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Air ions are electrically charged particles in air. They are ubiquitous in the natural environment and affect the Earth's radiation budget by accelerating the formation and growth of new aerosol particles. Despite this, few datasets exist exploring these effects in the urban environment. A neutral cluster and air ion spectrometer was deployed in Leipzig, Germany, to measure the number size distribution of charged particles from 0.8 to 42 nm, between 27 July and 25 August 2022. Following previous analyses, charged particles were classified into small (0.8–1.6 nm), intermediate (1.6–7.5 nm), and large (7.5–22 nm) fractions by mass diameter, and their mean concentrations (sum of positive and negative polarities) during the campaign were 405, 71.6, and 415 cm−3, respectively. The largest peaks in intermediate and large ions were explained by new particle formation (NPF), with intermediate ions correlating well with sulfuric acid dimer. Smaller morning and evening peaks were coincident with black carbon concentrations and attributed to primary emissions. NPF events, observed on 30 % of days, coincided with intense solar radiation and elevated sulfuric acid dimer. Small charged particles were primarily associated with radioactive decay and highest during the early hours, and they are unrelated to primary emissions or NPF. The apparent contributions of charged particles to 3 and 7.5 nm particle formation rates were 5.7 % and 12.7 %, respectively, with mean growth rates of 4.0 nm h−1 between 3–7.5 nm and 5.2 nm h−1 between 7.5 and 22 nm. The ratio of charged to total particle formation rates at 3 nm suggests a minor role for charged particles in NPF. We conclude that NPF is a primary source of > 3 nm ions in our data, with primary emissions being the major source in the absence of NPF.

Lockdown restrictions in response to the COVID-19 pandemic led to the curtailment of many activities and reduced emissions of primary air pollutants. Here, we applied positive matrix factorisation to particle size distribution (PSD) data from six monitoring sites (three urban background and three roadside) between four European cities (Helsinki, Leipzig, Budapest, and London) to evaluate how particle number concentrations (PNCs) and their sources changed during the respective 2020 lockdown periods compared to the reference years 2014–2019. A number of common factors were resolved between sites, including nucleation, road traffic semi-volatile fraction (road trafficsvf), road traffic solid fraction (road trafficsf), diffuse urban (wood smoke + aged traffic), ozone-associated secondary aerosol (O3-associated SA), and secondary inorganic aerosol (SIA). Nucleation, road traffic, and diffuse urban factors were the largest contributors to mean PNCs during the reference years and respective lockdown periods. However, SIA factors were the largest contributors to particle mass concentrations, irrespective of environment type. Total mean PNCs were lower at two of the urban-background and all roadside sites during lockdown. The response of nucleation and road trafficsvf factors to lockdown restrictions was highly variable, although road trafficsf factors were consistently lower at roadside sites. The responses of diffuse urban factors were largely consistent and were mostly lower at urban-background sites. Secondary aerosols (O3-associated SA and SIA) exhibited extensive reductions in their mean PNCs at all sites. These variegated responses to lockdowns across Europe point to a complex network of sources and aerosol sinks contributing to PSDs.

Antarctica and the Southern Ocean (SO) are the most pristine areas of the globe and represent ideal places to investigate aerosol–climate interactions in an unperturbed atmosphere. In this study, we present submicrometer aerosol (PM1) source apportionment for two sample sets collected in parallel at the British Antarctic Survey stations of Signy and Halley during the austral summer of 2018–2019. Water-soluble organic matter (WSOM) is a major aerosol component at both sites (37 % and 29 % of water-soluble PM1, on average, at Signy and Halley, respectively). Remarkable differences between pelagic (open-ocean) and sympagic (influenced by sea ice) air mass histories and related aerosol sources are found. The application of factor analysis techniques to series of spectra obtained by means of proton-nuclear magnetic resonance (H-NMR) spectroscopy on the samples allows the identification of five organic aerosol (OA) sources: two primary organic aerosol (POA) types, characterized by sugars, polyols, and degradation products of lipids and associated with open-ocean and sympagic/coastal waters, respectively; two secondary organic aerosol (SOA) types, one enriched in methanesulfonic acid (MSA) and dimethylamine (DMA) and associated with pelagic waters and the other characterized by trimethylamine (TMA) and linked to sympagic environments; and a fifth component of unclear origin, possibly associated with the atmospheric aging of primary emissions. Overall, our results strongly indicate that the emissions from sympagic and pelagic ecosystems affect the variability in the submicrometer aerosol composition in the study area, with atmospheric circulation establishing marked latitudinal gradients only for some of the aerosol components (e.g., the sympagic components) while distributing the others (e.g., pelagic and/or aged components) both in maritime and inner Antarctic regions.

Anthropogenic non-methane volatile organic compounds (VOCs) in the United Kingdom have been substantially reduced since 1990, which is, in part, attributed to controls on evaporative and vehicle tailpipe emissions. Over time, other sources with a different speciation (for example, alcohols from solvent use and industry processes) have grown in both relative importance and, in some cases, in absolute terms. The impact of this change in speciation and the resulting photochemical reactivities of VOCs are evaluated using a photochemical box model constrained by observational data during a summertime ozone event (Birmingham, UK) and apportionment of sources based on the UK National Atmospheric Emission Inventory (NAEI) data over the period 1990–2019. Despite road transport sources representing only 3.3 % of UK VOC emissions in 2019, road transport continued being the sector with the largest influence on the local O3 production rate (P(O3)). Under case study conditions, the 96 % reduction in road transport VOC emissions that has been achieved between 1990 and 2019 has likely reduced daytime P(O3) by ∼ 1.67 ppbv h−1. Further abatement of fuel fugitive emissions was modeled to have had less impact on P(O3) reduction than abatement of VOCs from industrial processes and solvent use. The long-term trend of increased emissions of ethanol and methanol has somewhat weakened the benefits of reducing road transport emissions, increasing P(O3) by ∼ 0.19 ppbv h−1 in the case study. Abatement of VOC emissions from multiple sources has been a notable technical and policy success in the UK, but some future benefits (from an ozone perspective) of the phase-out of internal combustion engine passenger cars may be offset if domestic and commercial solvent use of VOCs continue to increase.

The impact of heterogeneous uptake of HO2 on aerosol surfaces on radical concentrations and the O3 production regime in Beijing in summertime was investigated. The uptake coefficient of HO2 onto aerosol surfaces, γHO2, was calculated for the AIRPRO campaign in Beijing, in summer 2017, as a function of measured aerosol soluble copper concentration, [Cu2+]eff, aerosol liquid water content, [ALWC], and particulate matter concentration, [PM]. An average γHO2 across the entire campaign of 0.070±0.035 was calculated, with values ranging from 0.002 to 0.15, and found to be significantly lower than the value of γHO2=0.2, commonly used in modelling studies. Using the calculated γHO2 values for the summer AIRPRO campaign, OH, HO2 and RO2 radical concentrations were modelled using a box model incorporating the Master Chemical Mechanism (v3.3.1), with and without the addition of γHO2, and compared to the measured radical concentrations. The rate of destruction analysis showed the dominant HO2 loss pathway to be HO2 + NO for all NO concentrations across the summer Beijing campaign, with HO2 uptake contributing % to the total loss of HO2 on average. This result for Beijing summertime would suggest that under most conditions encountered, HO2 uptake onto aerosol surfaces is not important to consider when investigating increasing O3 production with decreasing [PM] across the North China Plain. At low [NO], however, i.e. ppb, which was often encountered in the afternoons, up to 29 % of modelled HO2 loss was due to HO2 uptake on aerosols when calculated γHO2 was included, even with the much lower γHO2 values compared to γHO2= 0.2, a result which agrees with the aerosol-inhibited O3 regime recently proposed by Ivatt et al. (2022). As such it can be concluded that in cleaner environments, away from polluted urban centres where HO2 loss chemistry is not dominated by NO but where aerosol surface area is high still, changes in PM concentration and hence aerosol surface area could still have a significant effect on both overall HO2 concentration and the O3 production regime. Using modelled radical concentrations, the absolute O3 sensitivity to NOx and volatile organic compounds (VOCs) showed that, on average across the summer AIRPRO campaign, the O3 production regime remained VOC-limited, with the exception of a few days in the afternoon when the NO mixing ratio dropped low enough for the O3 regime to shift towards being NOx-limited. The O3 sensitivity to VOCs, the dominant regime during the summer AIRPRO campaign, was observed to decrease and shift towards a NOx-sensitive regime both when NO mixing ratio decreased and with the addition of aerosol uptake. This suggests that if [NOx] continues to decrease in the future, ozone reduction policies focussing solely on NOx reductions may not be as efficient as expected if [PM] and, hence, HO2 uptake to aerosol surfaces continue to decrease. The addition of aerosol uptake into the model, for both the γHO2 calculated from measured data and when using a fixed value of γHO2=0.2, did not have a significant effect on the overall O3 production regime across the campaign. While not important for this campaign, aerosol uptake could be important for areas of lower NO concentration that are already in a NOx-sensitive regime.

The Arctic is a rapidly changing ecosystem, with complex ice–ocean–atmosphere feedbacks. An important process is new particle formation (NPF), from gas-phase precursors, which provides a climate forcing effect. NPF has been studied comprehensively at different sites in the Arctic, ranging from those in the High Arctic and those at Svalbard to those in the continental Arctic, but no harmonised analysis has been performed on all sites simultaneously, with no calculations of key NPF parameters available for some sites. Here, we analyse the formation and growth of new particles from six long-term ground-based stations in the Arctic (Alert, Villum, Tiksi, Zeppelin Mountain, Gruvebadet, and Utqiaġvik). Our analysis of particle formation and growth rates in addition to back-trajectory analysis shows a summertime maxima in the frequency of NPF and particle formation rate at all sites, although the mean frequency and particle formation rates themselves vary greatly between sites, with the highest at Svalbard and lowest in the High Arctic. The summertime growth rate, condensational sinks, and vapour source rates show a slight bias towards the southernmost sites, with vapour source rates varying by around an order of magnitude between the northernmost and southernmost sites. Air masses back-trajectories during NPF at these northernmost sites are associated with large areas of sea ice and snow, whereas events at Svalbard are associated with more sea ice and ocean regions. Events at the southernmost sites are associated with large areas of land and sea ice. These results emphasise how understanding the geographical variation in surface type across the Arctic is key to understanding secondary aerosol sources and providing a harmonised analysis of NPF across the Arctic.

Knowledge of air pollution sources is important in policymaking and air pollution mitigation. Until recently, source apportion analyses were limited and only possible with the use of expensive regulatory-grade instruments. In the present study we applied a two-step positive matrix factorisation (PMF) receptor analysis at a background site in Birmingham, UK using data acquired by low-cost sensors (LCSs). The application of PMF allowed for the identification of the sources that affect the local air quality, clearly separating different sources of particulate matter (PM) pollution. Furthermore, the method allowed for the contribution of different air pollution sources to the overall air quality at the site to be estimated, thereby providing pollution source apportionment. The use of data from regulatory-grade (RG) instruments further confirmed the reliability of the results, as well as further clarifying the particulate matter composition and origin. Compared with the results from a previous analysis, in which a k-means clustering algorithm was used, a good consistency between the k means and PMF results was found in pinpointing and separating the sources of pollution that affect the site. The potential and limitations of each method when used with low-cost sensor data are highlighted. The analysis presented in this study paves the way for more extensive use of LCSs for atmospheric applications, receptor modelling and source apportionment. Here, we present the infrastructure for understanding the factors that affect air quality at a significantly lower cost than previously possible. This should provide new opportunities for regulatory and indicative monitoring for both scientific and industrial applications.

