Potential underestimation of ultrafine particle exposure when using proxy pollutants

Air pollution exposure prediction models can make use of many types of air monitoring data. Fixed location passive samples typically measure concentrations averaged over several days to weeks. Mobile monitoring data can generate near continuous concentration measurements. It is not known whether mobile monitoring data are suitable for generating well-performing exposure prediction models or how they compare with other types of monitoring data in generating exposure models. Measurements from fixed site passive samplers and mobile monitoring platform were made over a 2-week period in Baltimore in the summer and winter months in 2012. Performance of exposure prediction models for long-term nitrogen oxides (NOX) and ozone (O3) concentrations were compared using a state-of-the-art approach for model development based on land use regression (LUR) and geostatistical smoothing. Model performance was evaluated using leave-one-out cross-validation (LOOCV). Models performed well using the mobile peak traffic monitoring data for both NOX and O3, with LOOCV R2s of 0.70 and 0.71, respectively, in the summer, and 0.90 and 0.58, respectively, in the winter. Models using 2-week passive samples for NOX had LOOCV R2s of 0.60 and 0.65 in the summer and winter months, respectively. The passive badge sampling data were not adequate for developing models for O3. Mobile air monitoring data can be used to successfully build well-performing LUR exposure prediction models for NOX and O3 and are a better source of data for these models than 2-week passive badge data.

Formation of Ultrafine particles (UFPs) in the urban atmosphere is expected to be less favored than in the rural atmosphere due to the high existing particle surface area acting as a sink for newly-formed particles Despite the large condensation sink (CS) values, previous comparative studies between rural and urban site reported higher frequency of new particle formation (NPF) events over urban sites in comparison to background sites as well as higher particle formation and growth rates attributed to the higher concentration of condensable species. The present study aims to better understand the environmental factors favoring, or disfavoring, atmospheric NPF over Lille, a large city North of France and to analyze their impact on particle number concentration using a long-term dataset (4 years : 1st July 2017 to 31st December 2020). The results highlight a strong seasonal variation of the NPF occurrences with a maximum observed during spring (27 events) and summer (53 events). It was found that high temperature (T > 295 K), low RH (RH < 45 %) and high solar radiation are ideal to observe NPF events over Lille. Relatively high values of condensation sink (CS ~ 2.10-2 s-1) are reported during event days suggesting that high CS does not inhibit the occurrence of NPFt over our site. Moreover, the particle Growth Rate (GR15.7-30 nm) was positively correlated with the temperature most probably linked to the higher emissions of precursors. Finally, the nucleation strength factor (NSF) was calculated to highlight the impact of those NPF events on particle number concentrations. NSF15.7-100 reaches a maximum of 4 in summer, indicating an enormous contribution of NPF events to particle number concentration at this time of the year.

Abstract. The strictest ever clean air action (CAA) plan has been implemented by the Chinese government since 2013 to alleviate the severe haze pollution. The PM2.5 mass concentration was found to largely be reduced in response to emission mitigation policies, but the response of particle number concentrations (PNCs) to CAA was less evaluated in the previous studies, which may be significantly different from PM2.5 mass due to newly formed particle impacts. In this work, the first in situ observation of particle number size distributions (PNSDs) during 2012–2019 in urban Lanzhou was used to analyze long-term PNC variations and CAA impacts. The average number of particles in nucleation (N13−25, particle number in the size range of 13–25 nm), Aitken (N25−100, particle number in the size range of 25–100 nm) and accumulation (N100−800, particle number in the size range of 100–800 nm) modes were respectively 2514.0, 10 768.7 and 3258.4 cm−3, and N25−100 accounted for about 65.1 % of total PNCs during the campaign. The k-means clustering technique was used to classify the hourly mean PNSDs into six clusters, and each cluster corresponded to a specific source and influencing factor. The polluted clusters governed the winter PNCs before 2016, and their occurrence was less and less frequent after 2016, which was largely dominated by reduction in primary emissions. However, the contribution of new particle formation (NPF) events to summer N13−25 decreased from 50 % to about 10 % during 2013 to 2015 and then increased to reach around 60 % in 2019. The trends of size-resolved PNCs for each cluster were quantified by Theil–Sen regression. The size-segregated PNCs exhibited downward trends for all clusters during 2012–2015, especially in spring. The annual relative slopes of spring PNCs varied from −54.7 % to −17.2 %, −42.6 % to −14.1 %, and −40.7 % to −17.5 % per year for 13–25, 25–100, and 100–800 nm size ranges, and the reduction in the polluted clusters was much larger than NPF clusters. The ultrafine particle number was increased, and the amplitude was much greater during 2016–2019. The annual relative slopes of N13−25 varied between 8.0 % in fall and 135.5 % in spring for the NPF cluster. In response to CAA, the increased daytime net radiation, higher ambient temperature and lower relative humidity at noon for NPF events also could partly explain the higher N13−25 induced by the more frequent nucleation events after 2016, especially in spring. The air masses were mainly from the adjacent regions of urban Lanzhou and less affected by long-range transport for NPF events, and thus the particles were not easily grown by coagulation during transport processes, which was helpful for the occurrence of NPF events. Therefore, some effective measures to cooperatively control particle number concentration and mass should be taken for the Chinese megacities.

