The 50 most-cited articles in Atmospheric chemistry and physics, 2022

Abstract. We review the capability of current and scheduled satellite observations of atmospheric methane in the shortwave infrared (SWIR) to quantify methane emissions from the global scale down to point sources. We cover retrieval methods, precision and accuracy requirements, inverse and mass balance methods to infer emissions, source detection thresholds, and observing system completeness. We classify satellite instruments as area flux mappers and point source imagers, with complementary attributes. Area flux mappers are high-precision (< 1 %) instruments with 0.1–10 km pixel size designed to quantify total methane emissions on regional to global scales. Point source imagers are fine-pixel (< 60 m) instruments designed to quantify individual point sources by imaging of the plumes. Current area flux mappers include GOSAT (2009–present), which provides a high-quality record for interpretation of long-term methane trends, and TROPOMI (2018–present) which provides global continuous daily mapping to quantify emissions on regional scales. Current point source imagers include the GHGSat…

Abstract. This review provides a community’s perspective on air quality research focussing mainly on developments over the past decade. The article provides perspectives on current and future challenges as well as research needs for selected key topics. While this paper is not an exhaustive review of all research areas in the field of air quality, we have selected key topics that we feel are important from air quality research and policy perspectives. After providing a short historical overview, this review focuses on improvements in characterising sources and emissions of air pollution, new air quality observations and instrumentation, advances in air quality prediction and forecasting, understanding interactions of air quality with meteorology and climate, exposure and health assessment, and air quality management and policy. In conducting the review, specific objectives were (i) to address current developments that push the boundaries of air quality research forward, (ii) to highlight the emerging prominent gaps of knowledge in air quality research and (iii) and to make…

Abstract. Hydrogen is quickly gaining attention as a “clean” fuel that can support a transition to a decarbonized energy system. Given the urgency to decarbonize global energy systems, governments and industry are moving ahead with efforts to increase hydrogen technologies, infrastructure, and applications at an unprecedented pace, including billions in national incentives and direct investments. While zero- and low-carbon hydrogen hold great promise to help solve some of the world’s most pressing energy challenges, hydrogen is also a short-lived indirect greenhouse gas whose warming impact is not well-characterized. There are multiple areas of uncertainty. To date, hydrogen’s warming effects have been primarily characterized using the GWP-100 metric—which is misleading for short-lived gases, such as hydrogen, as it obscures impacts on shorter timescales. Furthermore, hydrogen is a small molecule known to easily leak into the atmosphere; however, the total amount of leakage in current hydrogen systems remains unknown, with the analytical capacity to accurately measure leakage in…

Abstract. In the past decade, ozone (O3) pollution has become a severe environmental problem in major cities in China. Here, based on available observational records, we investigated the long-term trend of ozone pollution in China during 2014–2020. Ozone concentrations were higher in urban areas than in non-urban areas. During these seven years, the highest ozone concentrations primarily occurred in summer in northern China, and in autumn or spring in southern China. Although ozone precursors, including nitrogen oxides (NOx) and carbon monoxide (CO), continuously decreased throughout the seven years, four ozone metrics that were used to characterize ozone exposure levels increased from 2014 to 2017 and reached a plateau after 2017. The long-term trend of ozone concentrations differed across seasons; especially from 2019 to 2020 when ozone concentrations decreased in summer and increased in winter. To analyze the causes of this observed trend, a photochemical box model was used to investigate the change in ozone sensitivity regime in two representative cities – Beijing and Shanghai.…

Abstract. Particulate matter (PM2.5) concentrations in China have decreased significantly in recent years, but surface ozone (O3) concentrations showed upward trends at more than 71 % of air quality monitoring stations from 2015 to 2021. To reveal causes of O3 increases, O3 production sensitivity is accurately diagnosed by deriving regional threshold values of satellite tropospheric formaldehyde-to-NO2 ratio (HCHO / NO2), and O3 responses to precursors changes are evaluated by tracking volatile organic compounds (VOCs) and NOx with satellite HCHO and NO2. Results showed that the HCHO / NO2 ranges of transition from VOC-limited to NOx-limited regimes vary apparently among Chinese regions. VOC-limited regimes are widespread found over megacity clusters (North China Plain, Yangtze River Delta, and Pearl River Delta) and concentrated in developed cities (such as Chengdu, Chongqing, Xi’an, and Wuhan). NOx-limited regimes dominate most of the remaining areas. From 2013 to 2021, satellite NO2 and HCHO columns showed an annual decrease of 3.7 % and an increase of 0.1 %, respectively,…

A typical multi-day ozone (O 3 ) pollution event was chosen to explore the atmospheric oxidation capacity (AOC), OH reactivity, radical chemistry, and O 3 pollution mechanism in a coastal city of southeastern China, with an observation-based model coupled to the Master Chemical Mechanism (OBM-MCM). The hydroxyl radical (OH) was the predominant oxidant (90 ± 25 %) for daytime AOC, while the NO 3 radical played an important role in AOC during the nighttime (72 ± 9 %). Oxygenated volatile organic compounds (OVOCs; 30 ± 8 %), NO 2 (29 ± 8 %), and CO (25 ± 5 %) were the dominant contributors to OH reactivity, accelerating the production of O 3 and recycling of RO x radicals (RO x = OH + HO 2 + RO 2 ). Photolysis of nitrous acid (HONO, 33 ± 14 %), O 3 (25 ± 13 %), formaldehyde (HCHO, 20 ± 5 %), and other OVOCs (17 ± 2 %) was a major RO x source, which played an initiation role in atmospheric oxidation processes. Combined with regional transport analysis, the reasons for this O 3 episode were the accumulation of local photochemical production and regional transport. The results of…