Delhi is one of the world's most polluted cities, with very high concentrations of airborne particulate matter. However, little is known about the factors controlling the characteristics of wide-range particle number size distributions. Here, new measurements are reported from three field campaigns conducted in winter and pre-monsoon and post-monsoon seasons at the Indian Institute of Technology campus in the south of the city. Particle number size distributions were measured simultaneously, using a scanning mobility particle sizer and a GRIMM optical particle monitor, covering 15 nm to >10 µm diameter. The merged, wide-range size distributions were categorized into the following five size ranges: nucleation (15–20 nm), Aitken (20–100 nm), accumulation (100 nm–1 µm), large fine (1–2.5 µm), and coarse (2.5–10 µm) particles. The ultrafine fraction (15–100 nm) accounts for about 52 % of all particles by number (PN10 is the total particle number from 15 nm to 10 µm) but just 1 % by PM10 volume (PV10 is the total particle volume from 15 nm to 10 µm). The measured size distributions are markedly coarser than most from other parts of the world but are consistent with earlier cascade impactor data from Delhi. Our results suggest substantial aerosol processing by coagulation, condensation, and water uptake in the heavily polluted atmosphere, which takes place mostly at nighttime and in the morning hours. Total number concentrations are highest in winter, but the mode of the distribution is largest in the post-monsoon (autumn) season. The accumulation mode particles dominate the particle volume in autumn and winter, while the coarse mode dominates in summer. Polar plots show a huge variation between both size fractions in the same season and between seasons for the same size fraction. The diurnal pattern of particle numbers is strongly reflective of a road traffic influence upon concentrations, especially in autumn and winter, although other sources, such as cooking and domestic heating, may influence the evening peak. There is a clear influence of diesel traffic at nighttime, when it is permitted to enter the city, and also indications in the size distribution data of a mode < 15 nm, which is probably attributable to CNG/LPG vehicles. New particle formation appears to be infrequent and is, in this dataset, limited to 1 d in the summer campaign. Our results reveal that the very high emissions of airborne particles in Delhi, particularly from traffic, determine the variation in particle number size distributions.

This study presents the source apportionment of PM2.5 performed by positive matrix factorization (PMF) on data presented here which were collected at urban (Institute of Atmospheric Physics – IAP) and rural (Pinggu – PG) sites in Beijing as part of the Atmospheric Pollution and Human Health in a Chinese megacity (APHH-Beijing) field campaigns. The campaigns were carried out from 9 November to 11 December 2016 and from 22 May to 24 June 2017. The PMF analysis included both organic and inorganic species, and a seven-factor output provided the most reasonable solution for the PM2.5 source apportionment. These factors are interpreted as traffic emissions, biomass burning, road dust, soil dust, coal combustion, oil combustion, and secondary inorganics. Major contributors to PM2.5 mass were secondary inorganics (IAP: 22 %; PG: 24 %), biomass burning (IAP: 36 %; PG: 30 %), and coal combustion (IAP: 20 %; PG: 21 %) sources during the winter period at both sites. Secondary inorganics (48 %), road dust (20 %), and coal combustion (17 %) showed the highest contribution during summer at PG, while PM2.5 particles were mainly composed of soil dust (35 %) and secondary inorganics (40 %) at IAP. Despite this, factors that were resolved based on metal signatures were not fully resolved and indicate a mixing of two or more sources. PMF results were also compared with sources resolved from another receptor model (i.e. chemical mass balance – CMB) and PMF performed on other measurements (i.e. online and offline aerosol mass spectrometry, AMS) and showed good agreement for some but not all sources. The biomass burning factor in PMF may contain aged aerosols as a good correlation was observed between biomass burning and oxygenated fractions (r2= 0.6–0.7) from AMS. The PMF failed to resolve some sources identified by the CMB and AMS and appears to overestimate the dust sources. A comparison with earlier PMF source apportionment studies from the Beijing area highlights the very divergent findings from application of this method.

New particle formation (NPF) events occur almost everywhere in the world and can play an important role as a particle source. The frequency and characteristics of NPF events vary spatially, and this variability is yet to be fully understood. In the present study, long-term particle size distribution datasets (minimum of 3 years) from 13 sites of various land uses and climates from across Europe were studied, and NPF events, deriving from secondary formation and not traffic-related nucleation, were extracted and analysed. The frequency of NPF events was consistently found to be higher at rural background sites, while the growth and formation rates of newly formed particles were higher at roadsides (though in many cases differences between the sites were small), underlining the importance of the abundance of condensable compounds of anthropogenic origin found there. The growth rate was higher in summer at all rural background sites studied. The urban background sites presented the highest uncertainty due to greater variability compared to the other two types of site. The origin of incoming air masses and the specific conditions associated with them greatly affect the characteristics of NPF events. In general, cleaner air masses present higher probability for NPF events, while the more polluted ones show higher growth rates. However, different patterns of NPF events were found, even at sites in close proximity (< 200 km), due to the different local conditions at each site. Region-wide events were also studied and were found to be associated with the same conditions as local events, although some variability was found which was associated with the different seasonality of the events at two neighbouring sites. NPF events were responsible for an increase in the number concentration of ultrafine particles of more than 400 % at rural background sites on the day of their occurrence. The degree of enhancement was less at urban sites due to the increased contribution of other sources within the urban environment. It is evident that, while some variables (such as solar radiation intensity, relative humidity, or the concentrations of specific pollutants) appear to have a similar influence on NPF events across all sites, it is impossible to predict the characteristics of NPF events at a site using just these variables, due to the crucial role of local conditions.

Understanding aerosol–cloud–climate interactions in the Arctic is key to predicting the climate in this rapidly changing region. Whilst many studies have focused on submicrometer aerosol (diameter less than 1 µm), relatively little is known about the supermicrometer aerosol (diameter above 1 µm). Here, we present a cluster analysis of multiyear (2015–2019) aerodynamic volume size distributions, with diameter ranging from 0.5 to 20 µm, measured continuously at the Gruvebadet Observatory in the Svalbard archipelago. Together with aerosol chemical composition data from several online and offline measurements, we apportioned the occurrence of the coarse-mode aerosols during the study period (mainly from March to October) to anthropogenic (two sources, 27 %) and natural (three sources, 73 %) origins. Specifically, two clusters are related to Arctic haze with high levels of black carbon, sulfate and accumulation mode (0.1–1 µm) aerosol. The first cluster (9 %) is attributed to ammonium sulfate-rich Arctic haze particles, whereas the second one (18 %) is attributed to larger-mode aerosol mixed with sea salt. The three natural aerosol clusters were open-ocean sea spray aerosol (34 %), mineral dust (7 %) and an unidentified source of sea spray-related aerosol (32 %). The results suggest that sea-spray-related aerosol in polar regions may be more complex than previously thought due to short- and long-distance origins and mixtures with Arctic haze, biogenic and likely blowing snow aerosols. Studying supermicrometer natural aerosol in the Arctic is imperative for understanding the impacts of changing natural processes on Arctic aerosol.

Measurement and source apportionment of atmospheric pollutants are crucial for the assessment of air quality and the implementation of policies for their improvement. In most cases, such measurements use expensive regulatory-grade instruments, which makes it difficult to achieve wide spatial coverage. Low-cost sensors may provide a more affordable alternative, but their capability and reliability in separating distinct sources of particles have not been tested extensively yet. The present study examines the ability of a low-cost optical particle counter (OPC) to identify the sources of particles and conditions that affect particle concentrations at an urban background site in Birmingham, UK. To help evaluate the results, the same analysis is performed on data from a regulatory-grade instrument (SMPS, scanning mobility particle sizer) and compared to the outcomes from the OPC analysis. The analysis of the low-cost sensor data manages to separate periods and atmospheric conditions according to the level of pollution at the site. It also successfully identifies a number of sources for the observed particles, which were also identified using the regulatory-grade instruments. The low-cost sensor, due to the particle size range measured (0.35 to 40 µm), performed rather well in differentiating sources of particles with sizes greater than 1 µm, though its ability to distinguish their diurnal variation, as well as to separate sources of smaller particles, at the site was limited. The current level of source identification demonstrated makes the technique useful for background site studies, where larger particles with smaller temporal variations are of significant importance. This study highlights the current capability of low-cost sensors in source identification and differentiation using clustering approaches. Future directions towards particulate matter source apportionment using low-cost OPCs are highlighted.

Fine particles were sampled from 9 November to 11 December 2016 and 22 May to 24 June 2017 as part of the Atmospheric Pollution and Human Health in a Chinese Megacity (APHH-China) field campaigns in urban Beijing, China. Inorganic ions, trace elements, organic carbon (OC), elemental carbon (EC), and organic compounds, including biomarkers, hopanes, polycyclic aromatic hydrocarbons (PAHs), n-alkanes, and fatty acids, were determined for source apportionment in this study. Carbonaceous components contributed on average 47.2 % and 35.2 % of total reconstructed PM2.5 during the winter and summer campaigns, respectively. Secondary inorganic ions (sulfate, nitrate, ammonium; SNA) accounted for 35.0 % and 45.2 % of total PM2.5 in winter and summer. Other components including inorganic ions (K+, Na+, Cl−), geological minerals, and trace metals only contributed 13.2 % and 12.4 % of PM2.5 during the winter and summer campaigns. Fine OC was explained by seven primary sources (industrial and residential coal burning, biomass burning, gasoline and diesel vehicles, cooking, and vegetative detritus) based on a chemical mass balance (CMB) receptor model. It explained an average of 75.7 % and 56.1 % of fine OC in winter and summer, respectively. Other (unexplained) OC was compared with the secondary OC (SOC) estimated by the EC-tracer method, with correlation coefficients (R2) of 0.58 and 0.73 and slopes of 1.16 and 0.80 in winter and summer, respectively. This suggests that the unexplained OC by the CMB model was mostly associated with SOC. PM2.5 apportioned by the CMB model showed that the SNA and secondary organic matter were the two highest contributors to PM2.5. After these, coal combustion and biomass burning were also significant sources of PM2.5 in winter. The CMB results were also compared with results from the positive matrix factorization (PMF) analysis of co-located aerosol mass spectrometer (AMS) data. The CMB model was found to resolve more primary organic aerosol (OA) sources than AMS-PMF, but the latter could apportion secondary OA sources. The AMS-PMF results for major components, such as coal combustion OC and oxidized OC, correlated well with the results from the CMB model. However, discrepancies and poor agreements were found for other OC sources, such as biomass burning and cooking, some of which were not identified in AMS-PMF factors.

Carbonaceous aerosol is a dominant component of fine particles in Beijing. However, it is challenging to apportion its sources. Here, we applied a newly developed method which combined radiocarbon (14C) with organic tracers to apportion the sources of fine carbonaceous particles at an urban (IAP) and a rural (PG) site of Beijing. PM2.5 filter samples (24 h) were collected at both sites from 10 November to 11 December 2016 and from 22 May to 24 June 2017. 14C was determined in 25 aerosol samples (13 at IAP and 12 at PG) representing low pollution to haze conditions. Biomass burning tracers (levoglucosan, mannosan, and galactosan) in the samples were also determined using gas chromatography–mass spectrometry (GC-MS). Higher contributions of fossil-derived OC (OCf) were found at the urban site. The OCf / OC ratio decreased in the summer samples (IAP: 67.8 ± 4.0 % in winter and 54.2 ± 11.7 % in summer; PG: 59.3 ± 5.7 % in winter and 50.0 ± 9.0 % in summer) due to less consumption of coal in the warm season. A novel extended Gelencsér (EG) method incorporating the 14C and organic tracer data was developed to estimate the fossil and non-fossil sources of primary and secondary OC (POC and SOC). It showed that fossil-derived POC was the largest contributor to OC (35.8 ± 10.5 % and 34.1 ± 8.7 % in wintertime for IAP and PG, 28.9 ± 7.4 % and 29.1 ± 9.4 % in summer), regardless of season. SOC contributed 50.0 ± 12.3 % and 47.2 ± 15.5 % at IAP and 42.0 ± 11.7 % and 43.0 ± 13.4 % at PG in the winter and summer sampling periods, respectively, within which the fossil-derived SOC was predominant and contributed more in winter. The non-fossil fractions of SOC increased in summer due to a larger biogenic component. Concentrations of biomass burning OC (OCbb) are resolved by the extended Gelencsér method, with average contributions (to total OC) of 10.6 ± 1.7 % and 10.4 ± 1.5 % in winter at IAP and PG and 6.5 ± 5.2 % and 17.9 ± 3.5 % in summer, respectively. Correlations of water-insoluble OC (WINSOC) and water-soluble OC (WSOC) with POC and SOC showed that although WINSOC was the major contributor to POC, a non-negligible fraction of WINSOC was found in SOC for both fossil and non-fossil sources, especially during winter. In summer, a greater proportion of WSOC from non-fossil sources was found in SOC. Comparisons of the source apportionment results with those obtained from a chemical mass balance model were generally good, except for the cooking aerosol.

