Size-partitioning of an urban aerosol to identify particle determinants involved in the proinflammatory response induced in airway epithelial cells

<p>Abstract</p> <p>Background</p> <p>The contribution of air particles in human cardio-respiratory diseases has been enlightened by several epidemiological studies. However the respective involvement of coarse, fine and ultrafine particles in health effects is still unclear. The aim of the present study is to determine which size fraction from a chemically characterized background aerosol has the most important short term biological effect and to decipher the determinants of such a behaviour.</p> <p>Results</p> <p>Ambient aerosols were collected at an urban background site in Paris using four 13-stage low pressure cascade impactors running in parallel (winter and summer 2005) in order to separate four size-classes (PM_0.03–0.17(defined here as ultrafine particles), PM_0.17–1(fine), PM_1–2.5(intermediate) and PM_2.5–10(coarse)). Accordingly, their chemical composition and their pro-inflammatory potential on human airway epithelial cells were investigated. Considering isomass exposures (same particle concentrations for each size fractions) the pro-inflammatory response characterized by Granulocyte Macrophage-Colony Stimulating Factor (GM-CSF) release was found to decrease with aerosol size with no seasonal dependency. When cells were exposed to isovolume of particle suspensions in order to respect the particle proportions observed in ambient air, the GM-CSF release was maximal with the fine fraction. In presence of a recombinant endotoxin neutralizing protein, the GM-CSF release induced by particles is reduced for all size-fractions, with exception of the ultra-fine fraction which response is not modified. The different aerosol size-fractions were found to display important chemical differences related to the various contributing primary and secondary sources and aerosol age. The GM-CSF release was correlated to the organic component of the aerosols and especially its water soluble fraction. Finally, Cytochrome P450 1A1 activity that reflects PAH bioavailability varied as a function of the season: it was maximal for the fine fraction in winter and for the ultrafine fraction in summer.</p> <p>Conclusion</p> <p>In the frame of future regulations, a particular attention should thus be paid to the ultrafine/fine (here referred to as PM1) fraction due to their overwhelming anthropogenic origin and predominance in the urban aerosol and their pro-inflammatory potential.</p

Meteorology-driven variability of air pollution (PM₁) revealed with explainable machine learning

Air pollution, in particular high concentrations of particulate matter smaller than 1 µm in diameter (PM1), continues to be a major health problem, and meteorology is known to substantially influence atmospheric PM concentrations. However, the scientific understanding of the ways in which complex interactions of meteorological factors lead to high-pollution episodes is inconclusive. In this study, a novel, data-driven approach based on empirical relationships is used to characterize and better understand the meteorology-driven component of PM1 variability. A tree-based machine learning model is set up to reproduce concentrations of speciated PM1 at a suburban site southwest of Paris, France, using meteorological variables as input features. The model is able to capture the majority of occurring variance of mean afternoon total PM1 concentrations (coefficient of determination (R2) of 0.58), with model performance depending on the individual PM1 species predicted. Based on the models, an isolation and quantification of individual, season-specific meteorological influences for process understanding at the measurement site is achieved using SHapley Additive exPlanation (SHAP) regression values. Model results suggest that winter pollution episodes are often driven by a combination of shallow mixed layer heights (MLHs), low temperatures, low wind speeds, or inflow from northeastern wind directions. Contributions of MLHs to the winter pollution episodes are quantified to be on average ∼5 µg/m3 for MLHs below <500 m a.g.l. Temperatures below freezing initiate formation processes and increase local emissions related to residential heating, amounting to a contribution to predicted PM1 concentrations of as much as ∼9 µg/m3. Northeasterly winds are found to contribute ∼5 µg/m3 to predicted PM1 concentrations (combined effects of u- and v-wind components), by advecting particles from source regions, e.g. central Europe or the Paris region. Meteorological drivers of unusually high PM1 concentrations in summer are temperatures above ∼25 ∘C (contributions of up to ∼2.5 µg/m3), dry spells of several days (maximum contributions of ∼1.5 µg/m3), and wind speeds below ∼2 m/s (maximum contributions of ∼3 µg/m3), which cause a lack of dispersion. High-resolution case studies are conducted showing a large variability of processes that can lead to high-pollution episodes. The identification of these meteorological conditions that increase air pollution could help policy makers to adapt policy measures, issue warnings to the public, or assess the effectiveness of air pollution measures

Population exposure to outdoor NO2, black carbon, particle mass, and number concentrations over Paris with multi-scale modelling down to the street scale