Abstract. Although a remarkable reduction in the frequency of sand and dust storms (SDSs) in the past several decades has been reported over northern China (NC), two unexpected mega SDSs occurred on March 15–20, 2021 and March 27–29, 2021 (abbreviated as the “3.15” and “3.27” SDS events), which has reawakened widespread concern. This study characterizes the origins, transport processes, magnitudes of impact, and meteorological causes of these two SDS events using a long-term (2000–2021) dust optical depth (DOD) dataset retrieved from MODIS measurements and a comprehensive set of multiple satellite and ground-based observations combined with atmospheric reanalysis data. During the 3.15/3.27 event, the invasion of dust plumes greatly degraded the air quality over large areas of NC, reaching extremely hazardous levels, with the maximum daily mean PM10 concentration of 7058 µg m−3 (2670 µg m−3) recorded on March 15 (28). CALIOP observations show that during the 3.15 event the dust plume was lifted to an altitude of 4–8 km, and its range of impact extended from the dust source to the…

Abstract. We quantify methane emissions in China and the contributions from different sectors by inverse analysis of 2019 TROPOMI satellite observations of atmospheric methane. The inversion uses as prior estimate the national sector-resolved anthropogenic emission inventory reported by the Chinese government to the United Nations Framework Convention on Climate Change (UNFCCC) and thus serves as a direct evaluation of that inventory. Emissions are optimized with a Gaussian mixture model (GMM) at up to 0.25° × 0.3125° resolution. The optimization is done analytically assuming lognormally distributed errors on prior emissions. Errors and information content on the optimal estimates are obtained directly from the analytical solution and also through a 36-member inversion ensemble. Our optimal estimate for total anthropogenic emissions in China is 65.0 (57.7–68.4) Tg a-1, where parentheses indicate uncertainty range. Contributions from individual sectors include 16.6 (15.6–17.6) Tg a-1 for coal, 2.3 (1.8–2.5) for oil, 0.29 (0.23–0.32) for gas, 17.8 (15.1–21.0) for livestock, 9.3…

Abstract. The Orbiting Carbon Observatory 2 (OCO-2) satellite has been provided information to estimate carbon dioxide (CO2) fluxes at global and regional scales since 2014 through the combination of CO2 retrievals with top-down atmospheric inversion methods. Column average CO2 dry air mole fraction retrievals has been constantly improved. A bias correction has been applied in the OCO-2 version 9 retrievals compared to the previous OCO-2 version 7r improving data accuracy and coverage. We study an ensemble of ten atmospheric inversions all characterized by different transport models, data assimilation algorithm and prior fluxes using first OCO-2 v7 in 2015-2016 and then OCO-2 version 9 land observations for the longer period 2015- 2018. Inversions assimilating in situ (IS) measurements have been also used to provide a baseline against which to compare the satellite-driven results. The times series at different scales (going from global to regional scales) of the models emissions are analyzed and compared to each experiments using either OCO-2 or IS data. We then evaluate the…

Abstract. Mineral dust impacts key processes in the Earth system, including the radiation budget, clouds, and nutrient cycles. We evaluate dust aerosols in 16 models participating in the sixth phase of the Coupled Model Intercomparison Project (CMIP6) against multiple reanalyses and satellite observations. Most models, and particularly the multi-model ensemble mean (MEM), capture the spatial patterns and seasonal cycles of global dust processes well. However, large uncertainties and inter-model diversity are found. For example, global dust emissions, primarily driven by model-simulated surface winds, vary by a factor of 5 across models, while the MEM estimate is double the amount in reanalyses. The ranges of CMIP6 model-simulated global dust emission, deposition, burden and optical depth (DOD) are larger than previous generations of models. Models present considerable disagreement in dust seasonal cycles over North China and North America. Here, DOD values are overestimated by most CMIP6 models, with the MEM estimate 1.2–1.7 times larger compared to satellite and reanalysis…

Abstract. Anthropogenic aerosols exert a cooling influence that offsets part of the greenhouse gas warming. Due to their short tropospheric lifetime of only up to several days, the aerosol forcing responds quickly to emissions. Here we present and discuss the evolution of the aerosol forcing since 2000. There are multiple lines of evidence that allow to robustly conclude that the anthropogenic aerosol effective radiative forcing – both aerosol-radiation and aerosol-cloud interactions – has become globally less negative, i.e. that the trend in aerosol effective radiative forcing changed sign from negative to positive. Bottom-up inventories show that anthropogenic primary aerosol and aerosol precursor emissions declined in most regions of the world; observations related to aerosol burden show declining trends, in particular of the fine-mode particles that make up most of the anthropogenic aerosols; satellite retrievals of cloud droplet numbers show trends consistent in sign, as do observations of top-of-atmosphere radiation. Climate model results, including a revised set that is…

Abstract. Coordinated control of fine particulate matter (PM2.5) and ozone (O3) has become a new and urgent issue for China’s air pollution control. Biogenic volatile organic compounds (BVOCs) are important precursors of O3 and secondary organic aerosol (SOA) formation. China experienced a rapid increase in BVOC emissions as a result of increased vegetation biomass. We applied WRF-Chem3.8 coupling with MEGAN2.1 to conduct long-term simulations for impacts of BVOC emissions on O3 and SOA during 1981–2018, using the emission factors extrapolated by localized emission rates and annual vegetation biomass. In summer of 2018, BVOC emissions are 9.91 Tg (in June), which lead to an average increase of 8.6 ppb (16.75 % of the total) in daily maximum 8-h (MDA8) O3 concentration and 0.84 μg m−3 (73.15 % of the total) in SOA over China. The highest contribution to O3 is concentrated in the Great Khingan Mountains, Qinling Mountains, and most southern regions, while southern areas for SOA. Isoprene has the greatest contribution to O3 while monoterpene has the largest SOA production. BVOC…