New particle formation (NPF) in the atmosphere i.e. nucleation of gas phase precursors and continuing condensa- tional growth is a crucial secondary transformation process. The freshly nucleated particles can grow into sizes where they can act as cloud condensation nuclei (CCN) and further influence cloud and climate-relevant properties. Hence, the detailed knowledge on the formation mechanisms of new particles and their subsequent growth will help us to improve our under- standing on the regional air pollution and global climate change. Recent-developed measurement techniques enable to ex- plore atmospheric nucleation by measuring particles/clusters down to 1 nm. NPF events have been observed in a variety of atmospheric environments. Several methods including field observation, laboratory simulations and model calculations are implemented to investigate the nucleation mechanisms and growth properties. Good agreement between particle formation rates and gaseous sulfuric acid concentrations is observed, indicating that sulfuric acid is a key compnent in the atmospheric nucleation process. In addition, the low-volatile organic vapors are found to be involved in new particle formation. However, the huge variations of the particle formation and growth rates in diverse atmospheric environments suggest that a consistent picture on formation mechanisms of new particles does not achieve. Long-term continuous measurements of NPF events have been first performed in the urban atmosphere of Beijing since 2004. Up to now, NPF events have been observed in many different environments, including coastal area, high-elevation mountain, rural site as well as urban region in China. The cur- rent nucleation mechanisms are developed based on the observation in clean environment. Hence, whether it could well ex- plain the NPF events occurred in the polluted atmosphere with strong oxidation capacity is a key issue to be addressed in further studies. This paper reviews the measurement techniques for investigating atmospheric new particle formation and growth, summarizes the observation results in various typical environments, introduces the current understanding of the nu- cleation mechanisms and discusses the main scientific questions that need further researches. Keywords new particle formation; nucleation mechanism; growth property; measurement technique; precursor 1 引言

Abstract. The spatial and temporal variability of the number size distribution of aerosol particles is an indicator of the dynamic behavior of Beijing's atmospheric pollution cocktail. This variation reflects the strength of different primary and secondary sources, such as traffic and new particle formation, as well as the main processes affecting the particle population. In this paper, we report size-segregated particle number concentrations observed at a newly developed Beijing station during the winter of 2018. Our measurements covered particle number size distributions over the diameter range of 1.5 nm–1 µm (cluster mode, nucleation mode, Aitken mode and accumulation mode), thus being descriptive of a major fraction of the processes taking place in the atmosphere of Beijing. Here we focus on explaining the concentration variations in the observed particle modes, by relating them to the potential aerosol sources and sinks, and on understanding the connections between these modes. We considered haze days and new particle formation event days separately. Our results show that during the new particle formation (NPF) event days increases in cluster mode particle number concentration were observed, whereas during the haze days high concentrations of accumulation mode particles were present. There was a tight connection between the cluster mode and nucleation mode on both NPF event and haze days. In addition, we correlated the particle number concentrations in different modes with concentrations of trace gases and other parameters measured at our station. Our results show that the particle number concentration in all the modes correlated with NOx, which reflects the contribution of traffic to the whole submicron size range. We also estimated the contribution of ion-induced nucleation in Beijing, and we found this contribution to be negligible.

