Comparison of airborne measurements of NO, NO₂, HONO, NO_y and CO during FIREX-AQ

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.

Large contribution of biomass burning emissions to ozone throughout the global remote troposphere

Ozone is the third most important anthropogenic greenhouse gas after carbon dioxide and methane but has a larger uncertainty in its radiative forcing, in part because of uncertainty in the source characteristics of ozone precursors, nitrogen oxides, and volatile organic carbon that directly affect ozone formation chemistry. Tropospheric ozone also negatively affects human and ecosystem health. Biomass burning (BB) and urban emissions are significant but uncertain sources of ozone precursors. Here, we report global-scale, in situ airborne measurements of ozone and precursor source tracers from the NASA Atmospheric Tomography mission. Measurements from the remote troposphere showed that tropospheric ozone is regularly enhanced above background in polluted air masses in all regions of the globe. Ozone enhancements in air with high BB and urban emission tracers (2.1 to 23.8 ppbv [parts per billion by volume]) were generally similar to those in BB-influenced air (2.2 to 21.0 ppbv) but larger than those in urban-influenced air (−7.7 to 6.9 ppbv). Ozone attributed to BB was 2 to 10 times higher than that from urban sources in the Southern Hemisphere and the tropical Atlantic and roughly equal to that from urban sources in the Northern Hemisphere and the tropical Pacific. Three independent global chemical transport models systematically underpredict the observed influence of BB on tropospheric ozone. Potential reasons include uncertainties in modeled BB injection heights and emission inventories, export efficiency of BB emissions to the free troposphere, and chemical mechanisms of ozone production in smoke. Accurately accounting for intermittent but large and widespread BB emissions is required to understand the global tropospheric ozone burden.

Advances in altimetric snow depth estimates using bi-frequency SARAL and CryoSat-2 Ka–Ku measurements

Although snow depth on sea ice is a key parameter for sea ice thickness (SIT) retrieval, there currently does not exist reliable estimations. In the Arctic, nearly all SIT products use a snow depth climatology (the modified Warren-99 climatology, W99m) constructed from in situ data obtained prior to the first significant impacts of climate change. In the Antarctic, the lack of information on snow depth remains a major obstacle in the development of reliable SIT products. In this study, we present the latest version of the altimetric snow depth (ASD) product computed over both hemispheres from the difference of the radar penetration into the snow pack between the Ka-band frequency SARAL/Altika and the Ku-band frequency CryoSat-2. The ASD solution is compared against a wide range of snow depth products including model data (Pan-Arctic Ice-Ocean Modelling and Assimilation System (PIOMAS) or its equivalent in the Antarctic the Global Ice-Ocean Modeling and Assimilation System (GIOMAS), the MERCATOR model, and NASA's Eulerian Snow On Sea Ice Model (NESOSIM, only in the Arctic)), the Advanced Microwave Scanning Radiometer-2 (AMSR2) passive radiometer data, and the Dual-altimeter Snow Thickness (DuST) Ka–Ku product (only in the Arctic). The ASD product is further validated in the Arctic against the ice mass balance (IMB) buoys, the CryoSat Validation Experiment (CryoVEx) and Operation Ice Bridge's (OIB) airborne measurements. These comparisons demonstrate that ASD is a relevant snow depth solution, with spatiotemporal patterns consistent with those of the alternative Ka–Ku DuST product but with a mean bias of about 6.5 cm. We also demonstrate that ASD is consistent with the validation data: comparisons with OIB's airborne snow radar in the Arctic during the period of 2014–2018 show a correlation of 0.66 and a RMSE of about 6 cm. Furthermore, a first-guess monthly climatology has been constructed in the Arctic from the ASD product, which shows a good agreement with OIB during 2009–2012. This climatology is shown to provide a better solution than the W99m climatology when compared with validation data. Finally, we have characterised the SIT uncertainty due to the snow depth from an ensemble of SIT solutions computed for the Arctic by using the different snow depth products previously used in the comparison with the ASD product. During the period of 2013–2019, we found a spatially averaged SIT mean standard deviation of 20 cm. Deviations between SIT estimations due to snow depths can reach up to 77 cm. Using the ASD data instead of W99m to estimate SIT over this time period leads to a reduction in the average SIT of about 30 cm.