Abstract. Aerosol indirect radiative forcing (IRF), which characterizes how aerosols alter cloud formation and properties, is very sensitive to the preindustrial (PI) aerosol burden. Dimethyl sulfide (DMS), emitted from the ocean, is a dominant natural precursor of non-sea-salt sulfate in the PI and pristine present-day (PD) atmospheres. Here we revisit the atmospheric oxidation chemistry of DMS, particularly under pristine conditions, and its impact on aerosol IRF. Based on previous laboratory studies, we expand the simplified DMS oxidation scheme used in the Community Atmospheric Model version 6 with chemistry (CAM6-chem) to capture the OH-addition pathway as well as the H-abstraction pathway and the associated isomerization branch. These additional oxidation channels of DMS produce several stable intermediate compounds, e.g., methanesulfonic acid (MSA) and hydroperoxymethyl thioformate (HPMTF), delay the formation of sulfate, and hence, alter the spatial distribution of sulfate aerosol and radiative impacts. The expanded scheme improves the agreement between modeled and observed…

Aerosol-cloud interactions (ACIs) are considered to be the most uncertain driver of present-day radiative forcing due to human activities. The nonlinearity of cloud-state changes to aerosol perturbations make it challenging to attribute causality in observed relationships of aerosol radiative forcing. Using correlations to infer causality can be challenging when meteorological variability also drives both aerosol and cloud changes independently. Natural and anthropogenic aerosol perturbations from well-defined sources provide "opportunistic experiments" (also known as natural experiments) to investigate ACI in cases where causality may be more confidently inferred. These perturbations cover a wide range of locations and spatiotemporal scales, including point sources such as volcanic eruptions or industrial sources, plumes from biomass burning or forest fires, and tracks from individual ships or shipping corridors. We review the different experimental conditions and conduct a synthesis of the available satellite datasets and field campaigns to place these opportunistic experiments on…

Abstract. Around 5 % of anthropogenic radiative forcing (RF) is attributed to aviation CO2 and non-CO2 impacts. This paper quantifies aviation emissions and contrail climate forcing in the North Atlantic, one of the world’s busiest air traffic corridors, over 5 years. Between 2016 and 2019, growth in CO2 (+3.13 % per annum, p.a.) and nitrogen oxide emissions (+4.5 % p.a.) outpaced increases in flight distance (+3.05 % p.a.). Over the same period, the annual mean contrail cirrus net RF (204–280 mW m-2) showed significant interannual variability caused by variations in meteorology. Responses to COVID-19 caused significant reductions in flight distance travelled (-66 %), CO2 emissions (-71 %), and the contrail net RF (-66 %) compared to the prior one-year period. Around 12 % of all flights in this region cause 80 % of the annual contrail energy forcing, and the factors associated with strongly warming/cooling contrails include seasonal changes in meteorology and radiation, time of day, background cloud fields, and engine-specific non-volatile particulate matter (nvPM) emissions.…

Abstract. Even though the Arctic is remote, aerosol properties observed there are strongly influenced by anthropogenic emissions from outside the Arctic. This is particularly true for the so-called Arctic haze season (January through April). In summer (June through September), when atmospheric transport patterns change, and precipitation is more frequent, local Arctic, i.e. natural sources of aerosols and precursors, play an important role. Over the last decades, significant reductions in anthropogenic emissions have taken place. At the same time a large body of literature shows evidence that the Arctic is undergoing fundamental environmental changes due to climate forcing, leading to enhanced emissions by natural processes that may impact aerosol properties. In this study, we analyze nine aerosol chemical species and four particle optical properties from ten Arctic observatories (Alert, Gruvebadet, Kevo, Pallas, Summit, Thule, Tiksi, Barrow, Villum, Zeppelin) to understand changes in anthropogenic and natural aerosol contributions. Variables include equivalent black carbon,…

Abstract. The tropopause layer plays a key role in manifold processes in atmospheric chemistry and physics. Here we compare the representation and characteristics of the lapse rate tropopause according to the definition of the World Meteorological Organization (WMO) as estimated from European Centre for Medium-Range Weather Forecasts (ECMWF) reanalysis data. Our study is based on ten-year records (2009 to 2018) of ECMWF's state-of-the-art reanalysis ERA5 and its predecessor ERA-Interim. The intercomparison reveals notable differences between ERA5 and ERA-Interim tropopause data, in particular on small spatiotemporal scales. The monthly mean differences of ERA5 minus ERA-Interim tropopause heights vary between −300 m at the transition from the tropics to the extratropics (near 30° S and 30° N) to 150 m around the equator. Mean tropopause temperatures are mostly lower in ERA5 than in ERA-Interim, with a maximum difference of up to −1.5 K in the tropics. Monthly standard deviations of tropopause heights of ERA5 are up to 350 m or 60 % larger than for ERA-Interim. Monthly standard…

Abstract. Surface ozone concentrations have been increasing in many regions of China for the past few years, in contrast to policy-driven declines in other key air pollutants such as particulate matter. While the central role of meteorology in modulating ozone pollution is widely acknowledged, its quantitative contribution remains highly uncertain. Here, we use a data-driven machine learning approach to assess the impacts of meteorology on surface ozone variations in China for the years 2015 to 2019, considering the months of highest ozone pollution from April to October. To quantify the importance of various meteorological driver variables, we apply non-linear random forest regression (RFR) and linear ridge regression (RR) to learn relationships between meteorological variability and surface ozone in China, and contrast the results to those obtained with the widely used multiple linear regression (MLR) and stepwise MLR. We show that RFR outperforms the three linear methods when predicting ozone using only local meteorological predictor variables. This implies the importance of…

Abstract. We have constructed an atmospheric inversion framework based on TM5 4DVAR to jointly assimilate measurements of methane and δ13C of methane in order to estimate source-specific methane emissions. Here we present global emission estimates from this framework for the period 1999–2016. We assimilate a newly constructed, multi-agency database of CH4 and δ13CH4 measurements. We find that traditional CH4-only atmospheric inversions are unlikely to estimate emissions consistent with atmospheric δ13CH4 data, and assimilating δ13CH4 data is necessary to deriving emissions consistent with both measurements. Our framework attributes ca. 85 % of the post-2007 growth in atmospheric methane to microbial sources, with about half of that coming from the Tropics between 23.5° N and 23.5° S. This contradicts the attribution of the recent growth in the methane budget of the Global Carbon Project (GCP). We find that the GCP attribution is only consistent with our top-down estimate in the absence of δ13CH4 data. We find that at global and continental scales, δ13CH4 data can separate microbial…