Abstract. Understanding the particle number size distributions in diversified atmospheric environments is important in order to design mitigation strategies related to submicron particles and their effects on regional air quality, haze and human health. In this study, we conducted 15 different field measurement campaigns between 2007 and 2011 at 13 individual sites in China, including five urban sites, four regional sites, three coastal/background sites and one ship cruise measurement along eastern coastline of China. Size resolved particles were measured in the 15–600 nm size range. The median particle number concentrations (PNCs) were found to vary in the range of 1.1−2.2 × 104 cm−3 at urban sites, 0.8−1.5 × 104 cm−3 at regional sites, 0.4−0.6 × 104 cm−3 at coastal/background sites, and 0.5 × 104 cm−3 during cruise measurement. Peak diameters at each of these sites varied greatly from 24 to 115 nm. Particles in the 15–25 nm (nucleation mode), 25–100 nm (Aitken mode) and 100–600 nm (accumulation mode) range showed different characteristics at each sites, indicating the features of primary emissions and secondary formation in these diversified atmospheric environments. Diurnal variations show a build-up of accumulation mode particles belt at regional sites, suggesting the contribution of regional secondary aerosol pollution. Frequencies of new particle formation (NPF) events were much higher at urban and regional sites than at coastal sites and during cruise measurement. The average growth rates (GRs) of nucleation mode particles were 8.0–10.9 nm h−1 at urban sites, 7.4–13.6 nm h−1 at regional sites and 2.8–7.5 nm h−1 at coastal sites and during cruise measurement. The high gaseous precursors and strong oxidation at urban and regional sites not only favored the formation of particles, but also accelerated the growth rate of the nucleation mode particles. No significant difference in condensation sink (CS) during NPF days were observed among different site types, suggesting that the NPF events in background areas were more influenced by the pollutant transport. In addition, average contributions of NPF events to potential cloud condensation nuclei (CCN) at 0.2% super-saturation in the afternoon of all sampling days were calculated as 11% and 6% at urban sites and regional sites, respectively. On the other hand, NPF events at coastal sites and during cruise measurement had little impact on potential production of CCN. This study provides a large data set of particle size distribution in diversified atmosphere of China, improving our general understanding of emission, secondary formation, new particle formation and corresponding CCN activity of submicron aerosols in Chinese environments.

The PEAK study aims to determine the association of particle size, microenvironment (ME) and peak exposure with respiratory effects in children with asthma. 25 children aged 8-17 with asthma were each followed for 4 consecutive days. Children&amp;#8217;s personal PM2.5 (particles with diameter less than 2.5 &amp;#956;m) and ultrafine particle (UFP, diameter less than 0.1 &amp;#956;m) exposures were measured at high spatiotemporal resolutions using a backpack containing personal PM2.5 and UFP (expressed as LDSA, lung-deposited surface area) monitors and a GPS for geographic location (logging interval&amp;#61; 10 seconds). Information about means of transportation used, places visited, and activities at home that may have resulted in high exposures were also obtained. Exposures were partitioned into five MEs: Home, School, Vehicle transport, Pedestrian transport, and Other. PM2.5 and UFP cumulative exposures were dominated by Home. Mean UFP exposure intensities while in Pedestrian transport and Vehicle transport were both greater than 1 and higher than PM2.5. Exposure intensities while in Pedestrian transport were also greater than Vehicle transport. Correlations between PM2.5 and LDSA concentrations were examined to evaluate the need for personal UFP exposure monitoring in addition to the commonly-monitored PM2.5. The highest and lowest mean PM2.5/LDSA correlation coefficients belonged to Home (r&amp;#61;0.47) and Vehicle transport (r&amp;#61;0.15). Home pollutant correlations were particularly weak (high UFP and low PM2.5) during evening hours and coincided with common household activities such as cooking, cleaning, and burning candles/incense. Our findings suggest that UFP exposure is only weakly to moderately correlated with fine PM exposure, suggesting that personal exposure monitoring at high spatiotemporal resolutions and including UFP to personal exposure monitoring campaigns, may be important to fully understand the effect of particulate exposures in susceptible populations such as children with asthma.

Volcanic emissions can significantly affect the Earth's radiation budget by emitting aerosol particles and gas‐phase species that can result in the new particle formation (NPF). These particles can scatter solar radiation or modify cloud properties, with consequences on health, weather, and climate. To our knowledge, this is the first dedicated study detailing how gas‐phase precursors emitted from volcanic plumes can influence the NPF. A series of airborne measurements were performed around the Etna and Stromboli volcanoes within the framework of the CLerVolc and STRAP projects. The ATR‐42 aircraft was equipped with a range of instrumentation allowing the measurement of particle number concentration in diameter range above 2.5 nm and gaseous species to investigate the aerosol dynamics and the processes governing the NPF and their growth within the volcanic plumes. We demonstrate that NPF occurs within the volcanic plumes in the free troposphere (FT) and boundary layer (BL). Typically, the NPF events were more pronounced in the FT, where the condensational sink was up to two orders of magnitude smaller and the temperature was ~20 °C lower than in the BL. Within the passive volcanic plume, the concentration of sulfur dioxide, sulfuric acid, and N2.5 were as high as 92 ppbV, 5.65 × 108 and 2.4 × 105 cm−3, respectively. Using these measurements, we propose a new parameterization for NPF rate (J2.5) within the passive volcanic plume in the FT. These results can be incorporated into mesoscale models to better assess the impact of the particle formed by natural processes, that is, volcanic plumes, on climate.