Epidemiological studies have consistently linked exposure to PM2.5 with adverse health effects. The oxidative potential (OP) of aerosol particles has been widely suggested as a measure of their potential toxicity. Several acellular chemical assays are now readily employed to measure OP; however, uncertainty remains regarding the atmospheric conditions and specific chemical components of PM2.5 that drive OP. A limited number of studies have simultaneously utilised multiple OP assays with a wide range of concurrent measurements and investigated the seasonality of PM2.5 OP. In this work, filter samples were collected in winter 2016 and summer 2017 during the atmospheric pollution and human health in a Chinese megacity campaign (APHH-Beijing), and PM2.5 OP was analysed using four acellular methods: ascorbic acid (AA), dithiothreitol (DTT), 2,7-dichlorofluorescin/hydrogen peroxidase (DCFH) and electron paramagnetic resonance spectroscopy (EPR). Each assay reflects different oxidising properties of PM2.5, including particle-bound reactive oxygen species (DCFH), superoxide radical production (EPR) and catalytic redox chemistry (DTT/AA), and a combination of these four assays provided a detailed overall picture of the oxidising properties of PM2.5 at a central site in Beijing. Positive correlations of OP (normalised per volume of air) of all four assays with overall PM2.5 mass were observed, with stronger correlations in winter compared to summer. In contrast, when OP assay values were normalised for particle mass, days with higher PM2.5 mass concentrations (µg m−3) were found to have lower mass-normalised OP values as measured by AA and DTT. This finding supports that total PM2.5 mass concentrations alone may not always be the best indicator for particle toxicity. Univariate analysis of OP values and an extensive range of additional measurements, 107 in total, including PM2.5 composition, gas-phase composition and meteorological data, provided detailed insight into the chemical components and atmospheric processes that determine PM2.5 OP variability. Multivariate statistical analyses highlighted associations of OP assay responses with varying chemical components in PM2.5 for both mass- and volume-normalised data. AA and DTT assays were well predicted by a small set of measurements in multiple linear regression (MLR) models and indicated fossil fuel combustion, vehicle emissions and biogenic secondary organic aerosol (SOA) as influential particle sources in the assay response. Mass MLR models of OP associated with compositional source profiles predicted OP almost as well as volume MLR models, illustrating the influence of mass composition on both particle-level OP and total volume OP. Univariate and multivariate analysis showed that different assays cover different chemical spaces, and through comparison of mass- and volume-normalised data we demonstrate that mass-normalised OP provides a more nuanced picture of compositional drivers and sources of OP compared to volume-normalised analysis. This study constitutes one of the most extensive and comprehensive composition datasets currently available and provides a unique opportunity to explore chemical variations in PM2.5 and how they affect both PM2.5 OP and the concentrations of particle-bound reactive oxygen species.

Although new particle formation (NPF) events have been studied extensively for some decades, the mechanisms that drive their occurrence and development are yet to be fully elucidated. Laboratory studies have done much to elucidate the molecular processes involved in nucleation, but this knowledge has yet to be conclusively linked to NPF events in the atmosphere. There is great difficulty in successful application of the results from laboratory studies to real atmospheric conditions due to the diversity of atmospheric conditions and observations found, as NPF events occur almost everywhere in the world without always following a clearly defined trend of frequency, seasonality, atmospheric conditions, or event development. The present study seeks common features in nucleation events by applying a binned linear regression over an extensive dataset from 16 sites of various types (combined dataset of 85 years from rural and urban backgrounds as well as roadside sites) in Europe. At most sites, a clear positive relation with the frequency of NPF events is found between the solar radiation intensity (up to R2=0.98), temperature (up to R2=0.98), and atmospheric pressure (up to R2=0.97), while relative humidity (RH) presents a negative relation (up to R2=0.95) with NPF event frequency, though exceptions were found among the sites for all the variables studied. Wind speed presents a less consistent relationship, which appears to be heavily affected by local conditions. While some meteorological variables (such as the solar radiation intensity and RH) appear to have a crucial effect on the occurrence and characteristics of NPF events, especially at rural sites, it appears that their role becomes less marked at higher average values. The analysis of chemical composition data presents interesting results. Concentrations of almost all chemical compounds studied (apart from O3) and the condensation sink (CS) have a negative relationship with NPF event frequency, though areas with higher average concentrations of SO2 had higher NPF event frequency. Particulate organic carbon (OC), volatile organic compounds (VOCs), and particulate-phase sulfate consistently had a positive relation with the growth rate of the newly formed particles. As with some meteorological variables, it appears that at increased concentrations of pollutants or the CS, their influence upon NPF frequency is reduced.

Water-soluble inorganic ions such as ammonium, nitrate and sulfate are major components of fine aerosols in the atmosphere and are widely used in the estimation of aerosol acidity. However, different experimental practices and instrumentation may lead to uncertainties in ion concentrations. Here, an intercomparison experiment was conducted in 10 different laboratories (labs) to investigate the consistency of inorganic ion concentrations and resultant aerosol acidity estimates using the same set of aerosol filter samples. The results mostly exhibited good agreement for major ions Cl−, SO42-, NO3-, NH4+ and K+. However, F−, Mg2+ and Ca2+ were observed with more variations across the different labs. The Aerosol Chemical Speciation Monitor (ACSM) data of nonrefractory SO42-, NO3- and NH4+ generally correlated very well with the filter-analysis-based data in our study, but the absolute concentrations differ by up to 42 %. Cl− from the two methods are correlated, but the concentration differ by more than a factor of 3. The analyses of certified reference materials (CRMs) generally showed a good detection accuracy (DA) of all ions in all the labs, the majority of which ranged between 90 % and 110 %. The DA was also used to correct the ion concentrations to showcase the importance of using CRMs for calibration check and quality control. Better agreements were found for Cl−, SO42-, NO3-, NH4+ and K+ across the labs after their concentrations were corrected with DA; the coefficient of variation (CV) of Cl−, SO42-, NO3-, NH4+ and K+ decreased by 1.7 %, 3.4 %, 3.4 %, 1.2 % and 2.6 %, respectively, after DA correction. We found that the ratio of anion to cation equivalent concentrations (AE / CE) and ion balance (anions–cations) are not good indicators for aerosol acidity estimates, as the results in different labs did not agree well with each other. In situ aerosol pH calculated from the ISORROPIA II thermodynamic equilibrium model with measured ion and ammonia concentrations showed a similar trend and good agreement across the 10 labs. Our results indicate that although there are important uncertainties in aerosol ion concentration measurements, the estimated aerosol pH from the ISORROPIA II model is more consistent.

This study investigates the chemical composition of PM2.5 collected at a central location in Beijing, China, during winter 2016 and summer 2017. The samples were characterised using direct-infusion negative-nano-electrospray-ionisation ultrahigh-resolution mass spectrometry to elucidate the composition and the potential primary and secondary sources of the organic fraction. The samples from the two seasons were compared with those from a road-tunnel site and an urban background site in Birmingham, UK, analysed in the course of an earlier study using the same method. There were strong differences in aerosol particle composition between the seasons, particularly regarding (poly-)aromatic compounds, which were strongly enhanced in winter, likely due to increased fossil fuel and biomass burning for heating. In addition to the seasonal differences, compositional differences between high- and low-pollution conditions were observed, with the contribution of sulfur-containing organic compounds strongly enhanced under high-pollution conditions. There was a correlation of the number of sulfur-containing molecular formulae with the concentration of particulate sulfate, consistent with a particle-phase formation process.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous pollutants in air, soil, and water and are known to have harmful effects on human health and the environment. The diurnal and nocturnal variations of 17 PAHs in ambient particle-bound PAHs were measured in urban Beijing (China) and Delhi (India) during the summer season using gas-chromatography–quadrupole time-of-flight mass spectrometry (GC-Q-TOF-MS). The mean concentration of particles less than 2.5 µm (PM2.5) observed in Delhi was 3.6 times higher than in Beijing during the measurement period in both the daytime and night-time. In Beijing, the mean concentration of the sum of the 17 PAHs (∑17 PAHs) was 8.2 ± 5.1 ng m−3 in daytime, with the highest contribution from indeno[1,2,3-cd]pyrene (12 %), while at night-time the total PAHs was 7.2 ± 2.0 ng m−3, with the largest contribution from benzo[b]fluoranthene (14 %). In Delhi, the mean ∑17 PAHs was 13.6 ± 5.9 ng m−3 in daytime and 22.7 ± 9.4 ng m−3 at night-time, with the largest contribution from indeno[1,2,3-cd]pyrene in both the day (17 %) and night (20 %). Elevated mean concentrations of total PAHs in Delhi observed at night were attributed to emissions from vehicles and biomass burning and to meteorological conditions leading to their accumulation from a stable and low atmospheric boundary layer. Local emission sources were typically identified as the major contributors to total measured PAHs in both cities. Major emission sources were characterized based on the contribution from each class of PAHs, with the four-, five- and six-ring PAHs accounting ∼ 95 % of the total PM2.5-bound PAHs mass in both locations. The high contribution of five-ring PAHs to total PAH concentration in summer Beijing and Delhi suggests a high contribution from petroleum combustion. In Delhi, a high contribution from six-ring PAHs was observed at night, suggesting a potential emission source from the combustion of fuel and oil in power generators, widely used in Delhi. The lifetime excess lung cancer risk (LECR) was calculated for Beijing and Delhi, with the highest estimated risk attributed to Delhi (LECR = 155 per million people), which is 2.2 times higher than the Beijing risk assessment value (LECR = 70 per million people). Finally, we have assessed the emission control policies in each city and identified those major sectors that could be subject to mitigation measures.

