Isotopic signatures of methane emissions from tropical fires, agriculture and wetlands: the MOYA and ZWAMPS flights.

We report methane isotopologue data from aircraft and ground measurements in Africa and South America. Aircraft campaigns sampled strong methane fluxes over tropical papyrus wetlands in the Nile, Congo and Zambezi basins, herbaceous wetlands in Bolivian southern Amazonia, and over fires in African woodland, cropland and savannah grassland. Measured methane δ13CCH4 isotopic signatures were in the range -55 to -49‰ for emissions from equatorial Nile wetlands and agricultural areas, but widely -60 ± 1‰ from Upper Congo and Zambezi wetlands. Very similar δ13CCH4 signatures were measured over the Amazonian wetlands of NE Bolivia (around -59‰) and the overall δ13CCH4 signature from outer tropical wetlands in the southern Upper Congo and Upper Amazon drainage plotted together was -59 ± 2‰. These results were more negative than expected. For African cattle, δ13CCH4 values were around -60 to -50‰. Isotopic ratios in methane emitted by tropical fires depended on the C3 : C4 ratio of the biomass fuel. In smoke from tropical C3 dry forest fires in Senegal, δ13CCH4 values were around -28‰. By contrast, African C4 tropical grass fire δ13CCH4 values were -16 to -12‰. Methane from urban landfills in Zambia and Zimbabwe, which have frequent waste fires, had δ13CCH4 around -37 to -36‰. These new isotopic values help improve isotopic constraints on global methane budget models because atmospheric δ13CCH4 values predicted by global atmospheric models are highly sensitive to the δ13CCH4 isotopic signatures applied to tropical wetland emissions. Field and aircraft campaigns also observed widespread regional smoke pollution over Africa, in both the wet and dry seasons, and large urban pollution plumes. The work highlights the need to understand tropical greenhouse gas emissions in order to meet the goals of the UNFCCC Paris Agreement, and to help reduce air pollution over wide regions of Africa. This article is part of a discussion meeting issue 'Rising methane: is warming feeding warming? (part 2)'.

The impact of spatially varying wetland source signatures on the atmospheric variability of δD-CH4.

We present the first spatially resolved distribution of the [Formula: see text] signature of wetland methane emissions and assess its impact on atmospheric [Formula: see text]. The [Formula: see text] signature map is derived by relating [Formula: see text] of precipitation to measured [Formula: see text] of methane wetland emissions at a variety of wetland types and locations. This results in strong latitudinal variation in the wetland [Formula: see text] source signature. When [Formula: see text] is simulated in a global atmospheric model, little difference is found in global mean, inter-hemispheric difference and seasonal cycle if the spatially varying [Formula: see text] source signature distribution is used instead of a globally uniform value. This is because atmospheric [Formula: see text] is largely controlled by OH fractionation. However, we show that despite these small differences, using atmospheric records of [Formula: see text] to infer changes in the wetland emissions distribution requires the use of the more accurate spatially varying [Formula: see text] source signature. We find that models will only be sensitive to changes in emissions distribution if spatial information can be exploited through the spatially resolved source signatures. In addition, we also find that on a regional scale, at sites measuring excursions of [Formula: see text] from background levels, substantial differences are simulated in atmospheric [Formula: see text] if using spatially varying or uniform source signatures. This article is part of a discussion meeting issue 'Rising methane: is warming feeding warming? (part 1)'.

Development of a Physiologically Relevant Online Chemical Assay To Quantify Aerosol Oxidative Potential.

Large-scale epidemiological studies have shown a close correlation between adverse human health effects and exposure to ambient particulate matter (PM). The oxidative potential (OP) of ambient PM has been implicated in inducing toxic effects associated with PM exposure. In particular, reactive oxygen species (ROS), either bound to PM or generated by particulate components in vivo, substantially contribute to the OP and therefore toxicity of PM by lowering antioxidant concentrations in the lung, which can subsequently lead to oxidative stress, inflammation, and disease. Traditional methods for measuring aerosol OP are labor intensive and have poor time resolution, with significant delays between aerosol collection and ROS analysis. These methods may underestimate ROS concentrations in PM because of the potentially short lifetime of some ROS species; therefore, continuous online, highly time-resolved measurement of ROS components in PM is highly advantageous. In this work, we develop a novel online method for measuring aerosol OP based on ascorbic acid chemistry, an antioxidant prevalent in the lung, thus combining the advantages of continuous online measurement with a physiologically relevant assay. The method limit of detection is estimated for a range of atmospherically important chemical components such as Cu(II) 0.22 ± 0.03 µg m-3, Fe(II) 47.8 ± 5.5 µg m-3, Fe(III) 0.63 ± 0.05 µg m-3, and secondary organic aerosol 41.2 ± 6.9 µg m-3, demonstrating that even at this early stage of development, the online method is capable of measuring the OP of PM in polluted urban environments and smog chamber studies.