Addressing the challenge of mapping hyperlocal air pollution in areas without local monitoring, we evaluated unsupervised transfer learning-based land-use regression (LUR) models developed using mobile monitoring data from other cities: CORrelation ALignment (Coral) and its inverse distance-weighted modification (IDW_Coral). These models mitigated domain shifts and transferred patterns learned from mobile air quality monitoring campaigns in Copenhagen and Rotterdam to estimate annual average air pollution levels in Amsterdam (50m road segments) without involving any Amsterdam measurements in model development. For nitrogen dioxide (NO2), IDW_Coral outperformed Copenhagen and Rotterdam LUR models directly applied to Amsterdam, achieving MAE (4.47 μg/m3) and RMSE (5.36 μg/m3) comparable to a locally fitted LUR model (AMS_SLR) developed using Amsterdam mobile measurements collected for 160 days. IDW_Coral yielded an R2 of 0.35, similar to that of the AMS_SLR based on 20 collection days, suggesting a minimum requirement of 20-day mobile monitoring to capture city-specific insights. For ultrafine particles (UFP), IDW_Coral's citywide predictions strongly correlated with previously published mixed-effect models fitted with 160-day Amsterdam measurements (Pearson correlation of 0.71 for UFP and 0.72 for NO2). IDW_Coral demands no direct measurements in the target area, showcasing its potential for large-scale applications and offering significant economic efficiencies in executing mobile monitoring campaigns.

Aerosol size distribution and new particle formation events in the suburb of Xi'an, northwest China

Accurate information about aerosol particle size distribution and its variation under different meteorological conditions are essential for reducing uncertainties related to aerosol-cloud-climate interaction processes. New particle formation (NPF) and the coagulation significantly affect the aerosol size distribution. Here we study the monthly and seasonal variability of aerosol particle size distribution at Delhi from December 2011 to January 2013. Analysis of aerosol particle size distribution using WRAS-GRIMM reveals that aerosol particle number concentration is highest during the post monsoon season owing to the effect of transported crop residue and biomass burning aerosols. Diurnal variations in number concentration show a bimodal pattern with two Aitken mode peaks in all the seasons. Monthly volume size distribution also shows bi-modal distribution with distinct coarse and fine modes. NPF events are observed less frequently in Delhi. Out of 222 days of WRAS data, only 17 NPF events have been observed, with higher NPF frequency during summer season. Growth rate of the nucleation mode of NPF events vary in the range 1.88–21.66 nm/h with a mean value of ∼8.45 ± 5.73 nm/h. It is found that during NPF events the Aitken and nucleation mode particles contribute more to the number concentration. Simultaneous measurement of UV flux and particulate matter (PM10and PM2.5) have also been done along with particle number size distribution measurement to understand the possible mechanisms for NPF events over the study location.

The formation of new atmospheric aerosol particles and their subsequent growth have been observed under different environmental conditions globally; such observations are few over northwest China. Here, we present an analysis of some case studies for new particle formation (NPF) events from two distinct suburban locations in northern China during May and June of two consecutive years, and provide more information to understand the characteristics of NPF events in North China. Particle number size distribution was measured at suburbs of Beijing (39.75° N, 116.96° E) during 1 June to 2 July 2013 and at suburbs of Xi’an (34.09° N, 108.55° E) during 1 to 25 May 2014. The average of total particle number concentration in the similar size range of 10–487 nm at the suburbs of Beijing (9.0 × 103 cm−3) was about two times higher than those observed at Xi’an (4.7 × 103 cm−3), and the mean particle mode diameter at Beijing was 1.4-fold higher than that at Xi’an. The estimated total condensation sink (CS) at Beijing (3.11 × 10−2 s−1) was also higher than at Xi’an (1.13 × 10−2 s−1). The frequency of NPF events at suburb of Beijing was 24%, lower than that in Xi’an (50%), and also lower than urban site of Beijing (35% in June) and another suburb of Beijing (over 50% in June). The NPF events with (Class I) or without (Class II) subsequent growth were both observed at the two suburb sites. The derived GR at the suburb of Beijing (range from 4.6 to 8.6 nm h−1) was a little higher than that at Xi’an (range from 3.3 to 6.7 nm h−1), which are generally comparable to typical values in mid-latitude reported in previous studies. The air masses coming from north or northwest China favor the occurrence of NPF event under low condensation sink and clear days. The number size distributions of freshly nucleated particles showed clear bimodal distributions on both sites. Additionally, Mode Dp of nucleated particles at the two sites was 17 ± 1 nm and 22 ± 4 nm, respectively during the periods with NPF events. The case study of NPF events at the two suburb sites shows that the surface area concentration and total scattering coefficient (SC) was significant decreased during the NPF events at both sites. High temperature, low condensation sink and low relative humidity furthered the occurrence of NPF events, and wind direction shifts were important for the subsequent growth of particles. NPF events in the suburbs of Beijing usually occurred when relative humidity (RH) &lt; 55%, CS &lt; 0.02 s−1, or 55% &lt; RH &lt; 68%, CS &lt; 0.01 s−1. However, there is no clear range for Xi’an. Furthermore, we observed that some NPF events occurred at higher RH and very low CS in this study on both sites, which means that low CS may be more important than low RH for the particle formation on clear days.

