Variability of ambient air ammonia in urban Europe (Finland, France, Italy, Spain, and the UK).

This study addressed the scarcity of NH3 measurements in urban Europe and the diverse monitoring protocols, hindering direct data comparison. Sixty-nine datasets from Finland, France, Italy, Spain, and the UK across various site types, including industrial (IND, 8), traffic (TR, 12), urban (UB, 22), suburban (SUB, 12), and regional background (RB, 15), are analyzed to this study. Among these, 26 sites provided 5, or more, years of data for time series analysis. Despite varied protocols, necessitating future harmonization, the average NH3 concentration across sites reached 8.0 ± 8.9 µg/m3. Excluding farming/agricultural hotspots (FAHs), IND and TR sites had the highest concentrations (4.7 ± 3.2 and 4.5 ± 1.0 µg/m3), followed by UB, SUB, and RB sites (3.3 ± 1.5, 2.7 ± 1.3, and 1.0 ± 0.3 µg/m3, respectively) indicating that industrial, traffic, and other urban sources were primary contributors to NH3 outside FAH regions. When referring exclusively to the FAHs, concentrations ranged from 10.0 ± 2.3 to 15.6 ± 17.2 µg/m3, with the highest concentrations being reached in RB sites close to the farming and agricultural sources, and that, on average for FAHs there is a decreasing NH3 concentration gradient towards the city. Time trends showed that over half of the sites (18/26) observed statistically significant trends. Approximately 50 % of UB and TR sites showed a decreasing trend, while 30 % an increasing one. Meta-analysis revealed a small insignificant decreasing trend for non-FAH RB sites. In FAHs, there was a significant upward trend at a rate of 3.51[0.45,6.57]%/yr. Seasonal patterns of NH3 concentrations varied, with urban areas experiencing fluctuations influenced by surrounding emissions, particularly in FAHs. Diel variation showed differing patterns at urban monitoring sites, all with higher daytime concentrations, but with variations in peak times depending on major emission sources and meteorological patterns. These results offer valuable insights into the spatio-temporal patterns of gas-phase NH3 concentrations in urban Europe, contributing to future efforts in benchmarking NH3 pollution control in urban areas.

Global organic and inorganic aerosol hygroscopicity and its effect on radiative forcing.

The climate effects of atmospheric aerosol particles serving as cloud condensation nuclei (CCN) depend on chemical composition and hygroscopicity, which are highly variable on spatial and temporal scales. Here we present global CCN measurements, covering diverse environments from pristine to highly polluted conditions. We show that the effective aerosol hygroscopicity, κ, can be derived accurately from the fine aerosol mass fractions of organic particulate matter (ϵorg) and inorganic ions (ϵinorg) through a linear combination, κ = ϵorg ⋅ κorg + ϵinorg ⋅ κinorg. In spite of the chemical complexity of organic matter, its hygroscopicity is well captured and represented by a global average value of κorg = 0.12 ± 0.02 with κinorg = 0.63 ± 0.01 as the corresponding value for inorganic ions. By showing that the sensitivity of global climate forcing to changes in κorg and κinorg is small, we constrain a critically important aspect of global climate modelling.

Airborne observations over the North Atlantic Ocean reveal the importance of gas-phase urea in the atmosphere.

Reduced nitrogen (N) is central to global biogeochemistry, yet there are large uncertainties surrounding its sources and rate of cycling. Here, we present observations of gas-phase urea (CO(NH2)2) in the atmosphere from airborne high-resolution mass spectrometer measurements over the North Atlantic Ocean. We show that urea is ubiquitous in the lower troposphere in the summer, autumn, and winter but was not detected in the spring. The observations suggest that the ocean is the primary emission source, but further studies are required to understand the responsible mechanisms. Urea is also observed aloft due to long-range transport of biomass-burning plumes. These observations alongside global model simulations point to urea being an important, and currently unaccounted for, component of reduced-N to the remote marine atmosphere. Airborne transfer of urea between nutrient-rich and -poor parts of the ocean can occur readily and could impact ecosystems and oceanic uptake of carbon dioxide, with potentially important climate implications.

