Direct Measurements of Covalently Bonded Sulfuric Anhydrides from Gas-Phase Reactions of SO3 with Acids under Ambient Conditions.

Sulfur trioxide (SO3) is an important oxide of sulfur and a key intermediate in the formation of sulfuric acid (H2SO4, SA) in the Earth's atmosphere. This conversion to SA occurs rapidly due to the reaction of SO3 with a water dimer. However, gas-phase SO3 has been measured directly at concentrations that are comparable to that of SA under polluted mega-city conditions, indicating gaps in our current understanding of the sources and fates of SO3. Its reaction with atmospheric acids could be one such fate that can have significant implications for atmospheric chemistry. In the present investigation, laboratory experiments were conducted in a flow reactor to generate a range of previously uncharacterized condensable sulfur-containing reaction products by reacting SO3 with a set of atmospherically relevant inorganic and organic acids at room temperature and atmospheric pressure. Specifically, key inorganic acids known to be responsible for most ambient new particle formation events, iodic acid (HIO3, IA) and SA, are observed to react promptly with SO3 to form iodic sulfuric anhydride (IO3SO3H, ISA) and disulfuric acid (H2S2O7, DSA). Carboxylic sulfuric anhydrides (CSAs) were observed to form by the reaction of SO3 with C2 and C3 monocarboxylic (acetic and propanoic acid) and dicarboxylic (oxalic and malonic acid)-carboxylic acids. The formed products were detected by a nitrate-ion-based chemical ionization atmospheric pressure interface time-of-flight mass spectrometer (NO3--CI-APi-TOF; NO3--CIMS). Quantum chemical methods were used to compute the relevant SO3 reaction rate coefficients, probe the reaction mechanisms, and model the ionization chemistry inherent in the detection of the products by NO3--CIMS. Additionally, we use NO3--CIMS ambient data to report that significant concentrations of SO3 and its acid anhydride reaction products are present under polluted, marine and polar, and volcanic plume conditions. Considering that these regions are rich in the acid precursors studied here, the reported reactions need to be accounted for in the modeling of atmospheric new particle formation.

Road Traffic Emissions Lead to Much Enhanced New Particle Formation through Increased Growth Rates.

New particle formation (NPF) is a major source of atmospheric aerosol particles, including cloud condensation nuclei (CCN), by number globally. Previous research has highlighted that NPF is less frequent but more intense at roadsides compared to urban background. Here, we closely examine NPF at both background and roadside sites in urban Central Europe. We show that the concentration of oxygenated organic molecules (OOMs) is greater at the roadside, and the condensation of OOMs along with sulfuric acid onto new particles is sufficient to explain the growth at both sites. We identify a hitherto unreported traffic-related OOM source contributing 29% and 16% to total OOMs at the roadside and background, respectively. Critically, this hitherto undiscovered OOM source is an essential component of urban NPF. Without their contribution to growth rates and the subsequent enhancements to particle survival, the number of >50 nm particles produced by NPF would be reduced by a factor of 21 at the roadside site. Reductions to hydrocarbon emissions from road traffic may thereby reduce particle numbers and CCN counts.

Estimates of Future New Particle Formation under Different Emission Scenarios in Beijing.

New particle formation (NPF) is a leading source of particulate matter by number and a contributor to particle mass during haze events. Reductions in emissions of air pollutants, many of which are NPF precursors, are expected in the move toward carbon neutrality or net-zero. Expected changes to pollutant emissions are used to investigate future changes to NPF processes, in comparison to a simulation of current conditions. The projected changes to SO2 emissions are key in changing future NPF number, with different scenarios producing either a doubling or near total reduction in sulfuric acid-amine particle formation rates. Particle growth rates are projected to change little in all but the strictest emission control scenarios. These changes will reduce the particle mass arising by NPF substantially, thus showing a further cobenefit of net-zero policies. Major uncertainties remain in future NPF including the volatility of oxygenated organic molecules resulting from changes to NOx and amine emissions.

Understanding Sources and Drivers of Size-Resolved Aerosol in the High Arctic Islands of Svalbard Using a Receptor Model Coupled with Machine Learning.