Implementation of HONO into the chemistry-climate model CHASER (V4.0): roles in tropospheric chemistry

Nitrous acid (HONO) is an important atmospheric gas given its contribution to the cycles of NOx and HOx, but its role in global atmospheric photochemistry is not fully understood. This study, for the first time, implemented three pathways of HONO formation in the chemistry-climate model CHASER (MIROC-ESM) to explore three physical phenomena: gas-phase kinetic reactions (GRs), direct emission (EM), and heterogeneous reactions on cloud/aerosol particles (HRs). We evaluated the simulations by the atmospheric measurements from the OMI (Ozone Monitoring Instrument), EANET (Acid Deposition Monitoring Network in eastern Asia) / EMEP (European Monitoring and Evaluation Programme) ground-based stationary observations, observations from the ship R/V Mirai, and aircraft-based measurements by ATom1 (atmospheric tomography) and EMeRGe-Asia-2018 (Effect of Megacities on the Transport and Transformation of Pollutants on the Regional to Global scales). We showed that the inclusion of the HONO chemistry in the modeling process reduces the model bias against the measurements for PM2.5, NO3−/HNO3, NO2, OH, O3, and CO, especially in the lower troposphere and the North Pacific (NP) region. We found that the retrieved global abundance of tropospheric HONO was 1.4 TgN. Of the three source pathways, HRs and EM contributed 63 % and 26 % to the net HONO production, respectively. We also observed that, reactions on the aerosol surfaces contributed larger amounts of HONO (51 %) than those on the cloud surfaces (12 %). The model exhibited significant negative biases for daytime HONO in the Asian off-coast region, compared with the airborne measurements by EMeRGe-Asia-2018, indicating the existence of unknown daytime HONO sources. Strengthening of aerosol uptake of NO2 near-surface and in the middle troposphere, cloud uptake, and direct HONO emission are all potential yet-unknown HONO sources. We also found that the simulated HONO abundance and its impact on NOx-O3 chemistry are sensitive to the yield of the heterogeneous conversion of NO2 to HONO (vs. HNO3). Inclusion of HONO reduces global tropospheric NOx (NO + NO2) levels by 20.4 %, thereby weakening the tropospheric oxidizing capacity, which in turn, increases CH4 lifetime (13 %) and CO abundance (8 %). HRs on the surfaces of cloud particles, which have been neglected in previous modeling studies, are the main drivers of these impacts. This effect is particularly salient for the substantial reductions of levels of OH (40–67 %) and O3 (30–45 %) in the NP region during summer given the significant reduction of NOx level (50–95 %). In contrast, HRs on aerosol surfaces in China (Beijing) enhance OH and O3 winter mean levels by 600–1700 % and 10–33 %, respectively, with regards to their minima in winter. Overall, our findings suggest that a global model that does not consider HONO heterogeneous mechanisms (especially HRs on cloud particle surfaces) may erroneously predict the effect of HONO in remote areas and polluted regions.

Biomass burning pollution in the South Atlantic upper troposphere: GLORIA trace gas observations and evaluation of the CAMS model

In this study, we present simultaneous airborne measurements of peroxyacetyl nitrate (PAN), ethane (C2H6), formic acid (HCOOH), methanol (CH3OH), and ethylene (C2H4) above the South Atlantic in September and October 2019. Observations were obtained from the Gimballed Limb Observer for Radiance Imaging of the Atmosphere (GLORIA), as two-dimensional altitude cross-sections along the flight path. The flights were part of the SouthTRAC (Transport and Composition in the Southern Hemisphere Upper Troposphere/Lower Stratosphere) campaign with the German High Altitude and Long range research Aircraft (HALO). On two flights (8 September 2019 and 7 October 2019), large enhancements of all these substances were found between 7 and 14 km altitude with maximum volume mixing ratios (VMRs) of 1000 pptv of PAN, 1400 pptv for C2H6, 800 pptv for HCOOH, 4500 pptv for CH3OH, and 200 pptv for C2H4. One flight shows a common filamentary structure in the trace gas distributions, while the second flight is characterized by one large plume. Using backward trajectories, we show that measured pollutants are likely originating from South America and central Africa, where elevated PAN VMRs are visible at the surface layer of the Copernicus Atmosphere Monitoring Service (CAMS) model during the weeks before both measurements. In comparison to simulation results of the CAMS reanalysis interpolated onto the GLORIA measurement geolocations, we show that the model is able to reproduce the overall structure of the measured pollution trace gas distributions. For PAN, the absolute VMRs are in agreement with the GLORIA measurements, too. However, C2H6 and HCOOH are generally underestimated by the model, while CH3OH and C2H4, the species with the shortest atmospheric lifetimes of the discussed pollution trace gases, are overestimated by CAMS. The good agreement between model and observations for PAN suggests that the general transport pathways and emissions locations are well captured by the model. The poorer agreement for other species is therefore most likely linked to model deficiencies in the representation of loss processes and emission strength.