Association of air pollution with dementia: a systematic review with meta-analysis including new cohort data from China.

It remains unclear whether a total exposure to air pollution (AP) is associated with an increased risk of dementia. Little is known on the association in low- and middle-income countries. Two cohort studies in China (in Anhui cohort 1402 older adults aged ≥ 60 followed up for 10 years; in Zhejiang cohort 6115 older adults followed up for 5 years) were conducted to examine particulate matter - PM2.5 associated with all dementia and air quality index (AQI) with Alzheimer's disease, respectively. A systematic literature review and meta-analysis was performed following worldwide literature searched until May 20, 2020 to identify 15 population-based cohort studies examining the association of AP with dementia (or any specific type of dementia) through PubMed, MEDLINE, PsycINFO, SocINDEX, CINHAL, and CNKI. The cohort studies in China showed a significantly increased relative risk (RR) of dementia in relation to AP exposure; in Anhui cohort the adjusted RR was 2.14 (95% CI 1.00-4.56) in people with PM2.5 exposure at ≥ 64.5 µg/m3 versus <63.5 µg/m3 and in Zhejiang cohort the adjusted RR was 2.28 (1.07-4.87) in AQI>90 versus ≤ 80. The systematic review revealed that all 15 studies were undertaken in high income countries/regions, with inconsistent findings. While they had reasonably good overall quality of studies, seven studies did not adjust smoking in analysis and 13 did not account for depression. Pooling all eligible data demonstrated that dementia risk increased with the total AP exposure (1.13, 1.08-1.19). Data analysis of air pollutants showed that the RR significantly increased with PM2.5 (1.06, 1.03-1.10 in 2nd tertile exposure; 1.13, 1.07-1.19 in 3rd tertile versus 1st tertile), PM10 (1.05, 0.86-1.29; 1.62, 0.60-4.36), carbon monoxide (1.69, 0.72-3.93; 1.52, 1.35-1.71), nitrogen dioxide (1.06, 1.03-1.09; 1.18, 1.10-1.28) and nitrogen oxides (1.09, 1.04-1.15; 1.26, 1.13-1.41), but not ozone. Controlling air pollution and targeting on specific pollutants would reduce dementia globally.

Compositional Constraints are Vital for Atmospheric PM2.5 Source Attribution over India.

India experiences some of the highest levels of ambient PM2.5 aerosol pollution in the world. However, due to the historical dearth of in situ measurements, chemical transport models that are often used to estimate PM2.5 exposure over the region are rarely evaluated. Here, we conduct a novel model comparison with speciated airborne measurements of fine aerosol, revealing large biases in the ammonium and nitrate simulations. To address this, we incorporate process-level changes to the model and use satellite observations from the Cross-track Infrared Sounder (CrIS) and the TROPOspheric Monitoring Instrument (TROPOMI) to constrain ammonia and nitrogen oxide emissions. The resulting simulation demonstrates significantly lower bias (NMBModified: 0.19; NMBBase: 0.61) when validated against the airborne aerosol measurements, particularly for the nitrate (NMBModified: 0.08; NMBBase: 1.64) and ammonium simulation (NMBModified: 0.49; NMBBase: 0.90). We use this validated simulation to estimate a population-weighted annual PM2.5 exposure of 61.4 µg m-3, with the RCO (residential, commercial, and other) and energy sectors contributing 21% and 19%, respectively, resulting in an estimated 961,000 annual PM2.5-attributable deaths. Regional exposure and sectoral source contributions differ meaningfully in the improved simulation (compared to the baseline simulation). Our work highlights the critical role of speciated observational constraints in developing accurate model-based PM2.5 aerosol source attribution for health assessments and air quality management in India.