Atmospheric aerosols are important drivers of Arctic climate change through aerosol-cloud-climate interactions. However, large uncertainties remain on the sources and processes controlling particle numbers in both fine and coarse modes. Here, we applied a receptor model and an explainable machine learning technique to understand the sources and drivers of particle numbers from 10 nm to 20 µm in Svalbard. Nucleation, biogenic, secondary, anthropogenic, mineral dust, sea salt and blowing snow aerosols and their major environmental drivers were identified. Our results show that the monthly variations in particles are highly size/source dependent and regulated by meteorology. Secondary and nucleation aerosols are the largest contributors to potential cloud condensation nuclei (CCN, particle number with a diameter larger than 40 nm as a proxy) in the Arctic. Nonlinear responses to temperature were found for biogenic, local dust particles and potential CCN, highlighting the importance of melting sea ice and snow. These results indicate that the aerosol factors will respond to rapid Arctic warming differently and in a nonlinear fashion.

Contribution of Water-Soluble Organic Matter from Multiple Marine Geographic Eco-Regions to Aerosols around Antarctica.

We present shipborne measurements of size-resolved concentrations of aerosol components across ocean waters next to the Antarctic Peninsula, South Orkney Islands, and South Georgia Island, evidencing aerosol features associated with distinct eco-regions. Nonmethanesulfonic acid Water-Soluble Organic Matter (WSOM) represented 6-8% and 11-22% of the aerosol PM1 mass originated in open ocean (OO) and sea ice (SI) regions, respectively. Other major components included sea salt (86-88% OO, 24-27% SI), non sea salt sulfate (3-4% OO, 35-40% SI), and MSA (1-2% OO, 11-12% SI). The chemical composition of WSOM encompasses secondary organic components with diverse behaviors: while alkylamine concentrations were higher in SI air masses, oxalic acid showed higher concentrations in the open ocean air. Our online single-particle mass spectrometry data exclude a widespread source from sea bird colonies, while the secondary production of oxalic acid and sulfur-containing organic species via cloud processing is suggested. We claim that the potential impact of the sympagic planktonic ecosystem on aerosol composition has been overlooked in past studies, and multiple eco-regions act as distinct aerosol sources around Antarctica.

Biogenic Sources of Ice Nucleating Particles at the High Arctic Site Villum Research Station.

The radiative balance in the Arctic region is sensitive to in-cloud processes, which principally depend on atmospheric aerosols, including ice nucleating particles (INPs). High temperature INPs (active at ≥-15 °C) are common in the Arctic. While laboratory and limited in situ studies show that the high-temperature active INPs are associated with bioaerosols and biogenic compounds, there is still little quantitative insight into the Arctic biogenic INPs and bioaerosols. We measured concentrations of bioaerosols, bacteria, and biogenic INPs at the Villum Research Station (VRS, Station Nord) in a large number of snow (15) and air (51) samples. We found that INPs active at high subzero temperatures were present both in spring and summer. Air INP concentrations were higher in summer (18 INP m-3 at ≥-10 °C) than in spring (<4 INP m-3 at ≥-10 °C), when abundant INPs were found in snowfall (1.4 INP mL-1 at ≥-10 °C). Also, in summer, a significantly higher number of microbial and bacterial cells were present compared to the spring. A large proportion (60%-100%) of INPs that were active between -6 °C and -20 °C could be deactivated by heating to 100 °C, which was indicative of their predominantly proteinaceous origin. In addition, there was a significant linear regression between the summer air concentrations of INPs active at ≥-10 °C and air concentrations of bacterial-marker-genes (p < 0.0001, R2 = 0.999, n = 6), pointing at bacterial cells as the source of high-temperature active INPs. In conclusion, the majority of INPs was of proteinaceous, and possibly of bacterial, origin and was found in air during summer and in snowfall during springtime.

Surface ozone climatology of South Eastern Brazil and the impact of biomass burning events.