Atmospheric aerosols contribute some of the greatest uncertainties to estimates of global radiative forcing and have significant effects on human health. New particle formation (NPF) is the process by which new aerosols of sub-2 nm diameter form from gas-phase precursors and contributes significantly to particle numbers in the atmosphere, accounting for approximately 50 % of cloud condensation nuclei globally. Here, we study summertime NPF in urban Barcelona in north-eastern Spain utilising particle counting instruments down to 1.9 nm and a Nitrate Chemical Ionisation Atmospheric Pressure interface Time of Flight Mass Spectrometer (CI-APi-ToF). The rate of formation of new particles is seen to increase linearly with sulfuric acid concentration, although particle formation rates fall short of chamber studies of H2SO4–DMA–H2O while exceeding those of H2SO4–BioOxOrg–H2O nucleation, although a role of highly oxygenated molecules (HOMs) cannot be ruled out. The sulfuric acid dimer : monomer ratio is significantly lower than that seen in experiments involving sulfuric acid and dimethylamine (DMA) in chambers, indicating that stabilisation of sulfuric acid clusters by bases is weaker in this dataset than in chambers, either due to rapid evaporation due to high summertime temperatures or limited pools of stabilising amines. Such a mechanism cannot be verified in these data, as no higher-order H2SO4–amine clusters nor H2SO4–HOM clusters were measured. The high concentrations of HOMs arise from isoprene, alkylbenzene, monoterpene and polycyclic aromatic hydrocarbon (PAH) oxidation, with alkylbenzenes providing greater concentrations of HOMs due to significant local sources. The concentration of these HOMs shows a dependence on temperature. The organic compounds measured primarily fall into the semivolatile organic compound (SVOC) volatility class arising from alkylbenzene and isoprene oxidation. Low-volatility organic compounds (LVOCs) largely arise from oxidation of alkylbenzenes, PAHs and monoterpenes, whereas extremely low-volatility organic compounds (ELVOCs) arise from primarily PAH and monoterpene oxidation. New particle formation without growth past 10 nm is also observed, and on these days oxygenated organic concentrations are lower than on days with growth by a factor of 1.6, and thus high concentrations of low-volatility oxygenated organics which primarily derive from traffic-emitted volatile organic compounds (VOCs) appear to be a necessary condition for the growth of newly formed particles in Barcelona. These results are consistent with prior observations of new particle formation from sulfuric acid–amine reactions in both chambers and the real atmosphere and are likely representative of the urban background of many European Mediterranean cities. A role for HOMs in the nucleation process cannot be confirmed or ruled out, and there is strong circumstantial evidence of the participation of HOMs across multiple volatility classes in particle growth.

The Southern Ocean and Antarctic region currently best represent one of the few places left on our planet with conditions similar to the preindustrial age. Currently, climate models have a low ability to simulate conditions forming the aerosol baseline; a major uncertainty comes from the lack of understanding of aerosol size distributions and their dynamics. Contrasting studies stress that primary sea salt aerosol can contribute significantly to the aerosol population, challenging the concept of climate biogenic regulation by new particle formation (NPF) from dimethyl sulfide marine emissions. We present a statistical cluster analysis of the physical characteristics of particle size distributions (PSDs) collected at Halley (Antarctica) for the year 2015 (89 % data coverage; 6–209 nm size range; daily size resolution). By applying the Hartigan–Wong k-mean method we find eight clusters describing the entire aerosol population. Three clusters show pristine average low particle number concentrations (< 121–179 cm−3) with three main modes (30, 75–95 and 135–160 nm) and represent 57 % of the annual PSD (up to 89 %–100 % during winter and 34 %–65 % during summer based on monthly averages). Nucleation and Aitken mode PSD clusters dominate summer months (September–January, 59 %–90 %), whereas a clear bimodal distribution (43 and 134 nm, respectively; Hoppel minimum at mode 75 nm) is seen only during the December–April period (6 %–21 %). Major findings of the current work include: (1) NPF and growth events originate from both the sea ice marginal zone and the Antarctic plateau, strongly suggesting multiple vertical origins, including the marine boundary layer and free troposphere; (2) very low particle number concentrations are detected for a substantial part of the year (57 %), including summer (34 %–65 %), suggesting that the strong annual aerosol concentration cycle is driven by a short temporal interval of strong NPF events; (3) a unique pristine aerosol cluster is seen with a bimodal size distribution (75 and 160 nm, respectively), strongly associated with high wind speed and possibly associated with blowing snow and sea spray sea salt, dominating the winter aerosol population (34 %–54 %). A brief comparison with two other stations (Dome C – Concordia – and King Sejong Station) during the year 2015 (240 d overlap) shows that the dynamics of aerosol number concentrations and distributions are more complex than the simple sulfate–sea-spray binary combination, and it is likely that an array of additional chemical components and processes drive the aerosol population. A conceptual illustration is proposed indicating the various atmospheric processes related to the Antarctic aerosols, with particular emphasis on the origin of new particle formation and growth.

Particle nucleation is one of the main sources of atmospheric particulate matter by number, with new particles having great relevance for human health and climate. Highly oxidized multifunctional organic molecules (HOMs) have been recently identified as key constituents in the growth and, sometimes, in initial formation of new particles. While there have been many studies of HOMs in atmospheric chambers, flow tubes, and clean environments, analyses of data from polluted environments are scarce. Here, measurements of HOMs and particle size distributions down to small molecular clusters are presented alongside volatile organic compounds (VOCs) and trace-gas data from a campaign in June 2017, in Beijing. Many gas-phase HOMs have been characterized and their temporal trends and behaviours analysed in the context of new particle formation. The HOMs identified have a degree of oxidation comparable to that seen in other, cleaner, environments, likely due to an interplay between the higher temperatures facilitating rapid hydrogen abstractions and the higher concentrations of NOx and other RO2⚫ terminators ending the autoxidation sequence more rapidly. Our data indicate that alkylbenzenes, monoterpenes, and isoprene are important precursor VOCs for HOMs in Beijing. Many of the C5 and C10 compounds derived from isoprene and monoterpenes have a slightly greater degree of average oxidation state of carbon compared to those from other precursors. Most HOMs except for large dimers have daytime peak concentrations, indicating the importance of OH⚫ chemistry in the formation of HOMs, as O3 tends to be lower on days with higher HOM concentrations; similarly, VOC concentrations are lower on the days with higher HOM concentrations. The daytime peaks of HOMs coincide with the growth of freshly formed new particles, and their initial formation coincides with the peak in sulfuric acid vapours, suggesting that the nucleation process is sulfuric-acid-dependent, with HOMs contributing to subsequent particle growth.

A 5-year Clean Air Action Plan was implemented in 2013 to reduce air pollutant emissions and improve ambient air quality in Beijing. Assessment of this action plan is an essential part of the decision-making process to review its efficacy and to develop new policies. Both statistical and chemical transport modelling have been previously applied to assess the efficacy of this action plan. However, inherent uncertainties in these methods mean that new and independent methods are required to support the assessment process. Here, we applied a machine-learning-based random forest technique to quantify the effectiveness of Beijing's action plan by decoupling the impact of meteorology on ambient air quality. Our results demonstrate that meteorological conditions have an important impact on the year-to-year variations in ambient air quality. Further analyses show that the PM2.5 mass concentration would have broken the target of the plan (2017 annual PM2.5 µg m−3) were it not for the meteorological conditions in winter 2017 favouring the dispersion of air pollutants. However, over the whole period (2013–2017), the primary emission controls required by the action plan have led to significant reductions in PM2.5, PM10, NO2, SO2, and CO from 2013 to 2017 of approximately 34 %, 24 %, 17 %, 68 %, and 33 %, respectively, after meteorological correction. The marked decrease in PM2.5 and SO2 is largely attributable to a reduction in coal combustion. Our results indicate that the action plan has been highly effective in reducing the primary pollution emissions and improving air quality in Beijing. The action plan offers a successful example for developing air quality policies in other regions of China and other developing countries.

Organic matter is a major component of PM2.5 in megacities. In order to understand the detailed characteristics of organic compounds (≥ C6) at a molecular level on non-haze and haze days, we determined more than 300 organic compounds in the PM2.5 from an urban area of Beijing collected in November–December 2016 using two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC × GC-ToF-MS). The identified organic compounds have been classified into groups, and quantitative methods were used to calculate their concentrations. Primary emission sources make significant contributions to the atmospheric organic compounds, and six groups (including n-alkanes, polycyclic aromatic hydrocarbons – PAHs, levoglucosan, branched alkanes, n-alkenes and alkyl-benzenes) account for 66 % of total identified organic compound mass. In addition, PAHs and oxygenated PAHs (O-PAHs) were abundant amongst the atmospheric organic compounds on both haze and non-haze days. The most abundant hydrocarbon groups were observed with a carbon atom range of C19–C28. In addition, the total concentration of unidentified compounds present in the chromatogram was estimated in the present study. The total identified compounds account for approximately 47 % of total organic compounds (≥ C6) in the chromatogram on both the non-haze and haze days. The total mass concentrations of organic compounds (≥ C6) in the chromatogram were 4.0 and 7.4 µg m−3 on the non-haze and haze days, respectively, accounting for 26.4 % and 18.5 % of organic matter, respectively, on those days estimated from the total organic carbon concentration. Ratios of individual compound concentrations between haze and non-haze days do not give a clear indication of the degree of oxidation, but the overall distribution of organic compounds in the chromatogram provides strong evidence that the organic aerosol is less GC volatile and hence more highly oxidized on haze days.

Aerosols are an integral part of the Arctic climate system due to their direct interaction with radiation and indirect interaction through cloud formation. Understanding aerosol size distributions and their dynamics is crucial for the ability to predict these climate relevant effects. When of favourable size and composition, both long-range-transported – and locally formed particles – may serve as cloud condensation nuclei (CCN). Small changes of composition or size may have a large impact on the low CCN concentrations currently characteristic of the Arctic environment. We present a cluster analysis of particle size distributions (PSDs; size range 8–500 nm) simultaneously collected from three high Arctic sites during a 3-year period (2013–2015). Two sites are located in the Svalbard archipelago: Zeppelin research station (ZEP; 474 m above ground) and the nearby Gruvebadet Observatory (GRU; about 2 km distance from Zeppelin, 67 m above ground). The third site (Villum Research Station at Station Nord, VRS; 30 m above ground) is 600 km west-northwest of Zeppelin, at the tip of north-eastern Greenland. The GRU site is included in an inter-site comparison for the first time. K-means cluster analysis provided eight specific aerosol categories, further combined into broad PSD classes with similar characteristics, namely pristine low concentrations (12 %–14 % occurrence), new particle formation (16 %–32 %), Aitken (21 %–35 %) and accumulation (20 %–50 %). Confined for longer time periods by consolidated pack sea ice regions, the Greenland site GRU shows PSDs with lower ultrafine-mode aerosol concentrations during summer but higher accumulation-mode aerosol concentrations during winter, relative to the Svalbard sites. By association with chemical composition and cloud condensation nuclei properties, further conclusions can be derived. Three distinct types of accumulation-mode aerosol are observed during winter months. These are associated with sea spray (largest detectable sizes, >400 nm), Arctic haze (main mode at 150 nm) and aged accumulation-mode (main mode at 220 nm) aerosols. In contrast, locally produced particles, most likely of marine biogenic origin, exhibit size distributions dominated by the nucleation and Aitken mode during summer months. The obtained data and analysis point towards future studies, including apportioning the relative contribution of primary and secondary aerosol formation processes and elucidating anthropogenic aerosol dynamics and transport and removal processes across the Greenland Sea. In order to address important research questions in the Arctic on scales beyond a singular station or measurement events, it is imperative to continue strengthening international scientific cooperation.

The Atmospheric Pollution and Human Health in a Chinese Megacity (APHH-Beijing) programme is an international collaborative project focusing on understanding the sources, processes and health effects of air pollution in the Beijing megacity. APHH-Beijing brings together leading China and UK research groups, state-of-the-art infrastructure and air quality models to work on four research themes: (1) sources and emissions of air pollutants; (2) atmospheric processes affecting urban air pollution; (3) air pollution exposure and health impacts; and (4) interventions and solutions. Themes 1 and 2 are closely integrated and support Theme 3, while Themes 1–3 provide scientific data for Theme 4 to develop cost-effective air pollution mitigation solutions. This paper provides an introduction to (i) the rationale of the APHH-Beijing programme and (ii) the measurement and modelling activities performed as part of it. In addition, this paper introduces the meteorology and air quality conditions during two joint intensive field campaigns – a core integration activity in APHH-Beijing. The coordinated campaigns provided observations of the atmospheric chemistry and physics at two sites: (i) the Institute of Atmospheric Physics in central Beijing and (ii) Pinggu in rural Beijing during 10 November–10 December 2016 (winter) and 21 May–22 June 2017 (summer). The campaigns were complemented by numerical modelling and automatic air quality and low-cost sensor observations in the Beijing megacity. In summary, the paper provides background information on the APHH-Beijing programme and sets the scene for more focused papers addressing specific aspects, processes and effects of air pollution in Beijing.

