Stable carbon isotopic composition of biomass burning emissions - implications for estimating the contribution of C-3 and C-4 plants

Landscape fires are a significant contributor to atmospheric burdens of greenhouse gases and aerosols. Although many studies have looked at biomass burning products and their fate in the atmosphere, estimating and tracing atmospheric pollution from landscape fires based on atmospheric measurements are challenging due to the large variability in fuel composition and burning conditions. Stable carbon isotopes in biomass burning (BB) emissions can be used to trace the contribution of C-3 plants (e.g. trees or shrubs) and C-4 plants (e.g. savanna grasses) to various combustion products. However, there are still many uncertainties regarding changes in isotopic composition (also known as fractionation) of the emitted carbon compared to the burnt fuel during the pyrolysis and combustion processes. To study BB isotope fractionation, we performed a series of laboratory fire experiments in which we burned pure C-3 and C-4 plants as well as mixtures of the two. Using isotope ratio mass spectrometry (IRMS), we measured stable carbon isotope signatures in the pre-fire fuels and post-fire residual char, as well as in the CO2, CO, CH4, organic carbon (OC), and elemental carbon (EC) emissions, which together constitute over 98 % of the post-fire carbon. Our laboratory tests indicated substantial isotopic fractionation in combustion products compared to the fuel, which varied between the measured fire products. CO2, EC, and residual char were the most reliable tracers of the fuel C-13 signature. CO in particular showed a distinct dependence on burning conditions; flaming emissions were enriched in C-13 compared to smouldering combustion emissions. For CH4 and( )OC, the fractionation was the other way round for C3 emissions (C-13-enriched) and C-4 emissions (C-13-depleted). This indicates that while it is possible to distinguish between fires that were dominated by either C-3 or C-4 fuels using these tracers, it is more complicated to quantify their relative contribution to a mixed-fuel fire based on the delta C-13 signature of emissions. Besides laboratory experiments, we sampled gases and carbonaceous aerosols from prescribed fires in the Niassa Special Reserve (NSR) in Mozambique, using an unmanned aerial system (UAS)-mounted sampling set-up. We also provided a range of C-3:C-4 contributions to the fuel and measured the fuel isotopic signatures. While both OC and EC were useful tracers of the C-3-to-C-4 fuel ratio in mixed fires in the lab, we found particularly OC to be depleted compared to the calculated fuel signal in the field experiments. This suggests that either our fuel measurements were incomprehensive and underestimated the C-3:C-4 ratio in the field or other processes caused this depletion. Although additional field measurements are needed, our results indicate that C-3-vs.-C-4 source ratio estimation is possible with most BB products, albeit with varying uncertainty ranges