In the austral spring, biomass fires affect a vast area of South America each year. We combined in situ ozone (O3) data, measured in the states of São Paulo and Paraná, Brazil, in the period 2014-2017, with aerosol optical depth, co-pollutants (NOx, PM2.5 and PM10) and air backtrajectories to identify sources, transport and geographical patterns in the air pollution data. We applied cluster analysis to hourly O3 data and split the investigation area of approximately 290,000 km2 into five groups with similar features in terms of diurnal, weekly, monthly and seasonal O3 concentrations. All groups presented a peak in September and October, associated with the fire activities and enhanced photochemistry. The highest mean O3 concentrations were measured inland whilst, besides having lower concentrations, the coastal group was also associated with the smallest diurnal and seasonal variations. The latter was attributed to lower photochemical activity due to frequently occurring overcast weather situation. The mean annual regional contribution of O3 over the area was 61 µg/m3, with large seasonal and intersite variabilities (from 35 to 84 µg/m3). The long-range transport of smoke contributed with between 23 and 41% of the total O3 during the pollution events. A pollution outbreak in September 2015 caused many-fold increases in O3, PM2.5 and PM10 across the investigation area, which exceeded the World Health Organisation recommendations. We show that the regional transport of particulates and gas due to biomass burning overlays the local emissions in already highly polluted cities. Such an effect can outweigh local measures to curb anthropogenic air pollution in cities.

Source apportionment of wide range particle size spectra and black carbon collected at the airport of Venice (Italy).

Atmospheric particles are of high concern due to their toxic properties and effects on climate, and large airports are known as significant sources of particles. This study investigates the contribution of the Airport of Venice (Italy) to black carbon (BC), total particle number concentrations (PNC) and particle number size distributions (PNSD) over a large range (14 nm-20 µm). Continuous measurements were conducted between April and June 2014 at a site located 110 m from the main taxiway and 300 m from the runway. Results revealed no significantly elevated levels of BC and PNC, but exhibited characteristic diurnal profiles. PNSD were then analysed using both k-means cluster analysis and positive matrix factorization. Five clusters were extracted and identified as midday nucleation events, road traffic, aircraft, airport and nighttime pollution. Six factors were apportioned and identified as probable sources according to the size profiles, directional association, diurnal variation, road and airport traffic volumes and their relationships to micrometeorology and common air pollutants. Photochemical nucleation accounted for ∼44% of total number, followed by road + shipping traffic (26%). Airport-related emissions accounted for ∼20% of total PNC and showed a main mode at 80 nm and a second mode beyond the lower limit of the SMPS (<14 nm). The remaining factors accounted for less than 10% of number counts, but were relevant for total volume concentrations: nighttime nitrate, regional pollution and local resuspension. An analysis of BC levels over different wind sectors revealed no especially significant contributions from specific directions associated with the main local sources, but a potentially significant role of diurnal dynamics of the mixing layer on BC levels. The approaches adopted in this study have identified and apportioned the main sources of particles and BC at an international airport located in area affected by a complex emission scenario. The results may underpin measures for improving local and regional air quality, and health impact assessment studies.

Local and regional components of aerosol in a heavily trafficked street canyon in central London derived from PMF and cluster analysis of single-particle ATOFMS spectra.

Positive matrix factorization (PMF) has been applied to single particle ATOFMS spectra collected on a six lane heavily trafficked road in central London (Marylebone Road), which well represents an urban street canyon. PMF analysis successfully extracted 11 factors from mass spectra of about 700,000 particles as a complement to information on particle types (from K-means cluster analysis). The factors were associated with specific sources and represent the contribution of different traffic related components (i.e., lubricating oils, fresh elemental carbon, organonitrogen and aromatic compounds), secondary aerosol locally produced (i.e., nitrate, oxidized organic aerosol and oxidized organonitrogen compounds), urban background together with regional transport (aged elemental carbon and ammonium) and fresh sea spray. An important result from this study is the evidence that rapid chemical processes occur in the street canyon with production of secondary particles from road traffic emissions. These locally generated particles, together with aging processes, dramatically affected aerosol composition producing internally mixed particles. These processes may become important with stagnant air conditions and in countries where gasoline vehicles are predominant and need to be considered when quantifying the impact of traffic emissions.