Beijing has suffered from heavy local emissions as well as regional transport of air pollutants, resulting in severe atmospheric fine-particle (PM2.5) pollution. This study developed a combined method to investigate source types of PM2.5 and its source regions during winter 2016 in Beijing, which include the receptor model (positive matrix factorization, PMF), footprint and an air quality model. The PMF model was performed with high-time-resolution measurements of trace elements, water soluble ions, organic carbon and elemental carbon using online instruments during the wintertime campaign of the Air Pollution and Human Health in a Chinese Megacity – Beijing (APHH-Beijing) program in 2016. Source types and their contributions estimated by PMF model using online measurements were linked with source regions identified by the footprint model, and the regional transport contribution was estimated by an air quality model (the Nested Air Quality Prediction Model System, NAQPMS) to analyze the specific sources and source regions during haze episodes. Our results show that secondary and biomass-burning sources were dominated by regional transport, while the coal combustion source increased with local contribution, suggesting that strict control strategies for local coal combustion in Beijing and a reduction of biomass-burning and gaseous precursor emissions in surrounding areas were essential to improve air quality in Beijing. The combination of PMF with footprint results revealed that secondary sources were mainly associated with southern footprints (53 %). The northern footprint was characterized by a high dust source contribution (11 %), while industrial sources increased with the eastern footprint (10 %). The results demonstrated the power of combining receptor model-based source apportionment with other models in understanding the formation of haze episodes and identifying specific sources from different source regions affecting air quality in Beijing.

New particle formation (NPF) events have different patterns of development depending on the conditions of the area in which they occur. In this study, particle size distributions in the range of 16.6–604 nm (7 years of data) were analysed and NPF events occurring at three sites of differing characteristics – rural Harwell (HAR), urban background North Kensington (NK), urban roadside Marylebone Road (MR), London, UK – were extracted and studied. The different atmospheric conditions in each study area not only have an effect on the frequency of the events, but also affect their development. The frequency of NPF events is similar at the rural and urban background locations (about 7 % of days), with a high proportion of events occurring at both sites on the same day (45 %). The frequency of NPF events at the urban roadside site is slightly less (6 % of days), and higher particle growth rates (average 5.5 nm h−1 at MR compared to 3.4 and 4.2 nm h−1 at HAR and NK respectively) must result from rapid gas-to-particle conversion of traffic-generated pollutants. A general pattern is found in which the condensation sink increases with the degree of pollution of the site, but this is counteracted by increased particle growth rates at the more polluted location. A key finding of this study is that the role of the urban environment leads to an increment of 20 % in N16–20 nm in the urban background compared to that of the rural area in NPF events occurring at both sites. The relationship of the origin of incoming air masses is also considered and an association of regional events with cleaner air masses is found. Due to lower availability of condensable species, NPF events that are associated with cleaner atmospheric conditions have lower growth rates of the newly formed particles. The decisive effect of the condensation sink in the development of NPF events and the survivability of the newly formed particles is underlined, and influences the overall contribution of NPF events to the number of ultrafine particles in an area. The other key factor identified by this study is the important role that pollution, both from traffic and other sources in the urban environment (such as heating or cooking), plays in new particle formation events.

Some air pollution datasets contain multiple variables with a range of measurement units, and combined analysis using positive matrix factorization (PMF) can be problematic but can offer benefits through the greater information content. In this work, a novel method is devised and the source apportionment of a mixed unit dataset (PM10 mass and number size distribution, NSD) is achieved using a novel two-step approach to PMF. In the first step the PM10 data are PMF-analysed using a source apportionment approach in order to provide a solution which best describes the environment and conditions considered. The time series G values (and errors) of the PM10 solution are then taken forward into the second step, where they are combined with the NSD data and analysed in a second PMF analysis. This results in NSD data associated with the apportioned PM10 factors. We exemplify this approach using data reported in the study of Beddows et al. (2015), producing one solution which unifies the two separate solutions for PM10 and NSD data datasets together. We also show how regression of the NSD size bins and the G time series can be used to elaborate the solution by identifying NSD factors (such as nucleation) not influencing the PM10 mass.

Three groups of aliphatic carbonyl compounds, the n-alkanals (C8–C20), n-alkan-2-ones (C8–C26), and n-alkan-3-ones (C8–C19), were measured in both particulate and vapour phases in air samples collected in London from January to April 2017. Four sites were sampled including two rooftop background sites, one ground-level urban background site, and a street canyon location on Marylebone Road in central London. The n-alkanals showed the highest concentrations, followed by the n-alkan-2-ones and the n-alkan-3-ones, the latter having appreciably lower concentrations. It seems likely that all compound groups have both primary and secondary sources and these are considered in light of published laboratory work on the oxidation products of high-molecular-weight n-alkanes. All compound groups show a relatively low correlation with black carbon and NOx in the background air of London, but in street canyon air heavily impacted by vehicle emissions, stronger correlations emerge, especially for the n-alkanals. It appears that vehicle exhaust is likely to be a major contributor for concentrations of the n-alkanals, whereas it is a much smaller contributor to the n-alkan-2-ones and n-alkan-3-ones. Other primary sources such as cooking or wood burning may be contributors for the ketones but were not directly evaluated. It seems likely that there is also a significant contribution from the photo-oxidation of n-alkanes and this would be consistent with the much higher abundance of n-alkan-2-ones relative to n-alkan-3-ones if the formation mechanism were through the oxidation of condensed-phase alkanes. Vapour–particle partitioning fitted the Pankow model well for the n-alkan-2-ones but less well for the other compound groups, although somewhat stronger relationships were seen at the Marylebone Road site than at the background sites. The former observation gives support to the n-alkane-2-ones being a predominantly secondary product, whereas primary sources of the other groups are more prominent.

Particle number size distributions have been measured simultaneously by scanning mobility particle sizers (SMPSs) at five sites in central London for a 1 month campaign in January–February 2017. These measurements were accompanied by condensation particle counters (CPCs) to measure total particle number count at four of the sites and Aethalometers measuring black carbon (BC) at five sites. The spatial distribution and inter-relationships of the particle size distribution and SMPS total number counts with CPC total number counts and black carbon measurements have been analysed in detail as well as variations in the size distributions. One site (Marylebone Road) was in a street canyon with heavy traffic, one site (Westminster University) was on a rooftop adjacent to the Marylebone Road sampler, and a further sampler was located at Regent's University within a major park to the north of Marylebone Road. A fourth sampler was located nearby at 160 m above ground level on the BT tower and a fifth sampler was located 4 km to the west of the main sampling region at North Kensington. Consistent with earlier studies it was found that the mode in the size distribution had shifted to smaller sizes at the Regent's University (park) site, the mean particle shrinkage rate being 0.04 nm s−1 with slightly lower values at low wind speeds and some larger values at higher wind speeds. There was evidence of complete evaporation of the semi-volatile nucleation mode under certain conditions at the elevated BT Tower site. While the SMPS total count and black carbon showed typical traffic-dominated diurnal profiles, the CPC count data typically peaked during night-time as did CPC∕SMPS and CPC∕BC ratios. This is thought to be due to the presence of high concentrations of small particles (2.5–15 nm diameter) probably arising from condensational growth from traffic emissions during the cooler night-time conditions. Such behaviour was most marked at the Regent's University and Westminster University sites and less so at Marylebone Road, while at the elevated BT Tower site the ratio of particle number (CPC) to black carbon peaked during the morning rush hour and not at night-time, unlike the other sites. An elevation in nucleation mode particles associated with winds from the west and WSW sector was concluded to result from emissions from London Heathrow Airport, despite a distance of 22 km from the central London sites.

A recent study demonstrated that diesel particles in urban air undergo evaporative shrinkage when advected to a cleaner atmosphere (Harrison et al., 2016). We explore, in a structured and systematic way, the sensitivity of nucleation-mode diesel particles (diameter < 30 nm) to changes in particle composition, saturation vapour pressure, and the mass accommodation coefficient. We use a multicomponent aerosol microphysics model based on surrogate molecule (C16−C32 n-alkane) volatilities. For standard atmospheric conditions (298 K, 1013.25 hPa), and over timescales (ca. 100 s) relevant for dispersion on the neighbourhood scale (up to 1 km), the choice of a particular vapour pressure dataset changes the range of compounds that are appreciably volatile by two to six carbon numbers. The nucleation-mode peak diameter, after 100 s of model runtime, is sensitive to the vapour pressure parameterisations for particles with compositions centred on surrogate molecules between C22H46 and C24H50. The vapour pressure range, derived from published data, is between 9.23 × 10−3 and 8.94 × 10−6 Pa for C22H46 and between 2.26 × 10−3 and 2.46 × 10−7 Pa for C24H50. Therefore, the vapour pressures of components in this range are critical for the modelling of nucleation-mode aerosol dynamics on the neighbourhood scale and need to be better constrained. Laboratory studies have shown this carbon number fraction to derive predominantly from engine lubricating oil. The accuracy of vapour pressure data for other (more and less volatile) components from laboratory experiments is less critical. The influence of a core of non-volatile material is also considered; non-volatile core fractions of more than 5 % are inconsistent with the field measurements that we test the model against. We consider mass accommodation coefficient values less than unity and find that model runs with more volatile vapour pressure parameterisations and lower accommodation coefficients are similar to runs with less volatile vapour pressure parameterisations and higher accommodation coefficients. The new findings of this study may also be used to identify semi-volatile organic compound (SVOC) compositions that play dominating roles in the evaporative shrinkage of the nucleation mode observed in field measurements (Dall'Osto et al., 2011).

The vertical profile of new particle formation (NPF) events was studied by comparing the aerosol size number distributions measured aloft and at surface level in a suburban environment in Madrid, Spain, using airborne instruments. The horizontal distribution and regional impact of the NPF events was investigated with data from three urban, urban background, and suburban stations in the Madrid metropolitan area. Intensive regional NPF episodes followed by particle growth were simultaneously recorded at three stations in and around Madrid during a field campaign in July 2016. The urban stations presented larger formation rates compared to the suburban station. Condensation and coagulation sinks followed a similar evolution at all stations, with higher values at urban stations. However, the total number concentration of particles larger than 2.5 nm was lower at the urban station and peaked around noon, when black carbon (BC) levels are at a minimum. The vertical soundings demonstrated that ultrafine particles (UFPs) are formed exclusively inside the mixed layer. As convection becomes more effective and the mixed layer grows, UFPs are detected at higher levels. The morning soundings revealed the presence of a residual layer in the upper levels in which aged particles (nucleated and grown on previous days) prevail. The particles in this layer also grow in size, with growth rates significantly smaller than those inside the mixed layer. Under conditions with strong enough convection, the soundings revealed homogeneous number size distributions and growth rates at all altitudes, which follow the same evolution at the other stations considered in this study. This indicates that UFPs are detected quasi-homogenously in an area spanning at least 17 km horizontally. The NPF events extend over the full vertical extension of the mixed layer, which can reach as high as 3000 m in the area, according to previous studies. On some days a marked decline in particle size (shrinkage) was observed in the afternoon, associated with a change in air masses. Additionally, a few nocturnal nucleation-mode bursts were observed at the urban stations, for which further research is needed to elucidate their origin.