This study focuses on mapping the concentrations of pollutants of health interest (NO2, black carbon (BC), PM2.5, number of particles (PN)) down to the street scale to represent as accurately as possible the population exposure. Simulations are performed over the Greater Paris area with the WRF-CHIMERE/MUNICH/SSH-aerosol chain, using either the top-down inventory EMEP or the bottom-up inventory Airparif with correction of the traffic flow. The concentrations of the pollutants are higher in streets than in the regional-scale urban background, due to the strong influence of road-traffic emissions locally. Model-to-data comparisons were performed at urban background and traffic stations, and evaluated using two performance criteria from the literature. For BC, harmonized equivalent BC (eBC) concentrations were estimated from concomitant mea-surements of eBC and elemental carbon. Using the bottom-up inventory with corrected road-traffic flow, the strictest criteria are met for NO2, eBC, PM2.5, and PN. Using the EMEP top-down inventory, the strictest criteria are also met for NO2, eBC and PM2.5, but errors tend to be larger than with the bottom-up inventory for NO2, eBC and PN. Using the top-down inventory, the concentrations tend to be lower along the streets than those simulated using the bottom-up inventory, especially for NO2 con-centrations, resulting in less urban heterogeneities. The impact of the size-distribution of non-exhaust emissions was analyzed at both regional and local scales, and it is higher in heavy-traffic streets. To assess exposure, a french database detailing the number of inhabitants in each building was used. The population-weighted concentration (PWC) was calculated by weighting populations by the outdoor concentrations to which they are exposed at the precise location of their home. An exposure scaling factor (ESF) was determined for each pollutant to estimate the ratio needed to correct urban background concentrations in order to assess exposure. The average ESF in Paris and Paris Ring Road is higher than 1 for NO2, eBC, PM2.5, PN, because the concentrations simulated at the local scale in streets are higher than those modelled at the regional scale. It indicates that the Parisian population exposure is under-estimated using regional-scale concentrations. Although this underestimation is low for PM2.5, with an ESF of 1.04, it is very high for NO2 (1.26), eBC (between 1.22 and 1.24), and PN (1.12). This shows that urban heterogeneities are important to be considered in order to represent the population exposure to NO2, eBC, and PN, but less so for PM2.5

Detecting and Characterizing Particulate Organic Nitrates with an Aerodyne Long-ToF Aerosol Mass Spectrometer

Particulate organic nitrate (pON) can be a major part of secondary organic aerosol (SOA) and is commonly quantified by indirect means from aerosol mass spectrometer (AMS) data. However, pON quantification remains challenging. Here, we set out to quantify and characterize pON in the boreal forest, through direct field observations at Station for Measuring Ecosystem Atmosphere Relationships (SMEAR) II in Hyytia''la'', Finland, and targeted single precursor laboratory studies. We utilized a long time-of-flight AMS (LToF-AMS) for aerosol chemical characterization, with a particular focus to identify CxHyOzN+ ("CHON+") fragments. We estimate that during springtime at SMEAR II, pON (including both the organic and nitrate part) accounts for similar to 10% of the particle mass concentration (calculated by the NO+/NO2+ method) and originates mainly from the NO3 radical oxidation of biogenic volatile organic compounds. The majority of the background nitrate aerosol measured is organic. The CHON+ fragment analysis was largely unsuccessful at SMEAR II, mainly due to low concentrations of the few detected fragments. However, our findings may be useful at other sites as we identified 80 unique CHON+ fragments from the laboratory measurements of SOA formed from NO3 radical oxidation of three pON precursors (beta-pinene, limonene, and guaiacol). Finally, we noted a significant effect on ion identification during the LToF-AMS high-resolution data processing, resulting in too many ions being fit, depending on whether tungsten ions (W+) were used in the peak width determination. Although this phenomenon may be instrument-specific, we encourage all (LTOF-) AMS users to investigate this effect on their instrument to reduce the possibility of incorrect identifications.Peer reviewe

Estimation de la contribution des émissions Îhiculaires à l'échappement et hors-échappement aux teneurs atmosphériques en PM10 par Positive Matrix Factorization (PMF)