Inter-annual trends of ultrafine particles in urban Europe.

Ultrafine particles (UFP, those with diameters ≤ 100 nm), have been reported to potentially penetrate deeply into the respiratory system, translocate through the alveoli, and affect various organs, potentially correlating with increased mortality. The aim of this study is to assess long-term trends (5-11 years) in mostly urban UFP concentrations based on measurements of particle number size distributions (PNSD). Additionally, concentrations of other pollutants and meteorological variables were evaluated to support the interpretations. PNSD datasets from 12 urban background (UB), 5 traffic (TR), 3 suburban background (SUB) and 1 regional background (RB) sites in 15 European cities and 1 in the USA were evaluated. The non-parametric Theil-Sen's method was used to detect monotonic trends. Meta-analyses were carried out to assess the overall trends and those for different environments. The results showed significant decreases in NO, NO2, BC, CO, and particle concentrations in the Aitken (25-100 nm) and the Accumulation (100-800 nm) modes, suggesting a positive impact of the implementation of EURO 5/V and 6/VI vehicle standards on European air quality. The growing use of Diesel Particle Filters (DPFs) might also have clearly reduced exhaust emissions of BC, PM, and the Aitken and Accumulation mode particles. However, as reported by prior studies, there remains an issue of poor control of Nucleation mode particles (smaller than 25 nm), which are not fully reduced with current DPFs, without emission controls for semi-volatile organic compounds, and might have different origins than road traffic. Thus, contrasting trends for Nucleation mode particles were obtained across the cities studied. This mode also affected the UFP and total PNC trends because of the high proportion of Nucleation mode particles in both concentration ranges. It was also found that the urban temperature increasing trends might have also influenced those of PNC, Nucleation and Aitken modes.

Detecting high emitting vehicle subsets using emission remote sensing systems.

It is often assumed that a small proportion of a given vehicle fleet produces a disproportionate amount of air pollution emissions. If true, policy actions to target the highly polluting section of the fleet could lead to significant improvements in air quality. In this paper, high-emitter vehicle subsets are defined and their contributions to the total fleet emission are assessed. A new approach, using enrichment factor in cumulative Pareto analysis is proposed for detecting high emitter vehicle subsets within the vehicle fleet. A large dataset (over 94,000 remote-sensing measurements) from five UK-based EDAR (emission detecting and reporting system) field campaigns for the years 2016-17 is used as the test data. In addition to discussions about the high emitter screening criteria, the data analysis procedure and future issues of implementation are discussed. The results show different high emitter trends dependent on the pollutant investigated, and the vehicle type investigated. For example, the analysis indicates that 23 % and 51 % of petrol and diesel cars were responsible for 80 % of NO emissions within that subset of the fleet, respectively. Overall, the contributions of vehicles that account for 80 % of total fleet emissions usually reduce with EURO class improvement, with the subset fleet emissions becoming more homogenous. The high emitter constituent was more noticeable for pollutant PM compared with the other gaseous pollutants, and it was also more prominent for petrol cars when compared to diesel ones.

Limited impact of diesel particle filters on road traffic emissions of ultrafine particles.

Diesel engines are a major contributor to emissions of both Black Carbon (BC) and ultrafine particles. Analysis of data from the only roadside monitoring site in Europe with a continuous dataset for size-segregated particle number count (Marylebone Road, London) from 2010 to 2021 reveals that the growing number of vehicles fitted with a Diesel Oxidation Catalyst (DOC) and Diesel Particle Filter (DPF) has been very effective in controlling the emissions of solid particles and hence BC, but that there has been little change in the liquid mode (<30 nm) particles, and that concentrations of ultrafine particles (<100 nm) still well exceed the threshold for "high" concentrations (>104 cm-3 /24-hour mean) defined by WHO. BC declined by 81% between 2014 and 2021, but the ultrafine particle (<100 nm) count declined by only 26%. Consequently, in locations worldwide with heavy diesel traffic, concentrations of ultrafine particles are likely to remain "high" for the foreseeable future unless more effective abatement technologies are implemented.