Abstract. Satellite observations of the high-resolution instrument TROPOMI on Sentinel-5 Precursor can be used to observe nitrogen dioxide (NO2) at city scales, to quantify short time variability of NOx emissions and lifetime on a seasonal and daily basis. In this study, two years of TROPOMI NO2 data, having a spatial resolution of 3.5 km x 5.5 km, together with ECMWF ERA5 wind data have been analyzed. NOx lifetimes and emission fluxes are calculated for 45 different NOx sources comprising cities and power plants, distributed around the world. The retrieved emissions are lower than the bottom-up emission inventories from EDGAR v5.0 but are in good agreement with other TROPOMI based estimates. Separation into seasons shows a clear seasonal dependence of emissions with in general the highest emissions during winter, except for cities in hot dessert climates, where the opposite is found. The NOx lifetime shows a systematic latitudinal dependence with an increase in lifetime from two to eight hours with latitude but only a weak seasonal dependence. For most of the 45 sources, a clear…

Abstract. Quantification and attribution of long-term tropospheric ozone trends are critical for understanding the impact of human activity and climate change on atmospheric chemistry, but are also challenged by the limited coverage of long-term ozone observations in the free troposphere where ozone has higher production efficiency and radiative potential compared to that at the surface. In this study, we examine observed tropospheric ozone trends, their attributions, and radiative impacts from 1995–2017 using aircraft observations from the In-Service Aircraft for a Global Observing System database (IAGOS), ozonesondes, and a multi-decadal GEOS-Chem chemical model simulation. IAGOS observations above 11 regions in the Northern Hemisphere and 19 of 27 global ozonesonde sites have measured increases in tropospheric ozone (950–250 hPa) by 2.7 ± 1.7 and 1.9 ± 1.7 ppbv decade-1 on average, respectively, with particularly large increases in the lower troposphere (950–800 hPa) above East Asia, Persian Gulf, India, northern South America, Gulf of Guinea, and Malaysia/Indonesia by 2.8 to…

Abstract. We report on updated trends using different merged zonal mean total ozone datasets from satellite and ground-based observations for the period from 1979 to 2020. This work is an update from the trends reported in Weber et al. (2018) using the same datasets up to 2016. Merged datasets used in this study include NASA MOD v8.7 and NOAA Cohesive Data (COH) v8.6, both based on data from the series of Solar Backscatter UltraViolet (SBUV), SBUV-2, and Ozone Mapping and Profiler Suite (OMPS) satellite instruments (1978–present) as well as the Global Ozone Monitoring Experiment (GOME)-type Total Ozone (GTO-ECV) and GOME-SCIAMACHY-GOME-2 (GSG) merged datasets (both 1995–present), mainly comprising satellite data from GOME, SCIAMACHY, OMI, GOME-2A, -2B, and TROPOMI. The fifth dataset consists of the annual mean zonal mean data from ground-based measurements collected at the World Ozone and UV Radiation Data Center (WOUDC). Trends were determined by applying a multiple linear regression (MLR) to annual mean zonal mean data. The addition of four more years consolidated the fact that…

High spatial resolution PM 2.5 data covering a long time period are urgently needed to support population exposure assessment and refined air quality management. In this study, we provided complete-coverage PM 2.5 predictions with a 1 km spatial resolution from 2000 to the present under the Tracking Air Pollution in China (TAP, http://tapdata.org.cn/, last access: 3 October 2022) framework. To support high spatial resolution modeling, we collected PM 2.5 measurements from both national and local monitoring stations. To correctly reflect the temporal variations in land cover characteristics that affected the local variations in PM 2.5 , we constructed continuous annual geoinformation datasets, including the road maps and ensemble gridded population maps, in China from 2000 to 2021. We also examined various model structures and predictor combinations to balance the computational cost and model performance. The final model fused 10 km TAP PM 2.5 predictions from our previous work, 1 km satellite aerosol optical depth retrievals, and land use parameters with a random forest model. Our…

Abstract. The emissions of hydrofluorocarbons (HFCs) have increased significantly in the past two decades, primarily as a result of the phaseout of ozone depleting substances under the Montreal Protocol and the use of HFCs as their replacements. Projections from 2015 showed large increases in HFC use and emissions in this century in the absence of regulations, contributing up to 0.5 °C to global surface warming by 2100. In 2019, the Kigali Amendment to the Montreal Protocol came into force with the goal of limiting the use of HFCs globally, and currently, regulations to limit the use of HFCs are in effect in several countries. Here, we analyze trends in HFC emissions inferred from observations of atmospheric abundances and compare them with previous projections. Total CO2-eq inferred HFC emissions continue to increase through 2019 (to about 0.8 GtCO2-eq yr−1) but are about 20 % lower than previously projected for 2017–2019, mainly because of lower global emissions of HFC-143a. This indicates that HFCs are used much less in industrial and commercial refrigeration (ICR) applications…

Dust particles from high latitudes have a potentially large local, regional, and global significance to climate and the environment as short-lived climate forcers, air pollutants, and nutrient sources. Identifying the locations of local dust sources and their emission, transport, and deposition processes is important for understanding the multiple impacts of high-latitude dust (HLD) on the Earth's systems. Here, we identify, describe, and quantify the source intensity (SI) values, which show the potential of soil surfaces for dust emission scaled to values 0 to 1 concerning globally best productive sources, using the Global Sand and Dust Storms Source Base Map (G-SDS-SBM). This includes 64 HLD sources in our collection for the northern (Alaska, Canada, Denmark, Greenland, Iceland, Svalbard, Sweden, and Russia) and southern (Antarctica and Patagonia) high latitudes. Activity from most of these HLD sources shows seasonal character. It is estimated that high-latitude land areas with higher (SI ≥0.5), very high (SI ≥0.7), and the highest potential (SI ≥0.9) for dust emission cover >1…