A Four Carbon Organonitrate as a Significant Product of Secondary Isoprene Chemistry.

Oxidation of isoprene by nitrate radicals (NO3) or by hydroxyl radicals (OH) under high NOx conditions forms a substantial amount of organonitrates (ONs). ONs impact NOx concentrations and consequently ozone formation while also contributing to secondary organic aerosol. Here we show that the ONs with the chemical formula C4H7NO5 are a significant fraction of isoprene-derived ONs, based on chamber experiments and ambient measurements from different sites around the globe. From chamber experiments we found that C4H7NO5 isomers contribute 5%-17% of all measured ONs formed during nighttime and constitute more than 40% of the measured ONs after further daytime oxidation. In ambient measurements C4H7NO5 isomers usually dominate both nighttime and daytime, implying a long residence time compared to C5 ONs which are removed more rapidly. We propose potential nighttime sources and secondary formation pathways, and test them using a box model with an updated isoprene oxidation scheme.

Using highly time-resolved online mass spectrometry to examine biogenic and anthropogenic contributions to organic aerosol in Beijing.

Organic aerosols, a major constituent of fine particulate mass in megacities, can be directly emitted or formed from secondary processing of biogenic and anthropogenic volatile organic compound emissions. The complexity of volatile organic compound emission sources, speciation and oxidation pathways leads to uncertainties in the key sources and chemistry leading to formation of organic aerosol in urban areas. Historically, online measurements of organic aerosol composition have been unable to resolve specific markers of volatile organic compound oxidation, while offline analysis of markers focus on a small proportion of organic aerosol and lack the time resolution to carry out detailed statistical analysis required to study the dynamic changes in aerosol sources and chemistry. Here we use data collected as part of the joint UK-China Air Pollution and Human Health (APHH-Beijing) collaboration during a field campaign in urban Beijing in the summer of 2017 alongside laboratory measurements of secondary organic aerosol from oxidation of key aromatic precursors (1,3,5-trimethyl benzene, 1,2,4-trimethyl benzene, propyl benzene, isopropyl benzene and 1-methyl naphthalene) to study the anthropogenic and biogenic contributions to organic aerosol. For the first time in Beijing, this study applies positive matrix factorisation to online measurements of organic aerosol composition from a time-of-flight iodide chemical ionisation mass spectrometer fitted with a filter inlet for gases and aerosols (FIGAERO-ToF-I-CIMS). This approach identifies the real-time variations in sources and oxidation processes influencing aerosol composition at a near-molecular level. We identify eight factors with distinct temporal variability, highlighting episodic differences in OA composition attributed to regional influences and in situ formation. These have average carbon numbers ranging from C5-C9 and can be associated with oxidation of anthropogenic aromatic hydrocarbons alongside biogenic emissions of isoprene, α-pinene and sesquiterpenes.

Key Role of NO3 Radicals in the Production of Isoprene Nitrates and Nitrooxyorganosulfates in Beijing.

The formation of isoprene nitrates (IsN) can lead to significant secondary organic aerosol (SOA) production and they can act as reservoirs of atmospheric nitrogen oxides. In this work, we estimate the rate of production of IsN from the reactions of isoprene with OH and NO3 radicals during the summertime in Beijing. While OH dominates the loss of isoprene during the day, NO3 plays an increasingly important role in the production of IsN from the early afternoon onwards. Unusually low NO concentrations during the afternoon resulted in NO3 mixing ratios of ca. 2 pptv at approximately 15:00, which we estimate to account for around a third of the total IsN production in the gas phase. Heterogeneous uptake of IsN produces nitrooxyorganosulfates (NOS). Two mono-nitrated NOS were correlated with particulate sulfate concentrations and appear to be formed from sequential NO3 and OH oxidation. Di- and tri-nitrated isoprene-related NOS, formed from multiple NO3 oxidation steps, peaked during the night. This work highlights that NO3 chemistry can play a key role in driving biogenic-anthropogenic interactive chemistry in Beijing with respect to the formation of IsN during both the day and night.