Measurement of road traffic brake and tyre dust emissions using both particle composition and size distribution data.

Estimates of tyre and brake wear emission factors are presented, derived from data collected from roadside and urban background sites on the premises of the University of Birmingham, located in the UK's second largest city. Size-fractionated particulate matter samples were collected at both sites concurrently in the spring/summer of 2019 and analysed for elemental concentrations and magnetic properties. Using Positive Matrix Factorisation (PMF), three sources were identified in the roadside mass increment of the 1.0-9.9 µm stages of MOUDI impactors located at both sites, namely: brake dust (7.1%); tyre dust (9.6%); and crustal (83%). The large fraction of the mass apportioned to crustal material was suspected to be mainly from a nearby construction site rather than resuspension of road dust. By using Ba and Zn as elemental tracers, brake and tyre wear emission factors were estimated as 7.4 mg/veh.km and 9.9 mg/veh.km, respectively, compared with the PMF-derived equivalent values of 4.4 mg/veh.km and 11 mg/veh.km. Based on the magnetic measurements, an emission factor can be estimated independently for brake dust of 4.7 mg/veh.km. A further analysis was carried out on the concurrently measured roadside increment in the particle number size distribution (10 nm-10 µm). Four factors were identified in the hourly measurements: traffic exhaust nucleation; traffic exhaust solid particles; windblown dust; and an unknown source. The high increment of the windblown dust factor, 3.2 µg/m3, was comparable in magnitude to the crustal factor measured using the MOUDI samples (3.5 µg/m3). The latter's polar plot indicated that this factor was dominated by a large neighbouring construction site. The number emission factors of the exhaust solid particle and exhaust nucleation factors were estimated as 2.8 and 1.9 x 1012/veh.km, respectively.

Monitoring and apportioning sources of indoor air quality using low-cost particulate matter sensors.

Air quality is one of the most important factors in public health. While outdoor air quality is widely studied, the indoor environment has been less scrutinised, even though time spent indoors is typically much greater than outdoors. The emergence of low-cost sensors can help assess indoor air quality. This study provides a new methodology, utilizing low-cost sensors and source apportionment techniques, to understand the relative importance of indoor and outdoor air pollution sources upon indoor air quality. The methodology is tested with three sensors placed in different rooms inside an exemplar house (bedroom, kitchen and office) and one outdoors. When the family was present, the bedroom had the highest average concentrations for PM2.5 and PM10 (3.9 ± 6.8 ug/m3 and 9.6 ± 12.7 µg/m3 respectively), due to the activities undertaken there and the presence of softer furniture and carpeting. The kitchen, while presenting the lowest PM concentrations for both size ranges (2.8 ± 5.9 ug/m3 and 4.2 ± 6.9 µg/m3 respectively), presented the highest PM spikes, especially during cooking times. Increased ventilation in the office resulted in the highest PM1 concentration (1.6 ± 1.9 µg/m3), highlighting the strong effect of infiltration of outdoor air for the smallest particles. Source apportionment, via positive matrix factorisation (PMF), showed that up to 95 % of the PM1 was found to be of outdoor sources in all the rooms. This effect was reduced as particle size increased, with outdoor sources contributing >65 % of the PM2.5, and up to 50 % of the PM10, depending on the room studied. The new approach to elucidate the contributions of different sources to total indoor air pollution exposure, described in this paper, is easily scalable and translatable to different indoor locations.

Extreme Concentrations of Nitric Oxide Control Daytime Oxidation and Quench Nocturnal Oxidation Chemistry in Delhi during Highly Polluted Episodes.