Atmospheric new particle formation (NPF) is an important phenomenon in terms of global particle number concentrations. Here we investigated the frequency of NPF, formation rates of 10 nm particles, and growth rates in the size range of 10–25 nm using at least 1 year of aerosol number size-distribution observations at 36 different locations around the world. The majority of these measurement sites are in the Northern Hemisphere. We found that the NPF frequency has a strong seasonal variability. At the measurement sites analyzed in this study, NPF occurs most frequently in March–May (on about 30 % of the days) and least frequently in December–February (about 10 % of the days). The median formation rate of 10 nm particles varies by about 3 orders of magnitude (0.01–10 cm−3 s−1) and the growth rate by about an order of magnitude (1–10 nm h−1). The smallest values of both formation and growth rates were observed at polar sites and the largest ones in urban environments or anthropogenically influenced rural sites. The correlation between the NPF event frequency and the particle formation and growth rate was at best moderate among the different measurement sites, as well as among the sites belonging to a certain environmental regime. For a better understanding of atmospheric NPF and its regional importance, we would need more observational data from different urban areas in practically all parts of the world, from additional remote and rural locations in North America, Asia, and most of the Southern Hemisphere (especially Australia), from polar areas, and from at least a few locations over the oceans.

Diesel exhaust emissions were introduced into an atmospheric simulation chamber and measured using thermal desorption (TD) comprehensive two-dimensional gas chromatography coupled to a flame ionisation detector (GC  ×  GC-FID). An extensive set of measurements were performed to investigate the effect of different engine conditions (i.e. load, speed, driving scenarios) and emission control devices (with or without diesel oxidative catalyst, DOC) on the composition and abundance of unregulated exhaust gas emissions from a light-duty diesel engine, fuelled with ultra-low sulfur diesel (ULSD). A range of exhaust dilution ratios were investigated (range  =  1 : 60 to 1 : 1158), simulating the chemical and physical transformations of the exhaust gas from near to downwind of an emission source. In total, 16 individual and 8 groups of compounds (aliphatics and single-ring aromatics) were measured in the exhaust gas ranging from volatile to intermediate volatility (VOC-IVOC), providing both detailed chemical speciation and groupings of compounds based on their structure and functionality. Measured VOC-IVOC emission rates displayed excellent reproducibility from replicate experiments using similar exhaust dilution ratios. However, at the extremes of the investigated exhaust dilution ratios (comparison of 1 : 60 and 1 : 1158), measured VOC-IVOC emission rates displayed some disagreement owing to poor reproducibility and highlighted the importance of replicate sample measurements. The investigated DOC was found to remove 43±10 % (arithmetic mean ± experimental uncertainty) of the total speciated VOC-IVOC ( ∑ SpVOC-IVOC) emissions. The compound class-dependant removal efficiencies for the investigated DOC were 39±12 % and 83±3 % for the aliphatics and single-ring aromatics, respectively. The DOC aliphatic removal efficiency generally decreased with increasing carbon chain length. The ∑ SpVOC-IVOC emission rates varied significantly with different engine conditions, ranging from 70 to 9268 mg kg−1 (milligrams of mass emitted per kilogram of fuel burnt). ∑ SpVOC-IVOC emission rates generally decreased with increasing engine load and temperature, and to a lesser degree, engine speed. The exhaust gas composition changed considerably as a result of two influencing factors: engine combustion and DOC hydrocarbon (HC) removal efficiency. Increased engine combustion efficiency resulted in a greater percentage contribution of the C7 to C12 n-alkanes to the ∑ SpVOC-IVOC emission rate. Conversely, increased DOC HC removal efficiency resulted in a greater percentage contribution of the C7 to C12 branched aliphatics to the ∑ SpVOC-IVOC emission rate. At low engine temperatures ( n-alkanes in the exhaust gas increased with increasing combustion efficiency and may be important in urban environments, as n-alkanes are more efficient at producing secondary organic aerosol (SOA) than their branched counterparts. At very high engine temperatures (maximum applied engine speed and load, engine temperature  =  700 °C), the n-alkane contribution increased by a factor of 1.6 times greater than that observed in the cold-start experiment (most similar to unburnt fuel) and may suggest liquid-fuel-based estimates of SOA yields may be inconsistent with exhaust SOA yields, particularly at high engine speeds and loads (i.e. high engine temperatures). Emission rates were found to be 65 times greater from a cold-start experiment than at maximum applied engine speed and load. To our knowledge, this is the first study which uses an atmospheric simulation chamber to separate the effects of the DOC and combustion efficiency on the exhaust gas composition.

Various studies have reported that the photochemical nucleation of new ultrafine particles (UFPs) in urban environments within high insolation regions occurs simultaneously with high ground ozone (O3) levels. In this work, we evaluate the atmospheric dynamics leading to summer O3 episodes in the Madrid air basin (central Iberia) by means of measuring a 3-D distribution of concentrations for both pollutants. To this end, we obtained vertical profiles (up to 1200 m above ground level) using tethered balloons and miniaturised instrumentation at a suburban site located to the SW of the Madrid Metropolitan Area (MMA), the Majadahonda site (MJDH), in July 2016. Simultaneously, measurements of an extensive number of air quality and meteorological parameters were carried out at three supersites across the MMA. Furthermore, data from O3 soundings and daily radio soundings were also used to interpret atmospheric dynamics.The results demonstrate the concatenation of venting and accumulation episodes, with relative lows (venting) and peaks (accumulation) in O3 surface levels. Regardless of the episode type, the fumigation of high-altitude O3 (arising from a variety of origins) contributes the major proportion of surface O3 concentrations. Accumulation episodes are characterised by a relatively thinner planetary boundary layer ( 2400 m a.s.l.). This orographic–meteorological setting causes the vertical recirculation of air masses and enrichment of O3 in the lower tropospheric layers. When the highly polluted urban plume from Madrid is affected by these dynamics, the highest Ox (O3+ NO2) concentrations are recorded in the MMA.Vertical O3 profiles during venting episodes, with strong synoptic winds and a deepening of the planetary boundary layer reaching > 2000 m a.s.l., were characterised by an upward gradient in O3 levels, whereas a reverse situation with O3 concentration maxima at lower levels was found during the accumulation episodes due to local and/or regional production. The two contributions to O3 surface levels (fumigation from high-altitude strata, a high O3 background, and/or regional production) require very different approaches for policy actions. In contrast to O3 vertical top-down transfer, UFPs are formed in the planetary boundary layer (PBL) and are transferred upwards progressively with the increase in PBL growth.

Airborne particles and vapours, like many other environmental samples including water, soils and sediments, contain complex mixtures of hydrocarbons, often deriving from crude oil either before or after fractionation into fuels, lubricants and feedstocks. Comprehensive 2D gas chromatography time-of-flight mass spectrometry (GC × GC-ToF-MS), offers a very powerful technique that separates and identifies many compounds in complicated hydrocarbon mixtures. However, quantification and identification of individual constituents at high ionization energies would require hundreds of expensive (when available) standards for calibration. Although the precise chemical structure of hydrocarbons does matter for their environmental impact and fate, strong similarities can be expected for compounds having very similar chemical structures and carbon numbers. There is, therefore, a clear benefit in an analytical technique which is specific enough to separate different classes of compounds and to distinguish homologous series while avoiding the need to handle each isomer individually. Varying EI (electron impact) ionization mass spectrometry significantly enhances the identification of individual isomers and homologous compound groups, which we refer to as isomer sets. Advances are reported in mapping and quantifying isomer sets of hydrocarbons (≥ C12) in diesel fuel, lubricating oil and diesel exhaust emissions. By using this analysis we report mass closures of ca. 90 and 75 % for diesel fuel and lubricating oil, and identify 85 and 75 % of the total ion current for gas- and particulate-phase diesel exhaust emissions.

The international airport of Heathrow is a major source of nitrogen oxides, but its contribution to the levels of sub-micrometre particles is unknown and is the objective of this study. Two sampling campaigns were carried out during warm and cold seasons at a site close to the airfield (1.2 km). Size spectra were largely dominated by ultrafine particles: nucleation particles ( k means cluster analysis and positive matrix factorisation (PMF), respectively, to particle number size distributions; their interpretation was based on their modal structures, wind directionality, diurnal patterns, road and airport traffic volumes, and on the relationship with weather and other air pollutants. Airport emissions, fresh and aged road traffic, urban accumulation mode, and two secondary sources were then identified and apportioned. The fingerprint of Heathrow has a characteristic modal structure peaking at

Ground-level and vertical measurements (performed using tethered and non-tethered balloons), coupled with modelling, of ozone (O3), other gaseous pollutants (NO, NO2, CO, SO2) and aerosols were carried out in the plains (Vic Plain) and valleys of the northern region of the Barcelona metropolitan area (BMA) in July 2015, an area typically recording the highest O3 episodes in Spain. Our results suggest that these very high O3 episodes were originated by three main contributions: (i) the surface fumigation from high O3 reservoir layers located at 1500–3000 m a.g.l. (according to modelling and non-tethered balloon measurements), and originated during the previous day(s) injections of polluted air masses at high altitude; (ii) local/regional photochemical production and transport (at lower heights) from the BMA and the surrounding coastal settlements, into the inland valleys; and (iii) external (to the study area) contributions of both O3 and precursors. These processes gave rise to maximal O3 levels in the inland plains and valleys northwards from the BMA when compared to the higher mountain sites. Thus, a maximum O3 concentration was observed within the lower tropospheric layer, characterised by an upward increase of O3 and black carbon (BC) up to around 100–200 m a.g.l. (reaching up to 300 µg m−3 of O3 as a 10 s average), followed by a decrease of both pollutants at higher altitudes, where BC and O3 concentrations alternate in layers with parallel variations, probably as a consequence of the atmospheric transport from the BMA and the return flows (to the sea) of strata injected at certain heights the previous day(s). At the highest altitudes reached in this study with the tethered balloons (900–1000 m a.g.l.) during the campaign, BC and O3 were often anti-correlated or unrelated, possibly due to a prevailing regional or even hemispheric contribution of O3 at those altitudes. In the central hours of the days a homogeneous O3 distribution was evidenced for the lowest 1 km of the atmosphere, although probably important variations could be expected at higher levels, where the high O3 return strata are injected according to the modelling results and non-tethered balloon data. Relatively low concentrations of ultrafine particles (UFPs) were found during the study, and nucleation episodes were only detected in the boundary layer. Two types of O3 episodes were identified: type A with major exceedances of the O3 information threshold (180 µg m−3 on an hourly basis) caused by a clear daily concatenation of local/regional production with accumulation (at upper levels), fumigation and direct transport from the BMA (closed circulation); and type B with regional O3 production without major recirculation (or fumigation) of the polluted BMA/regional air masses (open circulation), and relatively lower O3 levels, but still exceeding the 8 h averaged health target. To implement potential O3 control and abatement strategies two major key tasks are proposed: (i) meteorological forecasting, from June to August, to predict recirculation episodes so that NOx and VOC abatement measures can be applied before these episodes start; (ii) sensitivity analysis with high-resolution modelling to evaluate the effectiveness of these potential abatement measures of precursors for O3 reduction.