Using a coupled LES aerosol-radiation model to investigate the importance of aerosol-boundary layer feedback in a Beijing haze episode.

Haze episodes, characterised by extremely high aerosol concentrations and a reduction in visibility to less than 10 km, are a frequent occurrence in wintertime Beijing, despite policy interventions leading to an overall improvement in average annual air quality. The main drivers in the onset of haze episodes in wintertime Beijing are changing synoptic conditions, however, aerosol-radiation interactions and their feedback on boundary layer meteorology are thought to play an essential role in the intensity and longevity of haze episodes. In this study we use a coupled LES aerosol-radiation model (UCLALES-SALSA), which we have recently configured for the urban environment of Beijing. The model's high resolution and control over meteorological and aerosol conditions as well as atmospheric processes means we can directly elucidate and quantify the importance of specific aspects of the aerosol-radiation-meteorology feedback in the cumulative stage of Beijing haze. The main results presented here show (a) synoptic scale meteorology has a larger impact on boundary layer suppression than high aerosol concentrations and (b) unlike previous results obtained using regional models or observationally driven analyses, there is no threshold value at which the aerosol-radiation-meteorology feedback has a significant effect on PBL height. Rather, our work shows that for the aerosol composition in this case study, the role of the feedback effect in reducing PBL height increases under shallow boundary layer conditions and with increasing pollution loading in an almost linear fashion. This lack of a threshold found for our case study has important policy implications since interventions based on such a value will not result in large reductions associated with turning off the feedback process. Furthermore, this work directly shows that although the right synoptic changes are a prerequisite for pollution episodes in Beijing, local and regional emissions drive increases in aerosol load that are sufficient to initiate the aerosol feedback loop. This further drives suppression of the boundary layer top and promotes stagnation of air and increased stability, which can be self-sustaining. This results in higher surface aerosol concentrations for extended periods of time, with severe consequences for human health [Lv et al., Atmos. Environ., 2016, 124, 98-108; Wang et al., Atmos. Chem. Phys., 2019, 19(10), 6949-6967].

Characterizing the Particle Composition and Cloud Condensation Nuclei from Shipping Emission in Western Europe.

Commercial shipping is considered as an important source of air pollution and cloud condensation nuclei (CCN). To assess the climatic and environmental impacts of shipping, detailed characterization of ship plumes near the point of emission and understanding of ship plume evolution further downwind are essential. This airborne measurement study presents the online characterization of particulate phase ship emissions in the region of Western Europe in 2019 prior to new international sulfur emission controls becoming enacted. More than 30 ships from both the sulfur emission control area (SECA) in the English Channel and the open sea (OS) are measured and compared. Ships within the SECA emitted much less sulfate (SO4) compared with those at OS. When shifted to a lower apparent fuel sulfur content (FSC) at similar engine loads, the peak of the fresh ship emitting the particle number size distribution shifted from around 60-80 nm in diameter to below 40 nm in diameter. The emission factors (EFs) of sulfate are predicted to decrease by around 94% after the 2020 regulation on ship sulfur emission in the open ocean. The EFs of refractory black carbon (rBC) and organic compounds (Org) do not appear to be directly affected by the lower sulfur contents. The total number concentration for condensation nuclei (CN) >2.5 nm and >0.1 µm are predicated to be reduced by 69 and 56%, respectively. Measured plume evolution results indicate that the S(IV) to S(VI) conversion rate was around 23.4% per hour at the beginning of plume evolution, and the CCN and CN >2.5 nm ratio increased with plume age primarily due to condensation and coagulation. We estimate that the new sulfur emission regulation will lead to a reduction of more than 80% in CCN from fresh ship emissions. The ship-emitted EFs results presented here will also inform emission inventories, policymaking, climate, and human health studies.

Non-deforestation drivers of fires are increasingly important sources of aerosol and carbon dioxide emissions across Amazonia.