Delhi, India, suffers from periods of very poor air quality, but little is known about the chemical production of secondary pollutants in this highly polluted environment. During the postmonsoon period in 2018, extremely high nighttime concentrations of NOx (NO and NO2) and volatile organic compounds (VOCs) were observed, with median NOx mixing ratios of ∼200 ppbV (maximum of ∼700 ppbV). A detailed chemical box model constrained to a comprehensive suite of speciated VOC and NOx measurements revealed very low nighttime concentrations of oxidants, NO3, O3, and OH, driven by high nighttime NO concentrations. This results in an atypical NO3 diel profile, not previously reported in other highly polluted urban environments, significantly perturbing nighttime radical oxidation chemistry. Low concentrations of oxidants and high nocturnal primary emissions coupled with a shallow boundary layer led to enhanced early morning photo-oxidation chemistry. This results in a temporal shift in peak O3 concentrations when compared to the premonsoon period (12:00 and 15:00 local time, respectively). This shift will likely have important implications on local air quality, and effective urban air quality management should consider the impacts of nighttime emission sources during the postmonsoon period.

The variability of mass concentrations and source apportionment analysis of equivalent black carbon across urban Europe.

This study analyzed the variability of equivalent black carbon (eBC) mass concentrations and their sources in urban Europe to provide insights into the use of eBC as an advanced air quality (AQ) parameter for AQ standards. This study compiled eBC mass concentration datasets covering the period between 2006 and 2022 from 50 measurement stations, including 23 urban background (UB), 18 traffic (TR), 7 suburban (SUB), and 2 regional background (RB) sites. The results highlighted the need for the harmonization of eBC measurements to allow for direct comparisons between eBC mass concentrations measured across urban Europe. The eBC mass concentrations exhibited a decreasing trend as follows: TR > UB > SUB > RB. Furthermore, a clear decreasing trend in eBC concentrations was observed in the UB sites moving from Southern to Northern Europe. The eBC mass concentrations exhibited significant spatiotemporal heterogeneity, including marked differences in eBC mass concentration and variable contributions of pollution sources to bulk eBC between different cities. Seasonal patterns in eBC concentrations were also evident, with higher winter concentrations observed in a large proportion of cities, especially at UB and SUB sites. The contribution of eBC from fossil fuel combustion, mostly traffic (eBCT) was higher than that of residential and commercial sources (eBCRC) in all European sites studied. Nevertheless, eBCRC still had a substantial contribution to total eBC mass concentrations at a majority of the sites. eBC trend analysis revealed decreasing trends for eBCT over the last decade, while eBCRC remained relatively constant or even increased slightly in some cities.

Ambient air particulate total lung deposited surface area (LDSA) levels in urban Europe.

This study aims to picture the phenomenology of urban ambient total lung deposited surface area (LDSA) (including head/throat (HA), tracheobronchial (TB), and alveolar (ALV) regions) based on multiple path particle dosimetry (MPPD) model during 2017-2019 period collected from urban background (UB, n = 15), traffic (TR, n = 6), suburban background (SUB, n = 4), and regional background (RB, n = 1) monitoring sites in Europe (25) and USA (1). Briefly, the spatial-temporal distribution characteristics of the deposition of LDSA, including diel, weekly, and seasonal patterns, were analyzed. Then, the relationship between LDSA and other air quality metrics at each monitoring site was investigated. The result showed that the peak concentrations of LDSA at UB and TR sites are commonly observed in the morning (06:00-8:00 UTC) and late evening (19:00-22:00 UTC), coinciding with traffic rush hours, biomass burning, and atmospheric stagnation periods. The only LDSA night-time peaks are observed on weekends. Due to the variability of emission sources and meteorology, the seasonal variability of the LDSA concentration revealed significant differences (p = 0.01) between the four seasons at all monitoring sites. Meanwhile, the correlations of LDSA with other pollutant metrics suggested that Aitken and accumulation mode particles play a significant role in the total LDSA concentration. The results also indicated that the main proportion of total LDSA is attributed to the ALV fraction (50 %), followed by the TB (34 %) and HA (16 %). Overall, this study provides valuable information of LDSA as a predictor in epidemiological studies and for the first time presenting total LDSA in a variety of European urban environments.

Phenomenology of ultrafine particle concentrations and size distribution across urban Europe.