Abstract. Volatile organic compounds (VOCs) regulate atmospheric oxidation capacity, and the reactions of VOCs are key in understanding ozone formation and its mitigation strategies. When evaluating its impact, most previous studies did not fully consider the role of oxygenated VOCs due to limitations of measurement technology. By using a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) combined with gas chromatography mass spectrometer (GC-MS) technology, we are able to quantify a large number of oxygenated VOCs in a representative urban environment in southern China. Based on the new dataset, we find that non – formaldehyde (HCHO) OVOCs can contribute large fractions (22–44 %) of total ROX radical production, comparable or larger than the contributions from nitrous acid and formaldehyde. We demonstrate that constraints using OVOCs observations are essential in modeling radical and ozone production, as modelled OVOCs can be substantially lower than measurements, potentially due to primary emissions and/or missing secondary sources. Our results show that models…

Abstract. Volatile organic compounds (VOCs) tend to be consumed by atmospheric oxidants, resulting in substantial photochemical loss during transport. An observation-based model is used to evaluate the influence of photochemical loss of VOCs on the sensitivity regime and mechanisms of ozone formation. Our results showed that a VOC-limited regime based on the observed VOC concentrations shifted to a transition regime with the photochemical initial concentration of VOCs (PIC-VOCs) in the morning. The net ozone formation rate was underestimated by 3 ppb h−1 (36 ppb day−1) based on the PIC-VOCs. The relative contribution of the RO2 path to ozone production based on the PIC-VOCs accordingly increased by 13.4 %, particularly, the contribution of alkenes derived RO2 increased around 10.2 %. The contribution of local photochemistry might be underestimated to both local and regional ozone pollution if the consumed VOCs was not accounted for, and policy-making on ozone pollution prevention should focus on high-reactivity VOCs.

Abstract. Emissions of ammonia (NH3) to the atmosphere impact human health, climate, and ecosystems through their critical contributions to secondary aerosol formation. Estimation of NH3 emissions is associated with large uncertainties because of inadequate knowledge about agricultural sources. Here, we use satellite observations from the Infrared Atmospheric Sounding Interferometer (IASI) and simulations from the GEOS-Chem model to constrain global NH3 emissions over the period of 2008–2018. We update the prior NH3 emission fluxes with the ratio between biases in simulated NH3 concentrations and effective NH3 lifetimes against the loss of the NHx family. In contrast to about a factor of two discrepancies between top-down and bottom-up emissions found in previous studies, our method results in a global land NH3 emission of 79 (71–96) Tg a-1, ~30 % higher than the bottom-up estimates. Regionally, we find that the bottom-up inventory underestimates NH3 emissions over the South America and tropical Africa by 60–70 %, indicating under-representation of agricultural sources in these…

Abstract. We present an updated version of the Global Fuel Exploitation Inventory (GFEI) for methane emissions and evaluate it with results from global inversions of atmospheric methane observations from satellite (GOSAT) and in situ platforms (GLOBALVIEWplus). GFEI allocates methane emissions from oil, gas, and coal sectors and subsectors to a 0.1° × 0.1° grid by using the national emissions reported by individual countries to the United Nations Framework Convention on Climate Change (UNFCCC) and mapping them to infrastructure locations. Our updated GFEI v2 gives annual emissions for 2010–2019 that incorporate the most recent UNFCCC national reports, new oil/gas well locations, and improved spatial distribution of emissions for Canada, Mexico, and China. Russia's oil/gas emissions decrease by 83 % in its latest UNFCCC report while Nigerian emissions increase sevenfold, reflecting changes in assumed emission factors. Global gas emissions in GFEI v2 show little net change from 2010 to 2019 while oil emissions decrease and coal emissions slightly increase. Global emissions in GFEI v2…

Abstract. Vanillin (VL), a phenolic aromatic carbonyl abundant in biomass burning emissions, forms triplet excited states (3VL*) under simulated sunlight leading to aqueous secondary organic aerosol (aqSOA) formation. This direct photosensitized oxidation of VL was compared with nitrate-mediated VL photo-oxidation under atmospherically relevant cloud and fog conditions, through examining the VL decay kinetics, product compositions, and light absorbance changes. The majority of the most abundant products from both VL photo-oxidation pathways were potential Brown carbon (BrC) chromophores. In addition, both pathways generated oligomers, functionalized monomers, and oxygenated ring-opening products, but nitrate promoted functionalization and nitration, which can be ascribed to its photolysis products (•OH, •NO2, and N(III), NO2- or HONO). Moreover, a potential imidazole derivative observed from nitrate-mediated VL photo-oxidation suggested that ammonium may be involved in the reactions. The effects of secondary oxidants from 3VL*, pH, the presence of volatile organic compounds (VOCs)…

Abstract. We use a combination of space-borne instruments (CALIOP, OMPS-LP, IASI, MLS, ALADIN, GEOs) to study the unprecedented stratospheric plume after the Hunga Tonga eruption of 15 January 2022. The plume was formed of two initial clouds at 30 and 28 km mostly composed of sub-micronic sulphate particles without ashes, washed-out within the first hours. The large amount of water vapour injected led to a fast conversion of SO2 to sulphates and the fast descent of the plume over the first three weeks. While SO2 returned to background levels by the end of January, the sulphate plume persisted until June, mainly confined between 20° N and 35° S due to the zonal symmetry of the summer stratospheric circulation at 24–25 km. As they grew through hydration and coagulation, the sedimenting sulphate particles separated from the ascending moisture entrained in the Brewer-Dobson circulation. IASI-derived sulphate aerosol optical depths show that the aerosol plume was not simply diluted and dispersed passively but rather organized in concentrated patches. ALADIN-AEOLUS winds suggest that…