The goal of this work is the development of a methodology allowing the assessment of road traffic exhaust and non-exhaust contributions (resuspension of road dusts, from brakes, tyres and road-surface-wear, from the corrosion of vehicle components...) to PM10 in an urban site. The approach used source apportionment modelling by PMF (Positive Matrix Factorization) with a chemical data set including chemical tracers. These data are obtained thanks to filter samples collected during short-time periods (4h temporal resolution). This study also includes the simultaneous sampling of chemical species on an urban background site (Grenoble-Les Frênes, France) and on a roadside site (Grenoble-Echirolles, France). This combination leads to accurate determination of traffic indicators sources. Finally, the source apportionment using PMF applied to this database gives possible contribution of sources to PM10. Results show that the road traffic source contribution to PM10 (exhaust + non-exhaust sources) was on average 34% and ranged from about 57% during the rush hours to 14% during less busy periods. Non-exhaust contribution is on average equivalent to the exhaust one.L'objectif de cette étude est de tester une méthodologie permettant de déterminer les contributions respectives aux teneurs atmosphériques en PM10 des émissions Îhiculaires à l'échappement et hors échappement (abrasion des freins, des pneus et de la route, remise en suspension des poussières de la chaussée...) dans un milieu urbain. La stratégie adoptée est d'appliquer une méthode de déconvolution des sources par un modèle statistique d'analyses multivariées (PMF, Positive Matrix Factorization) sur un jeu de données chimiques obtenues avec des filtres collectés sur des durées réduites (4h) et comprenant des traceurs spécifiques. Les prélèvements ont été réalisés simultanément sur un site de fond urbain (Grenoble-Les Frênes, France) et sur un site de proximité automobile (Grenoble-Échirolles, France). La discrimination des sources et la quantification de leur contribution par PMF sont ensuite obtenues sur la base de données établie. Les résultats montrent que les émissions Îhiculaires à l'échappement et hors échappement contribuent en moyenne à 34 % des PM10 et jusqu'à 57 % durant les heures de pointe, contre seulement 14 % durant les heures creuses. Sur la période de mesure, les émissions hors échappement sont en moyenne équivalentes aux émissions à l'échappement pour le site d'étude de proximité trafic

Towards a better understanding of fine PM sources: online and offline datasets combination in a single PMF

Co-located one-year measurements of non-refractory submicronic particulate matter (NR-PM1), black carbon (BC) and metals, obtained respectively, by a Q-ACSM (Aerodyne Research Inc.), an Aethalometer (Aerosol d.o.o.) and offline fine PM samples collected on quartz-fibre filters, were combined in a single PMF in two different resolutions (30 minutes for the NR-PM1 and BC, and 24h every 4 days for the offline samples). The multi-time resolution PMF (MTR-PMF) was run varying both the time resolution (averaging the dataset) and the uncertainty weightings of both datasets in order to assess the impact of these variations on the model output. The resolution assessment revealed that averaging the high-resolution data was disadvantageous in terms of model residuals and environmental feasibility. Regarding uncertainty weightings, overweighting the uncertainties of the 24-h dataset dividing them by two provided the most optimal scaled residuals adjustment. The MTR-PMF was run with the optimised time resolution and uncertainty weightings retrieving eight PM1 sources: ammonium sulphate (AS) + heavy oil combustion (24%), ammonium nitrate (AN) and ammonium chloride (15%), fresh SOA (15%), traffic (14%), biomass burning (11%), aged SOA + mineral dust (8%), urban mix (7%) and cooking-like organic aerosol + industry (6%). The MTR-PMF technique allowed the identification of two more sources respect a dataset containing the same species at a 24h time resolution (base case) and four more respect to the conventional offline and PMF, proving that the combination of both high and low time resolution data through MTR-PMF is significantly beneficial for SA. This is especially true for those sources which have been disentangled with respect to the conventional and base case PMFs.Peer reviewe

PM₁₀-bound trace elements in pan-European urban atmosphere

Although many studies have discussed the impact of Europe's air quality, very limited research focused on the detailed phenomenology of ambient trace elements (TEs) in PM10 in urban atmosphere. This study compiled long-term (2013–2022) measurements of speciation of ambient urban PM10 from 55 sites of 7 countries (Switzerland, Spain, France, Greece, Italy, Portugal, UK), aiming to elucidate the phenomenology of 20 TEs in PM10 in urban Europe. The monitoring sites comprised urban background (UB, n = 26), traffic (TR, n = 10), industrial (IN, n = 5), suburban background (SUB, n = 7), and rural background (RB, n = 7) types. The sampling campaigns were conducted using standardized protocols to ensure data comparability. In each country, PM10 samples were collected over a fixed period using high-volume air samplers. The analysis encompassed the spatio-temporal distribution of TEs, and relationships between TEs at each site. Results indicated an annual average for the sum of 20 TEs of 90 ± 65 ng/m3, with TR and IN sites exhibiting the highest concentrations (130 ± 66 and 131 ± 80 ng/m3, respectively). Seasonal variability in TEs concentrations, influenced by emission sources and meteorology, revealed significant differences (p &lt; 0.05) across all monitoring sites. Estimation of TE concentrations highlighted distinct ratios between non-carcinogenic and carcinogenic metals, with Zn (40 ± 49 ng/m3), Ti (21 ± 29 ng/m3), and Cu (23 ± 35 ng/m3) dominating non-carcinogenic TEs, while Cr (5 ± 7 ng/m3), and Ni (2 ± 6 ng/m3) were prominent among carcinogenic ones. Correlations between TEs across diverse locations and seasons varied, in agreement with differences in emission sources and meteorological conditions. This study provides valuable insights into TEs in pan-European urban atmosphere, contributing to a comprehensive dataset for future environmental protection policies