Several studies have investigated New Particle Formation (NPF) events from various sites ranging from pristine locations, including (boreal) forest sites to urban areas. However, there is still a dearth of studies investigating NPF processes and subsequent aerosol growth in coastal yet semi-urban sites, where the tropospheric layer is a concoction of biogenic and anthropogenic gases and particles. The investigation of factors leading to NPF becomes extremely complex due to the highly dynamic meteorological conditions at the coastline especially when combined with both continental and oceanic weather conditions. Herein, we engage a comprehensive study of particle number size distributions and aerosol-forming precursor vapors at the coastal semi-urban site in Helsinki, Finland. The measurement period, 25 June 2019–18 August 2019, was timed with the recurring cyanobacterial summer bloom in the Baltic Sea region and coastal regions of Finland. Our study recorded several regional/local NPF and aerosol burst events during this period. Although the overall anthropogenic influence on Sulfuric Acid (SA) concentrations was low during the measurement period, we observed that the regional or local NPF events, characterized by SA concentrations in the order of 107 molecules per cm−3 occurred mostly when the air mass travelled over the land areas. Interestingly, when the air mass travelled over the Baltic Sea, an area enriched with Algae and cyanobacterial blooms, high Iodic Acid (IA) concentration coincided with an aerosol burst or a spike event at the measurement site. Further, SA-rich bursts were seen when the air mass travelled over the Gulf of Bothnia, enriched with cyanobacterial blooms. The two most important factors affecting aerosol precursor vapor concentrations, and thus the aerosol formation, were (1) the type of phytoplankton species and intensity of bloom present in the coastal regions of Finland/ Baltic Sea and (2) the wind direction. During the events, most of the growth of sub-3 nm particles was probably due to SA, rather than IA or MSA, however much of the particle growth remained unexplained indicative of the strong role of organics in the growth of particles, especially in the 3–7 nm particle size range. Further studies are needed to explore the role of organics in NPF events and the potential influence of cyanobacterial blooms in coastal locations.

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

A field campaign has been performed in the Madrid region to study the VOC influence in the growth of new particles in ambient air. A number of instruments have been deployed to characterize the main pollutant gases and particle properties and composition. The measurements were performed simultaneously at three sites (rural, urban background and urban traffic influenced) in the period 1–17 July 2019. The sites: Tres Cantos (rural), CIEMAT (urban background) and Leganés (urban traffic) were located within the Madrid airshed. Particle size distributions, mass concentrations at fractions PM10, PM2.5 and PM1, black carbon, VOCs species and gaseous pollutants (NOx and O3) were obtained in the sites. Some supplementary measurements were obtained in at least one of the sites: meteorological parameters, non-refractory submicron aerosol species and vertical profiles of aerosol optical properties. It has been observed that the new particle formation (NPF) events, nucleation and subsequent growth, happened at a regional scale, although differently among the sites. In the rural site, fewer events than expected were observed because of the high temperatures that affected the BVOC emissions. In the urban background site, the highest number of events was reached. In this station, it is common to receive air masses from the nearby forest and from the urban area, producing a mix of conditions with high BVOC and AVOC concentrations. In the urban traffic site, several NPF cases appeared, being a site dominated by AVOCs. Among the BVOCs measured in the three stations, the most common were α-Pinene and Limonene. Among the AVOCs measured, aromatics and linear hydrocarbon compounds for C10 and above were found. The linear group was found to be predominant during the NPF event days in the urban background site. This work provides new insights about the aerosol-forming precursors and growth of new particles in the Madrid region.