Abstract. The aim of this paper is two-fold: to provide guidance on how to best interpret TROPOMI trace gas retrievals and to highlight how TROPOMI trace gas data can be used to understand event-based impacts on air quality from regional to city-scales around the globe. For this study, we present the observed changes in the atmospheric column amounts of five trace gases (NO2, SO2, CO, HCHO and CHOCHO) detected by the Sentinel-5P TROPOMI instrument, driven by reductions of anthropogenic emissions due to COVID-19 lockdown measures in 2020. We report clear COVID-19-related decreases in NO2 concentrations on all continents. For megacities, reductions in column amounts of tropospheric NO2 range between 14 % and 63 %. For China and India supported by NO2 observations, where the primary source of anthropogenic SO2 is coal-fired power generation, we were able to detect sector-specific emission changes using the SO2 data. For HCHO and CHOCHO, we consistently observe anthropogenic changes in two-week averaged column amounts over China and India during the early phases of the lockdown periods.…

A large population in China has been exposed to both severe ozone (O 3 ) pollution and extreme heat under global warming. Here, the spatiotemporal characteristics of coupled extremes in surface O 3 and heat (OPCs) over China are investigated using surface observations, a process-based chemical transport model (GEOS-Chem), and multi-model simulations from Phase 6 of the Coupled Model Intercomparison Project (CMIP6). North China Plain (NCP; 37–41 ∘ N; 114–120 ∘ E) is identified as a hot spot of OPCs, where more than half of the O 3 pollution days are accompanied by high temperature extremes. OPCs over NCP exceeded 40 d during 2014–2019, exhibiting an increasing trend. Both O 3 concentrations and temperatures are elevated during OPCs compared with O 3 pollution days occurring individually (OPIs). Therefore, OPCs impose more severe health impacts to humans than OPIs, but the stronger health effects are mainly driven by the higher temperatures. GEOS-Chem simulations further reveal that enhanced chemical production resulting from hot and stable atmospheric conditions under anomalous…

Abstract. The increasing ozone (O3) pollution and high fraction of secondary organic aerosols (SOA) in fine particle mass highlighted the importance of volatile organic compounds (VOCs) in air pollution control. In this work, a campaign of comprehensive field observations was conducted at an urban site in Beijing, from December 2018 to November 2019, to identify the composition, sources, and secondary transformation potential of VOCs. The total mixing ratio of the 95 quantified VOCs (TVOC) observed in this study ranged from 5.5–118.7 ppbv with the mean value of 34.9 ppbv, and the contemporaneous mixing ratios of TVOC was significantly lower than those observed in 2014 and 2016, confirming the effectiveness of VOCs emission control measures in Beijing in recent years. Alkanes, OVOCs and halocarbons were the dominant chemical groups, accounting for 75–81 % of the TVOCs across the sampling months. High and low-O3/PM2.5 months as well as several O3/PM2.5 polluted days were identified during the sampling period. By deweathered calculation, we found that high O3/PM2.5 levels were due to…

Abstract. Ambient nitrate has been of increasing concern in PM2.5, while there are still large uncertainties in quantifying the formation of nitrate aerosol. The formation pathways of nitrate aerosol at an urban site and a suburban site in the Pearl River Delta (PRD) are investigated using an observation-constrained box model. Throughout the campaigns, aerosol pollution episodes were constantly accompanied with the increase of nitrate concentrations and fractions at both urban and suburban sites. The simulations demonstrate that chemical reactions in the daytime and at night both contributed significantly to formation of nitrate in the boundary layer at the two sites. However, nighttime reactions predominately occurred aloft in the residual layer at the urban site and downward transport from the residual layer in the morning are important source (53 %) for surface nitrate at the urban site, whereas similar amounts of nitrate were produced in the nocturnal boundary layer and residual layer at the suburban site, which results in little downward transport of nitrate from the residual…

Abstract. Atmospheric deposition of nitrogen (N) and sulfur (S) compounds from human activity has greatly declined in the United States (US) over the past several decades in response to emission controls set by the Clean Air Act. While many studies have investigated the spatial and temporal trends of atmospheric deposition, few assess dry deposition, incorporate a measurement-model fusion approach to improve wet deposition estimates, or focus on changes within specific US climate regions. In this analysis, we evaluate wet, dry, and total N and S deposition from multiyear simulations across climatologically consistent regions within the contiguous US (CONUS). Community Multiscale Air Quality (CMAQ) model estimates from 2002 to 2017 from the EPA’s Air QUAlity TimE Series (EQUATES) project contain important model updates to atmospheric deposition algorithms compared to previous model data, including the new Surface Tiled Aerosol and Gaseous Exchange (STAGE) bidirectional deposition model and improvements to organic N chemistry. The model generally underestimates wet deposition of SO4,…

Abstract. Volatile organic compounds (VOCs) are key precursors of ozone and particulate matter that are the two dominant air pollutants in urban environments. However, compositions and sources of VOCs in urban air aloft were rarely reported by far. To address this matter, highly time-resolved measurements of VOCs were made by proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) at a 450-m platform on the Canton Tower in Guangzhou, China. A combination of in-situ measurements and modeling techniques was used to characterize variations and sources of VOCs. Five sources were identified from positive matrix factorization (PMF) analysis, namely daytime-mixed (e.g., biogenic emissions and secondary formation), visitor-related (e.g., human breath and volatilization of ethanol-containing products), vehicular+industrial, regional transport, and volatile chemical product (VCP)-dominated (i.e., volatilization of personal care products), contributing on average to 22 %, 30 %, 28 %, 10 %, and 11 % of total VOC (TVOC) mixing ratios, respectively. We observe that contributions of…