The 2017-2019 hourly particle number size distributions (PNSD) from 26 sites in Europe and 1 in the US were evaluated focusing on 16 urban background (UB) and 6 traffic (TR) sites in the framework of Research Infrastructures services reinforcing air quality monitoring capacities in European URBAN & industrial areaS (RI-URBANS) project. The main objective was to describe the phenomenology of urban ultrafine particles (UFP) in Europe with a significant air quality focus. The varying lower size detection limits made it difficult to compare PN concentrations (PNC), particularly PN10-25, from different cities. PNCs follow a TR > UB > Suburban (SUB) order. PNC and Black Carbon (BC) progressively increase from Northern Europe to Southern Europe and from Western to Eastern Europe. At the UB sites, typical traffic rush hour PNC peaks are evident, many also showing midday-morning PNC peaks anti-correlated with BC. These peaks result from increased PN10-25, suggesting significant PNC contributions from nucleation, fumigation and shipping. Site types to be identified by daily and seasonal PNC and BC patterns are: (i) PNC mainly driven by traffic emissions, with marked correlations with BC on different time scales; (ii) marked midday/morning PNC peaks and a seasonal anti-correlation with PNC/BC; (iii) both traffic peaks and midday peaks without marked seasonal patterns. Groups (ii) and (iii) included cities with high insolation. PNC, especially PN25-800, was positively correlated with BC, NO2, CO and PM for several sites. The variable correlation of PNSD with different urban pollutants demonstrates that these do not reflect the variability of UFP in urban environments. Specific monitoring of PNSD is needed if nanoparticles and their associated health impacts are to be assessed. Implementation of the CEN-ACTRIS recommendations for PNSD measurements would provide comparable measurements, and measurements of <10 nm PNC are needed for full evaluation of the health effects of this size fraction.

Non-linearity of secondary pollutant formation estimated from emissions data and measured precursor-secondary pollutant relationships.

In order to predict the impacts of reductions in air pollutant emissions, it is important to know whether secondary pollutant concentrations will decline in direct proportion to the reduction in their precursor, referred to as linearity. Trends in airborne concentrations of nitrate, sulfate, and SOC at sites in southern England are compared with emissions and concentration trends for sulfur dioxide (SO2), oxides of nitrogen (NO x ), and non-methane VOC, and show some increased ratios of concentrations to emissions, strongly suggestive of non-linearity in the primary-secondary pollutant relationships for nitrate, but not the other pollutants. Analysis of a further 20-year dataset from the AGANET network shows a decline of nitrate concentrations significantly lower than that of NO x emissions and ambient NO x concentrations. For sulfate, the decline lies between that of emissions and airborne concentrations of SO2. Back trajectory analysis and Potential Source Contribution Function mapping for 2014-2018 show that the highest concentrations of secondary constituents in southern England are associated with air masses originating in mainland Europe, with 42% of sulfate, 55% of nitrate, and 35% of SOC estimated to be associated with air masses entering the UK from the European mainland.

Leaching material from Antarctic seaweeds and penguin guano affects cloud-relevant aerosol production.

Within the Southern Ocean, the greatest warming is occurring on the Antarctic Peninsula (AP) where clear cryospheric and biological consequences are being observed. Antarctic coastal systems harbour a high diversity of marine and terrestrial ecosystems heavily influenced by Antarctic seaweeds (benthonic macroalgae) and bird colonies (mainly penguins). Primary sea spray aerosols (SSA) formed by the outburst of bubbles via the sea-surface microlayer depend on the organic composition of the sea water surface. In order to gain insight into the influence of ocean biology and biogeochemistry on atmospheric aerosol, we performed in situ laboratory aerosol bubble chamber experiments to study the effect of different leachates of biogenic material - obtained from common Antarctic seaweeds as well as penguin guano - on primary SSA. The addition of different leachate materials on a seawater sample showed a dichotomous effect depending on the leachate material added - either suppressing (up to 52%) or enhancing (22-88%) aerosol particle production. We found high ice nucleating particle number concentrations resulting from addition of guano leachate material. Given the evolution of upper marine polar coastal ecosystems in the AP, further studies on ocean-atmosphere coupling are needed in order to represent the currently poorly understood climate feedback processes.