Deforestation rates have declined substantially across the Brazilian Legal Amazon (BLA) over the period from 2000-2017. However, reductions in fire, aerosol and carbon dioxide have been far less significant than deforestation, even when accounting for inter-annual variability in precipitation. Our observations and analysis support a decoupling between fire and deforestation that has exacerbated forest degradation in the BLA. Basing aerosol and carbon dioxide emissions on deforestation rates, without accounting for forest degradation will bias these important climate and ecosystem-health parameters low, both now and in the future. Recent increases in deforestation rate since 2014 will enhance such degradation, particularly during drought-conditions, increasing emissions of aerosol and greenhouse gases. Given Brazil's committed Nationally Determined Contribution under the Paris Agreement, failure to account for forest degradation fires will paint a false picture of prior progress and potentially have profound implications for both regional and global climate.

Size-Related Physical Properties of Black Carbon in the Lower Atmosphere over Beijing and Europe.

The size-resolved properties of atmospheric black carbon (BC) importantly determine its absorption capacity and cloud condensation nuclei (CCN) ability. This study reports comprehensive vertical profiles of BC size-related properties over the Beijing area (BJ) and Continental Europe (CE). BC mass loadings over CE were in the range of clean background over BJ. For both planetary boundary layer (PBL) and lower free troposphere, the BC mass median core diameter over BJ during the cold season was 0.21 ± 0.02 µm, larger than the warm season over BJ and CE (0.18 ± 0.01 µm), which may reflect seasonal differences in emissions. The BC coatings were positively correlated with the pollution level, with background BC having a smaller coated count median diameter (0.19 ± 0.01 µm). The modeled absorption enhancement (Eabs) due to coatings was 1.23 ± 0.14 for the background but in the PBL following a linear expression (Eabs = 0.13 × MassBC,surface + 1.26). The CCN ability of BC was significantly enhanced in the polluted PBL, due to both enlarged size and increased hygroscopicity. In polluted BJ at predicted supersaturations, ∼0.08% half of the BC number could be activated, whereas the cleaner environment needs ∼0.14%. The results here suggest that the highly coated and absorbing BC can be efficiently incorporated into clouds and can exert important indirect radiative impacts over the polluted East Asia region.

Decrease in radiative forcing by organic aerosol nucleation, climate, and land use change.

Organic nucleation is an important source of atmospheric aerosol number concentration, especially in pristine continental regions and during the preindustrial period. Here, we improve on previous simulations that overestimate boundary layer nucleation in the tropics and add changes to climate and land use to evaluate climate forcing. Our model includes both pure organic nucleation and heteromolecular nucleation of sulfuric acid and organics and reproduces the profile of aerosol number concentration measured in the Amazon. Organic nucleation decreases the sum of the total aerosol direct and indirect radiative forcing by 12.5%. The addition of climate and land use change decreases the direct radiative forcing (-0.38 W m-2) by 6.3% and the indirect radiative forcing (-1.68 W m-2) by 3.5% due to the size distribution and number concentration change of secondary organic aerosol and sulfate. Overall, the total radiative forcing associated with anthropogenic aerosols is decreased by 16%.

Quantification of ash sedimentation dynamics through depolarisation imaging with AshCam.

Even modest ash-rich volcanic eruptions can severely impact a range of human activities, especially air travel. The dispersal of ash in these eruptions depends critically on aggregation and sedimentation processes - however these are difficult to quantify in volcanic plumes. Here, we image ash dynamics from mild explosive activity at Santiaguito Volcano, Guatemala, by measuring the depolarisation of scattered sunlight by non-spherical ash particles, allowing the dynamics of diffuse ash plumes to be investigated with high temporal resolution (>1 Hz). We measure the ash settling velocity downwind from the main plume, and compare it directly with ground sampled ash particles, finding good agreement with a sedimentation model based on particle size. Our new, cost-effective technique leverages existing technology, opening a new frontier of integrated ash visualisation and ground collection studies which could test models of ash coagulation and sedimentation, leading to improved ash dispersion forecasts. This will provide risk managers with improved data quality on ash location, reducing the economic and societal impacts of future ash-rich eruptions.