Abstract. Dust particles, serving as ice nucleating particles (INPs), may impact the Arctic surface energy budget and regional climate by modulating the mixed-phase cloud properties and lifetime. In addition to long-range transport from low latitude deserts, dust particles in the Arctic can originate from local sources. However, the importance of high latitude dust (HLD) as a source of Arctic INPs (compared to low latitude dust (LLD)) and its effects on Arctic mixed-phase clouds are overlooked. In this study, we evaluate the contribution to Arctic dust loading and INP population from HLD and six LLD source regions by implementing a source-tagging technique for dust aerosols in version 1 of the US Department of Energy’s Energy Exascale Earth System Model (E3SMv1). Our results show that HLD is responsible for 30.7 % of the total dust burden in the Arctic, whereas LLD from Asia and North Africa contribute 44.2 % and 24.2 %, respectively. Due to its limited vertical transport as a result of stable boundary layers, HLD contributes more in the lower troposphere, especially in boreal…

We use satellite methane observations from the Tropospheric Monitoring Instrument (TROPOMI), for May 2018 to February 2020, to quantify methane emissions from individual oil and natural gas (O/G) basins in the US and Canada using a high-resolution (∼25 km) atmospheric inverse analysis. Our satellite-derived emission estimates show good consistency with in situ field measurements ( R =0.96) in 14 O/G basins distributed across the US and Canada. Aggregating our results to the national scale, we obtain O/G-related methane emission estimates of 12.6±2.1 Tg a −1 for the US and 2.2±0.6 Tg a −1 for Canada, 80 % and 40 %, respectively, higher than the national inventories reported to the United Nations. About 70 % of the discrepancy in the US Environmental Protection Agency (EPA) inventory can be attributed to five O/G basins, the Permian, Haynesville, Anadarko, Eagle Ford, and Barnett basins, which in total account for 40 % of US emissions. We show more generally that our TROPOMI inversion framework can quantify methane emissions exceeding 0.2–0.5 Tg a −1 from individual O/G basins, thus…

Abstract. Nitrate aerosol plays an increasingly important role in wintertime haze pollution in China. Despite intensive research on the wintertime nitrate chemistry in recent years, quantitative constraints on the formation mechanisms of nitrate aerosol in the Yangtze River Delta (YRD), one of the most developed and densely populated regions in eastern China, remain inadequate. In this study, we identify the major nitrate formation pathways and their key controlling factors during the winter haze pollution period in the eastern YRD using two-year (2018–2019) field observations and detailed observation-constrained model simulations. We find that the high atmospheric oxidation capacity, coupled with high aerosol liquid water content (ALWC), made both the heterogeneous hydrolysis of dinitrogen pentoxide (N2O5) and the gas-phase OH oxidation of nitrogen dioxide (NO2) important pathways for wintertime nitrate formation in this region, with contribution percentages of 69 % and 29 % in urban areas and 63 % and 35 % in suburban areas, respectively. We further find that the gas-to-particle…

Abstract. We quantify methane emissions and their 2010–2017 trends by sector in the contiguous United States (CONUS), Canada, and Mexico by inverse analysis of in situ (GLOBALVIEWplus CH4 ObsPack) and satellite (GOSAT) atmospheric methane observations. The inversion uses as prior estimate the national anthropogenic emission inventories for the three countries reported by the US Environmental Protection Agency (EPA), Environment and Climate Change Canada (ECCC), and the Instituto Nacional de Ecologia y Cambio Climatico (INECC) in Mexico to the United Nations Framework Convention on Climate Change (UNFCCC), and thus serves as an evaluation of these inventories in terms of their magnitudes and trends. Emissions are optimized with a Gaussian mixture model (GMM) at 0.5° × 0.625° resolution and for individual years. Optimization is done analytically using log-normal error forms. This yields closed-form statistics of error estimates and information content on the posterior (optimized) estimates, allows better representation of the high tail of the emission distribution, and enables…

Abstract. We present 2019 global methane (CH4) emissions and uncertainties, by sector, at 1-degree and country-scale resolution based on a Bayesian integration of satellite data and inventories. Globally, we find that agricultural and fire emissions are 227 +/− 19 Tg CH4/yr, waste is 50 +/− 7 Tg CH4/yr , anthropogenic fossil emissions are 82 +/− 12 Tg CH4/yr, and natural wetland/aquatic emissions are 180 +/− 10 Tg CH4/yr. These estimates are intended as a pilot dataset for the Global Stock Take in support of the Paris Agreement. However, differences between the emissions reported here and widely-used bottom-up inventories should be used as a starting point for further research because of potential systematic errors of these satellite based emissions estimates. Calculation of emissions and uncertainties: We first apply a standard optimal estimation (OE) approach to quantify CH4 fluxes using Greenhouse Gases Observing Satellite (GOSAT) total column CH4 concentrations and the GEOS-Chem global chemistry transport model. Second, we use a new Bayesian algorithm that projects these…

Abstract. Brown carbon (BrC) aerosols exert vital impacts on climate change and atmospheric photochemistry due to their light absorption in the wavelength range from near-ultraviolet (UV) to visible light. However, the optical properties and formation mechanisms of ambient BrC remain poorly understood, limiting the estimation of their radiative forcing. In the present study, fine aerosols (PM2.5) were collected during 2016–2017 on a day/night basis over urban Tianjin, a megacity in North China, to obtain seasonal and diurnal patterns of atmospheric water-soluble BrC. There were obvious seasonal but no evident diurnal variations in light absorption properties of BrC. In winter, BrC showed much stronger light absorbing ability since mass absorption efficiency at 365 nm (MAE365) (1.54 ± 0.33 m2 g−1), which was 1.8 times larger than that (0.84 ± 0.22 m2 g−1) in summer. Direct radiative effects by BrC absorption relative to black carbon in the UV range were 54.3 ± 16.9 % and 44.6 ± 13.9 %, respectively. In addition, five fluorescent components in BrC, including three humic-like…

