Key challenges for tropospheric chemistry in the Southern Hemisphere

This commentary paper from the recently formed International Global Atmospheric Chemistry (IGAC) Southern Hemisphere Working Group outlines key issues in atmospheric composition research that particularly impact the Southern Hemisphere. In this article, we present a broad overview of many of the challenges for understanding atmospheric chemistry in the Southern Hemisphere, before focusing in on the most significant factors that differentiate it from the Northern Hemisphere. We present sections on the importance of biogenic emissions and fires in the Southern Hemisphere, showing that these emissions often dominate over anthropogenic emissions in many regions. We then describe how these and other factors influence air quality in different parts of the Southern Hemisphere. Finally, we describe the key role of the Southern Ocean in influencing atmospheric chemistry and conclude with a description of the aims and scope of the newly formed IGAC Southern Hemisphere Working Group.

Tropical tropospheric chemistry and climate change

A systematic programme of monitoring surface ozone and its precursor gases CH4, CO and NOx (NO + NO2) at some selected sites in the Indian region was started under ISRO's geosphere biosphere programme in 1991. Measurements have been made at Ahmedabad an urban polluted site, Gadanki a rural relatively clean site, Gurusikhar a high altitude site representative of the free troposphere and Trivandrum a coastal (relatively clean) site influenced by marine air. The data has been used to study different features of troposphere chemistry in the tropics. Some of the results from this programme relevant to the climate change problem are presented in this paper.

Investigation of weather conditions and tropospheric BrO transport during Bromine Explosion Events in the Arctic and ozone depletion in Ny-Ålesund observed by satellite and ground-based remote sensing

<p align="justify">Bromine Explosion Events (BEEs) have been observed since the late 1990s in the Arctic and Antarctic during polar spring and play an important role in tropospheric chemistry. In a heterogeneous, autocatalytic, chemical chain reaction cycle, inorganic bromine is released from the cryosphere into the troposphere and depletes ozone often to below detection limit. Ozone is a source of the most important tropospheric oxidizing agent OH and the oxidizing capacity and radiative forcing of the troposphere are thus being impacted. Bromine also reacts with gaseous mercury, thereby facilitating the deposition of toxic mercury, which has adverse environmental impacts. C<span lang="en-US">old saline surfaces, such as young sea ice, frost flowers, and snow are likely bromine sources </span><span lang="en-US">during BEEs. </span><span lang="en-US">D</span>ifferent meteorological conditions seem to favor the development of these events: on the one hand, low wind speeds and a stable boundary layer, where bromine can accumulate and deplete ozone, and on the other hand, high wind speeds above approximately 10 m/s with blowing snow and a higher unstable boundary layer. In high wind speed conditions – occurring for example along fronts of polar cyclones – recycling of bromine on snow and aerosol surfaces may take place aloft.</p> <p align="justify">To improve the understanding of weather conditions and bromine sources leading to the development of BEEs, case studies using high resolution S5P TROPOMI retrievals of tropospheric BrO together with meteorological simulations by the WRF model and Lagrangian transport simulations of BrO by FLEXPART-WRF are carried out. WRF simulations show, that high tropospheric BrO columns observed by TROPOMI often coincide with areas of high wind speeds. This probably points to release of bromine from blowing snow with cold temperatures favoring the bromine explosion reactions. However, some BrO plumes are observed over areas with very low wind speed and a stable low boundary layer. To monitor the amount of ozone depleted during a BEE, ozone sonde measurements from Ny-Ålesund are compared with MAX-DOAS BrO profiles. First evaluations show a drastic decrease in ozone, partly below the detection limit, while measuring enhanced BrO values at the same time. <span lang="en-US">In order to analyze </span><span lang="en-US">the possible origin</span><span lang="en-US"> of the BrO </span><span lang="en-US">plume </span><span lang="en-US">arriving in </span><span lang="en-US">Ny-</span><span lang="en-US">Å</span><span lang="en-US">lesund</span><span lang="en-US">, </span><span lang="en-US">and to investigate its transportation route, </span><span lang="en-US">FLEXPART-WRF runs are </span><span lang="en-US">executed </span><span lang="en-US">for the times of observed ozone depletion.</span></p> <p align="justify"> </p> <p align="justify"><em>This work was supported by the</em><em> DFG funded Transregio-project TR 172 “Arctic Amplification </em>(AC)<sup>3</sup><em>“.</em></p>

