover, our top-down results show a shift in the seasonality of the area source ffCO2 emissions around Heidelberg in 2019 compared with the bottom-up estimates from the Netherlands Organization for Applied Scientific Research (TNO). This highlights the huge potential of ΔCO-based ΔffCO2 to validate bottom-up ffCO2 emissions at urban stations if the ΔCO/ΔffCO2 ratios can be determined without biases.