Mixing State of Carbonaceous Aerosols of Primary Emissions from "Improved" African Cookstoves.

Designs of "improved" stoves are introduced recently to benefit the solid fuel consumption of cooking activities in developing countries, but the uncertainties concerning the combustion processes and particulate emissions remain poorly characterized. To help understand this, combustion in three examples of "improved" African cookstoves was investigated in the laboratory. A typical European heating stove was included for comparison purpose. Detailed aerosol emissions were studied in real-time with an Aerosol Mass Spectrometer and Single Particle Soot Photometer, to explore interactions between black carbon (BC) and organic carbon aerosols, which were parametrized according to modified combustion efficiency (MCE), a common metric used within the atmospheric emission community. Greater than 50% of the total organic matter (OM) was found in BC-containing particles when MCE was >0.95 for dry oak and coal fuels, whereas at lower MCE, over 80% of the total OM for most of the fuels existed in particles without detectable BC. When the OM mass fraction of total particulate matter (PM1) > 0.9, the mass ratio of OM to refractory BC in BC-containing particles was about 2-3, but only ∼0.8 when OM mass fraction <0.9. These findings are not currently included in models and such information should be considered in the future emission scenarios.

Online Chemical Characterization of Food-Cooking Organic Aerosols: Implications for Source Apportionment.

Food-cooking organic aerosols (COA) are one of the primary sources of submicron particulate matter in urban environments. However, there are still many questions surrounding source apportionment related to instrumentation as well as semivolatile partitioning because COA evolve rapidly in the ambient air, making source apportionment more complex. Online measurements of emissions from cooking different types of food were performed in a laboratory to characterize particles and gases. Aerosol mass spectrometer (AMS) measurements showed that the relative ionization efficiency for OA was higher (1.56-3.06) relative to a typical value of 1.4, concluding that AMS is over-estimating COA and suggesting that previous studies likely over-estimated COA concentrations. Food-cooking mass spectra were generated using AMS, and gas and particle food markers were identified with filter inlets for gases and aerosols-chemical ionization mass spectrometer (CIMS) measurements to be used in future food cooking-source apportionment studies. However, there is a considerable variability in both gas and particle markers, and dilution plays an important role in the particle mass budget, showing the importance of using these markers with caution during receptor modeling. These findings can be used to better understand the chemical composition of COA, and they provides useful information to be used in future source-apportionment studies.

First Chemical Characterization of Refractory Black Carbon Aerosols and Associated Coatings over the Tibetan Plateau (4730 m a.s.l).

Refractory black carbon (rBC) aerosol is an important climate forcer, and its impacts are greatly influenced by the species associated with rBC cores. However, relevant knowledge is particularly lacking at the Tibetan Plateau (TP). Here we report, for the first time, highly time-resolved measurement results of rBC and its coating species in central TP (4730 m a.s.l), using an Aerodyne soot particle aerosol mass spectrometer (SP-AMS), which selectively measured rBC-containing particles. We found that the rBC was overall thickly coated with an average mass ratio of coating to rBC (RBC) of ∼7.7, and the coating species were predominantly secondarily formed by photochemical reactions. Interestingly, the thickly coated rBC was less oxygenated than the thinly coated rBC, mainly due to influence of the transported biomass burning organic aerosol (BBOA). This BBOA was relatively fresh but formed very thick coating on rBC. We further estimated the "lensing effect" of coating semiquantitatively by comparing the measurement data from a multiangle absorption photometer and SP-AMS, and found it could lead to up to 40% light absorption enhancement at RBC > 10. Our findings highlight that BBOA can significantly affect the "lensing effect", in addition to its relatively well-known role as light-absorbing "brown carbon."