Measurement report: High contributions of halocarbon and aromatic compounds to atmospheric volatile organic compounds in an industrial area

Volatile organic compounds (VOCs) are key components of tropospheric chemistry. We investigated ambient VOCs in an industrial area in Nanjing, China, between July 2018 and May 2020. The sum of the suite of measured total VOC (TVOC) concentrations was 59.8 ± 28.6 ppbv (part per billion by volume) during the investigation period. About twice the TVOC concentrations were observed in the autumn (83 ± 20 ppbv) and winter (77.5 ± 16.8 ppbv) seasons compared to those in spring (39.6 ± 13.1 ppbv) and summer (38.8 ± 10.2 ppbv). In previous studies in Nanjing, oxygenated VOCs (OVOCs) and halocarbons were not measured, and the current TVOC concentration without halocarbons and OVOCs was similar to the previous investigation in the same study area. However, it was twofold higher than the one reported in the nonindustrial suburban area of Nanjing. Due to the industrial influence, the halocarbons VOC group (14.3 ± 7.3 ppbv, 24 %) was the second-largest contributor to the TVOCs after alkanes (21 ± 7 ppbv, 35 %), which is in contrast with the previous studies in Nanjing and also in almost all other regions in China. Relatively high proportions of halocarbons and aromatics were observed in autumn (25.7 % and 19.3 %, respectively) and winter (25.8 % and 17.6 %, respectively) compared to those in summer (20.4 % and 11.8 %, respectively) and spring (20.3 % and 13.6 %, respectively). According to the potential source contribution function (PSCF), short-distance transport from the surrounding industrial areas and cities was the main reason for the high VOC concentrations in the study area. According to positive matrix factorization (PMF) model results, vehicle-related emissions (33 %–48 %) contributed to the major portion of the ambient VOC concentrations. Aromatics, followed by alkenes, were the top contributors to the loss rate of OH radicals (LOH; 37 % and 32 %, respectively). According to the empirical kinetic modelling approach (EKMA) and relative incremental reactivity (RIR) analysis, the study area was in the VOC-sensitive regime for ozone (O3) formation during all measurement seasons. Therefore, alkenes and aromatics emissions from automobiles need to be decreased to reduce secondary air pollution formation in the study area.

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.

Volatile Organic Compound Composition of Urban Air in Nairobi, Kenya and Lagos, Nigeria

Sub-Saharan Africa is seeing rapid urbanization, with the population of cities such as Lagos and Nairobi growing at a rate of 3–4% a year. The region is extremely under-sampled for all air pollutants, particularly VOCs, which are useful markers for source apportionment as well as toxic in their own right. There are many contributors to air pollution in the region, and studies examining fine particulate pollution implicate traffic as the primary source in urban areas. In this pilot study, VOCs were analysed at a selection of roadside and urban background locations in Nairobi and Lagos, and 74 VOCs were quantified. GC×GC–MS/FID analysis revealed all locations were dominated by hydrocarbons typical of vehicle emissions, with the aromatic hydrocarbons benzene and toluene among the most abundant VOCs. Typical personal exposure scenarios for citizens of the cities were calculated to far exceed those of a resident in a city in Europe/US. Finally, the calculated ozone forming potential of the VOCs measured was found to be similarly high to other large cities studied with similar air pollution problems. Further study is therefore essential to determine the full extent of VOC pollution in the region and its impact on tropospheric chemistry.

Theoretical spectroscopic study of acetyl (CH3CO), vinoxy (CH2CHO), and 1-methylvinoxy (CH3COCH2) radicals. Barrierless formation processes of acetone in the gas phase

