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Since 2017 the Tropospheric Monitoring Instrument (TROPOMI) on board ESA's Copernicus Sentinel-5 satellite (S5-P) has provided the operational carbon monoxide (CO) data product with daily global coverage on a spatial resolution of 5.5×7 km2. The European Centre for Medium-Range Weather Forecasts (ECMWF) plans to assimilate the retrieved total columns and the corresponding vertical sensitivities in the Copernicus Atmosphere Monitoring Service Integrated Forecasting System (CAMS-IFS) to improve forecasts of the atmospheric chemical composition. The TROPOMI data will primarily constrain the vertical integrated CO field of CAMS-IFS but to a lesser extent also its vertical CO distribution. For clear-sky conditions, the vertical sensitivity of the TROPOMI CO data product is useful throughout the atmosphere, but for cloudy scenes it varies due to cloud shielding and light scattering. To assess the profile information, we deploy an a posteriori profile retrieval that combines an ensemble of TROPOMI CO column retrievals with different vertical sensitivities to obtain a vertical CO profile that is then a representative average for the chosen spatial and temporal domain. We demonstrate the approach on three CO pollution cases. For the so-called “Rabbit Foot Fire” in Idaho on 12 August 2018, we estimate a CO profile showing the pollution at an altitude of about 5 km in good agreement with airborne in situ measurements of the Biomass Burning Flux Measurements of Trace Gases and Aerosol (BB-FLUX) field campaign. The distinct CO enhancement in a plume aloft (length =212 km, width =34 km), decoupled from the ground, is sensed by TROPOMI but is not present in the CAMS-IFS model. For a large-scale event, we analyzed the CO pollution from Siberian wildfires that took place from 14 to 17 August 2018. The TROPOMI data estimate the height of the pollution plume over Canada at 7 km in agreement with CAMS-IFS. However, CAMS-IFS underestimates the enhanced CO vertical column densities sensed by TROPOMI within the plume by more than 100 ppb. Finally, we study the seasonal biomass burning in the Amazon. During the burning season the CO profile retrieved from the TROPOMI measurements (1–15 August 2019) agrees well with the one of CAMS-IFS with a similar vertical shape between ground and 14 km altitude. Hence, our results indicate that assimilating TROPOMI CO retrieval with different vertical sensitivities (e.g., under clear-sky and cloudy conditions) provides information about the vertical distribution of CO.

We present a comparison of fast-response instruments installed onboard the NASA DC-8 aircraft that measured nitrogen oxides (NO and NO2), nitrous acid (HONO), total reactive odd nitrogen (measured both as the total (NOy) and from the sum of individually measured species (SNOy)) and carbon monoxide (CO) in the troposphere during the 2019 Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) campaign. By targeting smoke from summertime wildfires, prescribed fires and agricultural burns across the continental United States, FIREX-AQ provided a unique opportunity to investigate measurement accuracy in concentrated plumes where hundreds of species coexist. Here, we compare NO measurements by chemiluminescence (CL) and laser induced fluorescence (LIF); NO2 measurements by CL, LIF and cavity enhanced spectroscopy (CES); HONO measurements by CES and iodide-adduct chemical ionization mass spectrometry (CIMS); and CO measurements by tunable diode laser absorption spectrometry (TDLAS) and integrated cavity output spectroscopy (ICOS). Additionally, total NOy measurements using the CL instrument were compared with SNOy (= NO + NO2 + HONO + nitric acid (HNO3) + acyl peroxy nitrates (APNs) + submicron particulate nitrate (pNO3)). The aircraft instrument intercomparisons demonstrate the following: 1) NO measurements by CL and LIF agreed well within instrument uncertainties, but with potentially reduced time response for the CL instrument; 2) NO2 measurements by LIF and CES agreed well within instrument uncertainties, but CL NO2 was on average 10 % higher; 3) CES and CIMS HONO measurements were highly correlated in each fire plume transect, but the correlation slope of CES vs. CIMS for all 1 Hz data during FIREX-AQ was 1.8, which we attribute to a reduction in the CIMS sensitivity to HONO in high temperature environments; 4) NOy budget closure was demonstrated for all flights within the combined instrument uncertainties of 25 %. However, we used a fluid dynamic flow model to estimate that average pNO3 sampling fraction through the NOy inlet in smoke was variable from one flight to another and ranged between 0.36 and 0.99, meaning that approximately 0–24 % on average of the total measured NOy in smoke may have been unaccounted for and may be due to unmeasured species such as organic nitrates; 5) CO measurements by ICOS and TDLAS agreed well within combined instrument uncertainties, but with a systematic offset that averaged 2.87 ppbv; and 6) integrating smoke plumes followed by fitting the integrated values of each plume improved the correlation between independent measurements.