A chemical reaction chamber system has been developed for the processing of oleic acid aerosol particles with ozone under two relative humidity conditions: dry and humidified to 65 %. The apparatus consists of an aerosol flow tube, in which the ozonolysis occurs, coupled to a scanning mobility particle sizer (SMPS) and an aerosol time-of-flight mass spectrometer (ATOFMS) which measure the evolving particle size and composition. Under both relative humidity conditions, ozonolysis results in a significant decrease in particle size and mass which is consistent with the formation of volatile products that partition from the particle to the gas phase. Mass spectra derived from the ATOFMS reveal the presence of the typically observed reaction products: azelaic acid, nonanal, oxononanoic acid and nonanoic acid, as well as a range of higher molecular weight products deriving from the reactions of reaction intermediates with oleic acid and its oxidation products. These include octanoic acid and 9- and 10-oxooctadecanoic acid, as well as products of considerably higher molecular weight. Quantitative evaluation of product yields with the ATOFMS shows a marked dependence upon both particle size association (from 0.3 to 2.1 µm diameter) and relative humidity. Under both relative humidity conditions, the percentage residual of oleic acid increases with increasing particle size and the main lower molecular weight products are nonanal and oxononanoic acid. Under dry conditions, the percentage of higher molecular weight products increases with increasing particle size due to the poorer internal mixing of the larger particles. Under humidified conditions, the percentage of unreacted oleic acid is greater, except in the smallest particle fraction, with little formation of high molecular weight products relative to the dry particles. It is postulated that water reacts with reactive intermediates, competing with the processes which produce high molecular weight products. Whilst the oleic acid model aerosol system is of limited relevance to complex internally mixed atmospheric aerosol, the generic findings presented in this paper give useful insights into the nature of heterogeneous chemical processes.

The aerosol time-of-flight mass spectrometer (ATOFMS) provides size-resolved information on the chemical composition of single particles with high time resolution. Within SAPUSS (Solving Aerosol Problems by Using Synergistic Strategies), continuous ATOFMS measurements of ambient particles were made simultaneously at two urban locations: urban background (UB) site and roadside (RS) site in the city of Barcelona (Spain) from 17 September to 18 October 2010. Two different instrumental configurations were used: ATOFMS (TSI 3800) with a converging nozzle inlet (high efficiency at about 800–2000 nm) at the UB site and ATOFMS (TSI 3800-100) with an aerodynamic lens inlet (high efficiency at about 300–700 nm) at the RS site. This is the first time, to our knowledge, that two ATOFMS instruments have been deployed in the same field study. The different instrument configurations had an impact on the observed particle types at the two sites. Nevertheless, 10 particle types were detected at both locations, including local and regional elemental carbon (22.7–58.9 % of total particles), fresh and aged sea salt (1.0–14.6 %), local and regional nitrate-containing aerosols (3–11.6 %), local lead-containing metallic particles (0.1–0.2 %), and transported Fe-nitrate particles (0.8–2.5 %). The ATOFMS at the UB also characterized four particle types: calcium-containing dust (0.9 %), Saharan dust (1.3 %), vanadium-containing particles (0.9 %), and vegetative debris (1.7 %). By contrast, the high statistical counts of fine particles detected at the RS allowed identification of eight particle types. Four of these contained organic nitrogen of primary and secondary origin, which highlights the complex nature of the sources and processes that contribute to this aerosol chemical component. Aminium salts were found related to coarse sulfate-rich particle types, suggesting heterogeneous reaction mechanisms for their formation. The other four particle types mainly containing organic carbon were found spiking at different types of the day, also showing a complex single-particle mixing state relationship between organic carbon and nitrate. This ATOFMS study clearly shows that the composition of atmospheric fine particles in Barcelona, and likely other Mediterranean urban areas, is complex, with a wide range of local and regional sources combining with chemical processing to produce at least 22 different particle types exhibiting different temporal behaviour. The advantage of using two ATOFMS instruments is also demonstrated, with the nozzle-skimmer configuration enabling detection of coarse dust particles and the aerodynamic lens configuration allowing better identification of particles rich in organic carbon and amines. Overall, we find that organic nitrogen is a considerable fraction of the single particles detected, especially at the traffic-dominated RS site. Further studies are needed, especially at high time resolution, to better understand the sources and properties of particulate organic nitrogen.

The AIRUSE-LIFE+ project aims at characterizing similarities and heterogeneities in particulate matter (PM) sources and contributions in urban areas from southern Europe. Once the main PMx sources are identified, AIRUSE aims at developing and testing the efficiency of specific and non-specific measures to improve urban air quality. This article reports the results of the source apportionment of PM10 and PM2.5 conducted at three urban background sites (Barcelona, Florence and Milan, BCN-UB, FI-UB and MLN-UB), one suburban background site (Athens, ATH-SUB) and one traffic site (Porto, POR-TR). After collecting 1047 PM10 and 1116 PM2.5 24 h samples during 12 months (from January 2013 on) simultaneously at the five cities, these were analysed for the contents of OC, EC, anions, cations, major and trace elements and levoglucosan. The USEPA PMF5 receptor model was applied to these data sets in a harmonized way for each city. The sum of vehicle exhaust (VEX) and non-exhaust (NEX) contributes between 3.9 and 10.8 µg m−3 (16–32 %) to PM10 and 2.3 and 9.4 µg m−3 (15–36 %) to PM2.5, although a fraction of secondary nitrate is also traffic-related but could not be estimated. Important contributions arise from secondary particles (nitrate, sulfate and organics) in PM2.5 (37–82 %) but also in PM10 (40–71 %), mostly at background sites, revealing the importance of abating gaseous precursors in designing air quality plans. Biomass burning (BB) contributions vary widely, from 14–24 % of PM10 in POR-TR, MLN-UB and FI-UB, 7 % in ATH-SUB, to 2.5, BB is the second most important source in MLN-UB (21 %) and in POR-TR (18 %), the third one in FI-UB (21 %) and ATH-SUB (11 %), but is again negligible (< 2 %) in BCN-UB. This large variability among cities is mostly due to the degree of penetration of biomass for residential heating. In Barcelona natural gas is very well supplied across the city and is used as fuel in 96 % of homes, while in other cities, PM levels increase on an annual basis by 1–9 µg m−3 due to biomass burning influence. Other significant sources are the following. – Local dust, 7–12 % of PM10 at SUB and UB sites and 19 % at the TR site, revealing a contribution from road dust resuspension. In PM2.5 percentages decrease to 2–7 % at SUB-UB sites and 15 % at the TR site. – Industry, mainly metallurgy, contributing 4–11 % of PM10 (5–12 % in PM2.5), but only at BCN-UB, POR-TR and MLN-UB. No clear impact of industrial emissions was found in FI-UB and ATH-SUB. – Natural contributions from sea salt (13 % of PM10 in POR-TR, but only 2–7 % in the other cities) and Saharan dust (14 % in ATH-SUB, but less than 4 % in the other cities). During high pollution days, the largest sources (i.e. excluding secondary aerosol factors) of PM10 and PM2.5 are VEX + NEX in BCN-UB (27–22 %) and POR-TR (31–33 %), BB in FI-UB (30–33 %) and MLN-UB (35–26 %) and Saharan dust in ATH-SUB (52–45 %). During those days, there are also quite important industrial contributions in BCN-UB (17–18 %) and local dust in POR-TR (28–20 %).

Positive matrix factorisation (PMF) analysis was applied to PM10 chemical composition and particle number size distribution (NSD) data measured at an urban background site (North Kensington) in London, UK, for the whole of 2011 and 2012. The PMF analyses for these 2 years revealed six and four factors respectively which described seven sources or aerosol types. These included nucleation, traffic, urban background, secondary, fuel oil, marine and non-exhaust/crustal sources. Urban background, secondary and traffic sources were identified by both the chemical composition and particle NSD analysis, but a nucleation source was identified only from the particle NSD data set. Analysis of the PM10 chemical composition data set revealed fuel oil, marine, non-exhaust traffic/crustal sources which were not identified from the NSD data. The two methods appear to be complementary, as the analysis of the PM10 chemical composition data is able to distinguish components contributing largely to particle mass, whereas the number particle size distribution data set – although limited to detecting sources of particles below the diameter upper limit of the SMPS (604 nm) – is more effective for identifying components making an appreciable contribution to particle number. Analysis was also conducted on the combined chemical composition and NSD data set, revealing five factors representing urban background, nucleation, secondary, aged marine and traffic sources. However, the combined analysis appears not to offer any additional power to discriminate sources above that of the aggregate of the two separate PMF analyses. Day-of-the-week and month-of-the-year associations of the factors proved consistent with their assignment to source categories, and bivariate polar plots which examined the wind directional and wind speed association of the different factors also proved highly consistent with their inferred sources. Source attribution according to the air mass back trajectory showed, as expected, higher concentrations from a number of source types in air with continental origins. However, when these were weighted according to their frequency of occurrence, air with maritime origins made a greater contribution to annual mean concentrations.

For the first time, the behaviour of non-refractory inorganic and organic submicron particulate through an entire annual cycle is investigated using measurements from an Aerodyne compact time-of-flight aerosol mass spectrometer (cToF-AMS) located at a UK urban background site in North Kensington, London. We show that secondary aerosols account for a significant fraction of the submicron aerosol burden and that high concentration events are governed by different factors depending on season. Furthermore, we demonstrate that on an annual basis there is no variability in the extent of secondary organic aerosol (SOA) oxidation, as defined by the oxygen content, irrespective of amount. This result is surprising given the changes in precursor emissions and contributions as well as photochemical activity throughout the year; however it may make the characterisation of SOA in urban environments more straightforward than previously supposed. Organic species, nitrate, sulphate, ammonium, and chloride were measured during 2012 with average concentrations (±1 standard deviation) of 4.32 (±4.42), 2.74 (±5.00), 1.39 (±1.34), 1.30 (±1.52), and 0.15 (±0.24) μg m−3, contributing 44, 28, 14, 13, and 2 % to the total non-refractory submicron mass (NR-PM1) respectively. Components of the organic aerosol fraction are determined using positive matrix factorisation (PMF), in which five factors are identified and attributed as hydrocarbon-like OA (HOA), cooking OA (COA), solid fuel OA (SFOA), type 1 oxygenated OA (OOA1), and type 2 oxygenated OA (OOA2). OOA1 and OOA2 represent more and less oxygenated OA with average concentrations of 1.27 (±1.49) and 0.14 (±0.29) μg m−3 respectively, where OOA1 dominates the SOA fraction (90%). Diurnal, monthly, and seasonal trends are observed in all organic and inorganic species due to meteorological conditions, specific nature of the aerosols, and availability of precursors. Regional and transboundary pollution as well as other individual pollution events influence London's total submicron aerosol burden. High concentrations of non-refractory submicron aerosols in London are governed by particulate emissions in winter, especially nitrate and SFOA, whereas SOA formation drives the high concentrations during the summer. The findings from this work could have significant implications for modelling of urban air pollution as well as for the effects of atmospheric aerosols on health and climate.

Road traffic emissions are often considered the main source of ultrafine particles (UFP, diameter smaller than 100 nm) in urban environments. However, recent studies worldwide have shown that – in high-insolation urban regions at least – new particle formation events can also contribute to UFP. In order to quantify such events we systematically studied three cities located in predominantly sunny environments: Barcelona (Spain), Madrid (Spain) and Brisbane (Australia). Three long-term data sets (1–2 years) of fine and ultrafine particle number size distributions (measured by SMPS, Scanning Mobility Particle Sizer) were analysed. Compared to total particle number concentrations, aerosol size distributions offer far more information on the type, origin and atmospheric evolution of the particles. By applying k-means clustering analysis, we categorized the collected aerosol size distributions into three main categories: "Traffic" (prevailing 44–63% of the time), "Nucleation" (14–19%) and "Background pollution and Specific cases" (7–22%). Measurements from Rome (Italy) and Los Angeles (USA) were also included to complement the study. The daily variation of the average UFP concentrations for a typical nucleation day at each site revealed a similar pattern for all cities, with three distinct particle bursts. A morning and an evening spike reflected traffic rush hours, whereas a third one at midday showed nucleation events. The photochemically nucleated particles' burst lasted 1–4 h, reaching sizes of 30–40 nm. On average, the occurrence of particle size spectra dominated by nucleation events was 16% of the time, showing the importance of this process as a source of UFP in urban environments exposed to high solar radiation. Nucleation events lasting for 2 h or more occurred on 55% of the days, this extending to > 4 h in 28% of the days, demonstrating that atmospheric conditions in urban environments are not favourable to the growth of photochemically nucleated particles. In summary, although traffic remains the main source of UFP in urban areas, in developed countries with high insolation urban nucleation events are also a main source of UFP. If traffic-related particle concentrations are reduced in the future, nucleation events will likely increase in urban areas, due to the reduced urban condensation sinks.