Background: Acetone is present in the earth´s atmosphere and extra-terrestrially. The knowledge of its chemical history in these environments represents a challenge with important implications for global tropospheric chemistry and astrochemistry. The results of a search for efficient barrierless pathways producing acetone from radicals in the gas phase are described in this paper. The spectroscopic properties of radicals needed for their experimental detection are provided. Methods: The reactants were acetone fragments of low stability and small species containing C, O and H atoms. Two exergonic bimolecular addition reactions involving the radicals CH3, CH3CO, and CH3COCH2, were found to be competitive according to the kinetic rates calculated at different temperatures. An extensive spectroscopic study of the radicals CH3COCH2 and CH3CO, as well as the CH2CHO isomer, was performed. Rovibrational parameters, anharmonic vibrational transitions, and excitations to the low-lying excited states are provided. For this purpose, RCCSD(T)-F12 and MRCI/CASSCF calculations were performed. In addition, since all the species presented non-rigid properties, a variational procedure of reduced dimensionality was employed to explore the far infrared region. Results: The internal rotation barriers were determined to be V3=143.7 cm-1 (CH3CO), V2=3838.7 cm-1 (CH2CHO) and V3=161.4 cm-1 and V2=2727.5 cm-1 (CH3COCH2).The splitting of the ground vibrational state due to the torsional barrier have been computed to be 2.997 cm-1, 0.0 cm-1, and 0.320 cm-1, for CH3CO, CH2CHO, and CH3COCH2, respectively. Conclusions: Two addition reactions, H+CH3COCH2 and CH3+CH3CO, could be considered barrierless formation processes of acetone after considering all the possible formation routes, starting from 58 selected reactants, which are fragments of the molecule. The spectroscopic study of the radicals involved in the formation processes present non-rigidity. The interconversion of their equilibrium geometries has important spectroscopic effects on CH3CO and CH3COCH2, but is negligible for CH2CHO.

Estimating lightning NOx production over South Africa

Nitrogen oxides (NOx = NO + NO2) are toxic air pollutants and play a significant role in tropospheric chemistry. Global NOx hotspots are the industrialised regions of the USA, Europe, Middle East, East Asia and eastern parts of South Africa. Lightning is one of the many natural and anthropogenic sources of NOx to the troposphere. It plays a role in the formation of particulate matter and tropospheric ozone, which are both linked to harmful health and climate effects. The discourse on NOx over the southern African continent has mainly focused on anthropogenic sources. However, lightning is known to be a main source of tropospheric NOx globally. It is therefore important to understand its contribution to the national and global NOx budget. Data from the South African Lightning Detection Network were used to approximate the influence of lightning on the NOx load over the country, and to develop a gridded data set of lightning-produced NOx (LNOx) emissions for the period 2008 2015. The Network monitors cloud-toground lightning strikes; and theoretically has a detection efficiency of 90% and a location accuracy of 0.5 km. An emission factor of 11.5 kg NO2/flash was employed to calculate the LNOx budget of ~270 kt NO2/year. The calculated LNOx was 14% of the total NOx emission estimates published in the EDGAR v4.2 data set for the year 2008. The LNOx emission inventory will improve model performance and prediction, and enhance the understanding of the contribution of lightning to ambient NO2.

Heterogeneity and chemical reactivity of the remote troposphere defined by aircraft measurements

The NASA Atmospheric Tomography (ATom) mission built a photochemical climatology of air parcels based on in situ measurements with the NASA DC-8 aircraft along objectively planned profiling transects through the middle of the Pacific and Atlantic oceans. In this paper we present and analyze a data set of 10 s (2 km) merged and gap-filled observations of the key reactive species driving the chemical budgets of O3 and CH4 (O3, CH4, CO, H2O, HCHO, H2O2, CH3OOH, C2H6, higher alkanes, alkenes, aromatics, NOx, HNO3, HNO4, peroxyacetyl nitrate, other organic nitrates), consisting of 146 494 distinct air parcels from ATom deployments 1 through 4. Six models calculated the O3 and CH4 photochemical tendencies from this modeling data stream for ATom 1. We find that 80 %–90 % of the total reactivity lies in the top 50 % of the parcels and 25 %–35 % in the top 10 %, supporting previous model-only studies that tropospheric chemistry is driven by a fraction of all the air. In other words, accurate simulation of the least reactive 50 % of the troposphere is unimportant for global budgets. Surprisingly, the probability densities of species and reactivities averaged on a model scale (100 km) differ only slightly from the 2 km ATom data, indicating that much of the heterogeneity in tropospheric chemistry can be captured with current global chemistry models. Comparing the ATom reactivities over the tropical oceans with climatological statistics from six global chemistry models, we find excellent agreement with the loss of O3 and CH4 but sharp disagreement with production of O3. The models sharply underestimate O3 production below 4 km in both Pacific and Atlantic basins, and this can be traced to lower NOx levels than observed. Attaching photochemical reactivities to measurements of chemical species allows for a richer, yet more constrained-to-what-matters, set of metrics for model evaluation.