New techniques have recently been developed and applied to capture reactive nitrogen species, including nitrogen oxides (NOx=NO+NO2), nitrous acid (HONO), nitric acid (HNO3), and particulate nitrate (pNO3-), for accurate measurement of their isotopic composition. Here, we report – for the first time – the isotopic composition of HONO from biomass burning (BB) emissions collected during the Fire Influence on Regional to Global Environments Experiment (FIREX, later evolved into FIREX-AQ) at the Missoula Fire Science Laboratory in the fall of 2016. We used our newly developed annular denuder system (ADS), which was verified to completely capture HONO associated with BB in comparison with four other high-time-resolution concentration measurement techniques, including mist chamber–ion chromatography (MC–IC), open-path Fourier transform infrared spectroscopy (OP-FTIR), cavity-enhanced spectroscopy (CES), and proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF). In 20 “stack” fires (direct emission within ∼5 s of production by the fire) that burned various biomass materials from the western US, δ15N–NOx ranges from −4.3 ‰ to +7.0 ‰, falling near the middle of the range reported in previous work. The first measurements of δ15N–HONO and δ18O–HONO in biomass burning smoke reveal a range of −5.3 ‰ to +5.8 ‰ and +5.2 ‰ to +15.2 ‰, respectively. Both HONO and NOx are sourced from N in the biomass fuel, and δ15N–HONO and δ15N–NOx are strongly correlated (R2=0.89, p), suggesting HONO is directly formed via subsequent chain reactions of NOx emitted from biomass combustion. Only 5 of 20 pNO3- samples had a sufficient amount for isotopic analysis and showed δ15N and δ18O of pNO3- ranging from −10.6 ‰ to −7.4 ‰ and +11.5 ‰ to +14.8 ‰, respectively. Our δ15N of NOx, HONO, and pNO3- ranges can serve as important biomass burning source signatures, useful for constraining emissions of these species in environmental applications. The δ18O of HONO and NO3- obtained here verify that our method is capable of determining the oxygen isotopic composition in BB plumes. The δ18O values for both of these species reflect laboratory conditions (i.e., a lack of photochemistry) and would be expected to track with the influence of different oxidation pathways in real environments. The methods used in this study will be further applied in future field studies to quantitatively track reactive nitrogen cycling in fresh and aged western US wildfire plumes.

New techniques have recently been developed to capture reactive nitrogen species for accurate measurement of their isotopic composition. Reactive nitrogen species play important roles in atmospheric oxidation capacity (hydroxyl radical and ozone formation) and may have impacts on air quality and climate. Tracking reactive nitrogen species and their chemistry in the atmosphere based upon concentration alone is challenging. Isotopic analysis provides a potential tool for tracking the sources and chemistry of species such as nitrogen oxides (NOx = NO + NO2), nitrous acid (HONO), nitric acid (HNO3) and particulate nitrate (NO3−(p)). Here we study direct biomass burning (BB) emissions during the Fire Influence on Regional to Global Environments Experiment (FIREX, later evolved into FIREX-AQ) laboratory experiments at the Missoula Fire Laboratory in the fall of 2016. An annular denuder system (ADS) developed to efficiently collect HONO for isotopic composition analysis was deployed to the Fire Lab study. Concentrations of HONO recovered from the ADS collection agree well with mean concentrations averaged over each fire measured by 4 other high time resolution techniques, including mist chamber/ion chromatography (MC/IC), open-path Fourier transform infrared spectroscopy (OP-FTIR), cavity enhanced spectroscopy (CES), proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF). The concentration validation ensures complete collection of BB emitted HONO, of which the isotopic composition is preserved during the collection process. In addition, the isotopic composition of NOx and NO3−(p) from direct BB emissions were also characterized. In 20 stack fires (direct emission within ~ 5 seconds of production by the fire) that burned various biomass materials, δ15N-NOx ranges from −4.3 ‰ to +7.0 ‰, falling near the middle of the range reported in previous work. The first measurements of δ15N-HONO and δ18O-HONO in biomass burning smoke reveal a range of −5.3 – +5.8 ‰ and +5.2 – +15.2 ‰ respectively. Both HONO and NOx are sourced from N in the biomass fuel and δ15N-HONO and δ15N-NOx are strongly correlated (R2 = 0.89, p x and HONO are connected via formation pathways. Our δ15N of NOx, HONO and NO3−(p) ranges can serve as important biomass burning source signatures, useful for constraining direct emissions of these species in environmental applications. The δ18O of HONO and NO3− obtained here verify our method is capable of determining oxygen isotopic composition in BB plumes. The δ18O for both species in this study reflect the laboratory conditions (i.e. a lack of photochemistry), and would be expected to track with the influence of ozone (O3), photochemistry and nighttime chemistry in real environments. The methods used in this study will be further applied in future field studies to quantitatively track reactive nitrogen cycling in fresh and aged Western US wildfire plumes.

Biomass burning (BB) is a large source of reactive compounds in the atmosphere. While the daytime photochemistry of BB emissions has been studied in some detail, there has been little focus on nighttime reactions despite the potential for substantial oxidative and heterogeneous chemistry. Here, we present the first analysis of nighttime aircraft intercepts of agricultural BB plumes using observations from the NOAA WP-3D aircraft during the 2013 Southeast Nexus (SENEX) campaign. We use these observations in conjunction with detailed chemical box modeling to investigate the formation and fate of oxidants (NO3, N2O5, O3, and OH) and BB volatile organic compounds (BBVOCs), using emissions representative of agricultural burns (rice straw) and western wildfires (ponderosa pine). Field observations suggest NO3 production was approximately 1 ppbv hr–1, while NO3 and N2O5 were at or below 3 pptv, indicating rapid NO3/N2O5 reactivity. Model analysis shows that >99% of NO3/N2O5 loss is due to BBVOC + NO3 reactions rather than aerosol uptake of N2O5. Nighttime BBVOC oxidation for rice straw and ponderosa pine fires is dominated by NO3 (72, 53%, respectively) but O3 oxidation is significant (25, 43%), leading to roughly 55% overnight depletion of the most reactive BBVOCs and NO2.