Determining the contribution of wood smoke to air pollution in large cities such as London is becoming increasingly important due to the changing nature of domestic heating in urban areas. During winter, biomass burning emissions have been identified as a major cause of exceedances of European air quality limits. The aim of this work was to quantify the contribution of biomass burning in London to concentrations of PM2.5 and determine whether local emissions or regional contributions were the main source of biomass smoke. To achieve this, a number of biomass burning chemical tracers were analysed at a site within central London and two sites in surrounding rural areas. Concentrations of levoglucosan, elemental carbon (EC), organic carbon (OC) and K+ were generally well correlated across the three sites. At all the sites, biomass burning was found to be a source of OC and EC, with the largest contribution of EC from traffic emissions, while for OC the dominant fraction included contributions from secondary organic aerosols, primary biogenic and cooking sources. Source apportionment of the EC and OC was found to give reasonable estimation of the total carbon from non-fossil and fossil fuel sources based upon comparison with estimates derived from 14C analysis. Aethalometer-derived black carbon data were also apportioned into the contributions from biomass burning and traffic and showed trends similar to those observed for EC. Mean wood smoke mass at the sites was estimated to range from 0.78 to 1.0 μg m−3 during the campaign in January–February 2012. Measurements on a 160 m tower in London suggested a similar ratio of brown to black carbon (reflecting wood burning and traffic respectively) in regional and London air. Peaks in the levoglucosan and K+ concentrations were observed to coincide with low ambient temperature, consistent with domestic heating as a major contributing local source in London. Overall, the source of biomass smoke in London was concluded to be a background regional source overlaid by contributions from local domestic burning emissions. This could have implications when considering future emission control strategies during winter and may be the focus of future work in order to better determine the contributing local sources.

Solid fuel emissions, including those from biomass burning, are increasing in urban areas across the European Union due to rising energy costs and government incentives to use renewable energy sources for heating. In order to help protect human health as well as to improve air quality and pollution abatement strategies, the sources of combustion aerosols, their contributions, and the processes they undergo need to be better understood. A high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was therefore deployed at an urban background site between January and February 2012 to investigate solid fuel organic aerosols (SFOA) in London. The variability of SFOA was examined and the factors governing the split between the two SFOA factors derived from Positive Matrix Factorisation (PMF) were assessed. The concentrations of both factors were found to increase during the night and during cold periods, consistent with domestic space heating activities. The split between the two factors is likely governed predominantly by differences in burn conditions where SFOA1 best represents more efficient burns and SFOA2 best represents less efficient burns. The differences in efficiency may be due to burner types or burn phase, for example. Different fuel types and levels of atmospheric processing also likely contribute to the two factors. As the mass spectral profile of SFOA is highly variable, the findings from this study may have implications for improving future source apportionment and factorisation analyses. During the winter, SFOA was found to contribute 38% to the total non-refractory submicron organic aerosol (OA) mass, with similar contributions from both SFOA factors (20% from SFOA1 and 18% from SFOA2). A similar contribution of SFOA was derived for the same period from a compact time-of-flight AMS (cToF-AMS), which measured for a full calendar year at the same site. The seasonality of SFOA was investigated using the year-long data set where concentrations were greatest in the autumn and winter. During the summer, SFOA contributed 11% to the organic fraction, where emissions resulted from different anthropogenic activities such as barbecues and domestic garden wood burning. The significant contribution of SFOA to total organic mass throughout the year suggests that the negative effects on health and air quality, as well as climate, are not just confined to winter as exposure to these aerosols and the associated black carbon can also occur during the summer, which may have significant implications for air-quality policies and mitigation strategies.

PM2.5 was collected during a winter campaign at two southern England sites, urban background North Kensington (NK) and rural Harwell (HAR), in January–February 2012. Multiple organic and inorganic source tracers were analysed and used in a Chemical Mass Balance (CMB) model, which apportioned seven separate primary sources, that explained on average 53% (NK) and 56% (HAR) of the organic carbon (OC), including traffic, woodsmoke, food cooking, coal combustion, vegetative detritus, natural gas and dust/soil. With the addition of source tracers for secondary biogenic aerosol at the NK site, 79% of organic carbon was accounted for. Secondary biogenic sources were represented by oxidation products of α-pinene and isoprene, but only the former made a substantial contribution to OC. Particle source contribution estimates for PM2.5 mass were obtained by the conversion of the OC estimates and combining with inorganic components ammonium nitrate, ammonium sulfate and sea salt. Good mass closure was achieved with 81% (92% with the addition of the secondary biogenic source) and 83% of the PM2.5 mass explained at NK and HAR respectively, with the remainder being secondary organic matter. While the most important sources of OC are vehicle exhaust (21 and 16%) and woodsmoke (15 and 28%) at NK and HAR respectively, food cooking emissions are also significant, particularly at the urban NK site (11% of OC), in addition to the secondary biogenic source, only measured at NK, which represented about 26%. In comparison, the major source components for PM2.5 at NK and HAR are inorganic ammonium salts (51 and 56%), vehicle exhaust emissions (8 and 6%), secondary biogenic (10% measured at NK only), woodsmoke (4 and 7%) and sea salt (7 and 8%), whereas food cooking (4 and 1%) showed relatively smaller contributions to PM2.5. Results from the CMB model were compared with source contribution estimates derived from the AMS-PMF method. The overall mass of organic matter accounted for is rather similar for the two methods. However, appreciably different concentrations were calculated for the individual primary organic matter contributions, although for most source categories the CMB and AMS-PMF results were highly correlated (r2 = 0.69–0.91). In comparison with the CMB model, the AMS appears to overestimate the biomass burning/coal and food cooking sources by a factor of around 1.5 to 2 while estimates of the traffic source are rather similar for each model. The largest divergence is in the primary/secondary organic matter split, with the AMS estimating an appreciably smaller secondary component. Possible reasons for these discrepancies are discussed, but despite these substantial divergences, the strong correlation of the two methods gives some confidence in their application.

The use of co-located multiple spectroscopic techniques can provide detailed information on the atmospheric processes regulating aerosol chemical composition and mixing state. So far, field campaigns heavily equipped with aerosol mass spectrometers have been carried out mainly in large conurbations and in areas directly affected by their outflow, whereas lesser efforts have been dedicated to continental areas characterised by a less dense urbanisation. We present here the results obtained at a background site in the Po Valley, Italy, in summer 2009. For the first time in Europe, six state-of-the-art spectrometric techniques were used in parallel: aerosol time-of-flight mass spectrometer (ATOFMS), two aerosol mass spectrometers (high-resolution time-of-flight aerosol mass spectrometer – HR-ToF-AMS and soot particle aerosol mass spectrometer – SP-AMS), thermal desorption aerosol gas chromatography (TAG), chemical ionisation mass spectrometry (CIMS) and (offline) proton nuclear magnetic resonance (1H-NMR) spectroscopy. The results indicate that, under high-pressure conditions, atmospheric stratification at night and early morning hours led to the accumulation of aerosols produced by anthropogenic sources distributed over the Po Valley plain. Such aerosols include primary components such as black carbon (BC), secondary semivolatile compounds such as ammonium nitrate and amines and a class of monocarboxylic acids which correspond to the AMS cooking organic aerosol (COA) already identified in urban areas. In daytime, the entrainment of aged air masses in the mixing layer is responsible for the accumulation of low-volatility oxygenated organic aerosol (LV-OOA) and also for the recycling of non-volatile primary species such as black carbon. According to organic aerosol source apportionment, anthropogenic aerosols accumulating in the lower layers overnight accounted for 38% of organic aerosol mass on average, another 21% was accounted for by aerosols recirculated in residual layers but still originating in northern Italy, while a substantial fraction (41%) was due to the most aged aerosols imported from transalpine areas. The different meteorological regimes also affected the BC mixing state: in periods of enhanced stagnation and recirculation of pollutants, the number fraction of the BC-containing particles determined by ATOFMS was 75% of the total, while in the days of enhanced ventilation of the planetary boundary layer (PBL), such fraction was significantly lower (50%) because of the relative greater influence of non-BC-containing aerosol local sources in the Po Valley. Overall, a full internal mixing between BC and the non-refractory aerosol chemical components was not observed during the experiment in this environment.

Black carbon aerosols (BC) at a London urban site were characterised in both winter- and summertime 2012 during the Clean Air for London (ClearfLo) project. Positive matrix factorisation (PMF) factors of organic aerosol mass spectra measured by a high-resolution aerosol mass spectrometer (HR-AMS) showed traffic-dominant sources in summer but in winter the influence of additional non-traffic sources became more important, mainly from solid fuel sources (SF). Measurements using a single particle soot photometer (SP2, DMT), showed the traffic-dominant BC exhibited an almost uniform BC core size (Dc) distribution with very thin coating thickness throughout the detectable range of Dc. However, the size distribution of sf (project average mass median Dc = 149 ± 22 nm in winter, and 120 ± 6 nm in summer) and BC coating thickness varied significantly in winter. A novel methodology was developed to attribute the BC number concentrations and mass abundances from traffic (BCtr) and from SF (BCsf), by using a 2-D histogram of the particle optical properties as a function of BC core size, as measured by the SP2. The BCtr and BCsf showed distinctly different sf distributions and coating thicknesses, with BCsf displaying larger Dc and larger coating thickness compared to BCtr. BC particles from different sources were also apportioned by applying a multiple linear regression between the total BC mass and each AMS-PMF factor (BC–AMS–PMF method), and also attributed by applying the absorption spectral dependence of carbonaceous aerosols to 7-wavelength Aethalometer measurements (Aethalometer method). Air masses that originated from westerly (W), southeasterly (SE), and easterly (E) sectors showed BCsf fractions that ranged from low to high, and whose mass median Dc values were 137 ± 10 nm, 143 ± 11 nm and 169 ± 29 nm, respectively. The corresponding bulk relative coating thickness of BC (coated particle size/BC core – Dp/Dc) for these same sectors was 1.28 ± 0.07, 1.45 ± 0.16 and 1.65 ± 0.19. For W, SE and E air masses, the number fraction of BCsf ranged from 6 ± 2% to 11 ± 5% to 18 ± 10%, respectively, but importantly the larger BC core sizes lead to an increased fraction of BCsf in terms of mass than number (for W, SE and E air masses, the BCsf mass fractions ranged from 16 ± 6%, 24 ± 10% and 39 ± 14%, respectively). An increased fraction of non-BC particles (particles that did not contain a BC core) was also observed when SF sources were more significant. The BC mass attribution by the SP2 method agreed well with the BC–AMS–PMF multiple linear regression method (BC–AMS–PMF : SP2 ratio = 1.05, r2 = 0.80) over the entire experimental period. Good agreement was found between BCsf attributed with the Aethalometer model and the SP2. However, the assumed absorption Ångström exponent (αwb) had to be changed according to the different air mass sectors to yield the best comparison with the SP2. This could be due to influences of fuel type or burn phase.