Abstract. Two Saharan dust layers observed over Leipzig in February and March 2021 were used to provide the first ever lidar measurements of the extinction coefficient at 1064 nm for desert dust. The advanced multiwavelength Raman polarization lidar was able to provide, for the first time, the lidar ratio (extinction-to-backscatter ratio) and particle linear depolarization ratio at all three classical lidar wavelengths (355, 532 and 1064 nm). The pure dust conditions during the first event exhibit lidar ratios of 47±8, 50±5 and 63±13 sr and particle linear depolarization ratios of 0.260±0.026, 0.298±0.017 and 0.214±0.025 at the wavelengths of 355, 532 and 1064 nm, respectively. The second, slightly polluted dust case shows a similar spectral behavior with values of the lidar ratio of 52±8, 47±5 and 61±10 sr and the depolarization ratio of 0.188±0.053, 0.270±0.017 and 0.242±0.007 at 355, 532 and 1064 nm, respectively. The results were compared to AERONET v3 inversions and GRASP retrievals at six and seven wavelengths, which could reproduce the spectral slope of the lidar ratio from…

Abstract. Vehicular emission is an important source for volatile organic compounds (VOCs) in urban and downwind regions. In this study, we conducted a chassis dynamometer study to investigate VOC emissions from vehicles using gasoline, diesel, and liquefied petroleum gas (LPG) as fuel. Time-resolved VOC emissions from vehicles are chemically characterized by a proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) with high frequency. Our results show that emission factors of VOCs generally decrease with the improvement of emission standard for gasoline vehicles, whereas variations of emission factors for diesel vehicles with emission standards are more diverse. Mass spectra analysis of PTR-ToF-MS suggest that cold start significantly influence VOCs emission of gasoline vehicles, while the influences are less important for diesel vehicles. Large differences of VOC emissions between gasoline and diesel vehicles are observed with emission factors of most VOC species from diesel vehicles were higher than gasoline vehicles, especially for most oxygenated volatile organic…

Abstract. It is being suggested that particle-bound or particle-induced reactive oxygen species (ROS), which significantly contribute to the oxidative potential (OP) of aerosol particles, are a promising metric linking aerosol compositions to toxicity and adverse health effects. However, accurate ROS quantification remains challenging due to the reactive and short-lived nature of many ROS components and the lack of appropriate analytical methods for a reliable quantification. Consequently, it remains difficult to gauge their impact on human health, especially to identify how aerosol particle sources and atmospheric processes drive particle-bound ROS formation in a real-world urban environment. In this study, using a novel online particle-bound ROS instrument (OPROSI), we comprehensively characterized and compared the formation of ROS in secondary organic aerosols (SOA) generated from organic compounds that represent anthropogenic (naphthalene, SOANAP) and biogenic (β-pinene, SOAβPIN) precursors. The SOA mass was condensed onto soot particles (SP) under varied atmospherically…

Abstract. This study presents an updated evaluation of stratospheric ozone profile trends in the 60° S–60° N latitude range over the 2000–2020 period, using an updated version of the Long-term Ozone Trends and Uncertainties in the Stratosphere (LOTUS) regression model that was used to evaluate such trends up to 2016 for the last WMO Ozone Assessment (2018). In addition to the derivation of detailed trends as a function of latitude and vertical coordinates, the regressions are performed with the data sets averaged over broad latitude bands, i.e. 60° S–35° S, 20° S–20° N and 35° N–60° N. The same methodology as in the last Assessment is applied to combine trends in these broad latitude bands in order to compare the results with the previous studies. Longitudinally resolved merged satellite records are also considered in order to provide a better comparison with trends retrieved from ground-based records, e.g. lidar, ozone sondes, Umkehr, microwave and Fourier Transform Infrared (FTIR) spectrometers at selected stations where long-term time series are available. The study includes a…

Abstract. Surface ozone concentrations typically peak in daytime driven by active photochemical production and decrease gradually after sunset by chemical destruction and dry deposition. Here, we report that nocturnal ozone enhancement (NOE, defined as ozone increase by at least 5 ppbv hour-1 in one of any two adjacent hours in 20:00–06:00 local time) events are observed at multiple monitoring sites in China at a high frequency that has not been recognized in previous studies. We present an overview of the general characteristics of NOE events in China and explore the possible mechanisms based on six-year observations from the national monitoring network. We find that the annual mean frequency of NOE events is 41±10 % averaged over all 814 Chinese sites in 2014–2019, which is 46 % larger than those over Europe and US. The NOE event frequency is higher in industrialized city clusters (>50 %) than regions with lighter ozone pollution, and is higher in the warm (46 %) than cold season (36 %), consistent with the spatiotemporal evolution of ozone levels. The mean ozone peak during NOE…

Abstract. A record-breaking severe ozone (O3) pollution episode occurred in the Pearl River Delta (PRD) in early Autumn 2019 when PRD was under the influence of a Pacific subtropical high followed by Typhoon Mina. In this study, we analyzed the effects of meteorological and photochemical processes on the O3 concentration in PRD during this episode by carrying out the Weather Research Forecast-Community Multiscale Air Quality (WRF-CMAQ) model simulations. Results showed that low relative humidity, high boundary layer height, northerly surface winds and strong downdrafts were the main meteorological factors contributing to O3 pollution. Moreover, delayed sea breezes that lasted into the night would transport O3 from the sea back to land and resulted in secondary O3 maxima at night. In addition, O3 and its precursors stored in the residual layer above the surface layer at night can be mixed down to the surface in the next morning, further enhancing the daytime ground-level O3 concentration the following day. Photochemical production of O3, with daytime average production rate of about…

Abstract. Over recent years there have been parallel advances in the development of stratosphere resolving numerical models, our understanding of stratosphere-troposphere interaction and the extension of long-range forecasts to explicitly include the stratosphere. These advances are now allowing new and improved capability in long range prediction. We present an overview of this development and show how the inclusion of the stratosphere in forecast systems aids monthly, seasonal and decadal climate predictions. We end with an outlook towards the future of climate forecasts and identify areas for improvement that could further benefit these rapidly evolving predictions.