The second ACTRIS inter-comparison (2016) for Aerosol Chemical Speciation Monitors (ACSM) : Calibration protocols and instrument performance evaluations

AbstractThis work describes results obtained from the 2016 Aerosol Chemical Speciation Monitor (ACSM) intercomparison exercise performed at the Aerosol Chemical Monitor Calibration Center (ACMCC, France). Fifteen quadrupole ACSMs (Q_ACSM) from the European Research Infrastructure for the observation of Aerosols, Clouds and Trace gases (ACTRIS) network were calibrated using a new procedure that acquires calibration data under the same operating conditions as those used during sampling and hence gets information representative of instrument performance. The new calibration procedure notably resulted in a decrease in the spread of the measured sulfate mass concentrations, improving the reproducibility of inorganic species measurements between ACSMs as well as the consistency with co-located independent instruments. Tested calibration procedures also allowed for the investigation of artifacts in individual instruments, such as the overestimation of m/z 44 from organic aerosol. This effect was quantified by the m/z (mass-to-charge) 44 to nitrate ratio measured during ammonium nitrate calibrations, with values ranging from 0.03 to 0.26, showing that it can be significant for some instruments. The fragmentation table correction previously proposed to account for this artifact was applied to the measurements acquired during this study. For some instruments (those with high artifacts), this fragmentation table adjustment led to an ?overcorrection? of the f44 (m/z 44/Org) signal. This correction based on measurements made with pure NH4NO3, assumes that the magnitude of the artifact is independent of chemical composition. Using data acquired at different NH4NO3 mixing ratios (from solutions of NH4NO3 and (NH4)2SO4) we observe that the magnitude of the artifact varies as a function of composition. Here we applied an updated correction, dependent on the ambient NO3 mass fraction, which resulted in an improved agreement in organic signal among instruments. This work illustrates the benefits of integrating new calibration procedures and artifact corrections, but also highlights the benefits of these intercomparison exercises to continue to improve our knowledge of how these instruments operate, and assist us in interpreting atmospheric chemistry.Peer reviewe

ACTRIS ACSM intercomparison – Part 2: Intercomparison of ME-2 organic source apportionment results from 15 individual, co-located aerosol mass spectrometers

Chemically resolved atmospheric aerosol data sets from the largest intercomparison of the Aerodyne aerosol chemical speciation monitors (ACSMs) performed to date were collected at the French atmospheric supersite SIRTA. In total 13 quadrupole ACSMs (Q-ACSM) from the European ACTRIS ACSM network, one time-of-flight ACSM (ToF-ACSM), and one high-resolution ToF aerosol mass spectrometer (AMS) were operated in parallel for about 3 weeks in November and December~2013. Part 1 of this study reports on the accuracy and precision of the instruments for all the measured species. In this work we report on the intercomparison of organic components and the results from factor analysis source apportionment by positive matrix factorisation (PMF) utilising the multilinear engine 2 (ME-2). Except for the organic contribution of mass-to-charge ratio m/z 44 to the total organics (f44), which varied by factors between 0.6 and 1.3 compared to the mean, the peaks in the organic mass spectra were similar among instruments. The m/z 44 differences in the spectra resulted in a variable f44 in the source profiles extracted by ME-2, but had only a minor influence on the extracted mass contributions of the sources. The presented source apportionment yielded four factors for all 15 instruments: hydrocarbon-like organic aerosol (HOA), cooking-related organic aerosol (COA), biomass burning-related organic aerosol (BBOA) and secondary oxygenated organic aerosol (OOA). ME-2 boundary conditions (profile constraints) were optimised individually by means of correlation to external data in order to achieve equivalent / comparable solutions for all ACSM instruments and the results are discussed together with the investigation of the influence of alternative anchors (reference profiles). A comparison of the ME-2 source apportionment output of all 15 instruments resulted in relative standard deviations (SD) from the mean between 13.7 and 22.7 % of the source's average mass contribution depending on the factors (HOA: 14.3 ± 2.2 %, COA: 15.0 ± 3.4 %, OOA: 41.5 ± 5.7 %, BBOA: 29.3 ± 5.0 %). Factors which tend to be subject to minor factor mixing (in this case COA) have higher relative uncertainties than factors which are recognised more readily like the OOA. Averaged over all factors and instruments the relative first SD from the mean of a source extracted with ME-2 was 17.2 %.JRC.H.2-Air and Climat

ACTRIS ACSM intercomparison – Part 1: Reproducibility of concentration and fragment results from 13 individual Quadrupole Aerosol Chemical Speciation Monitors (Q-ACSM) and consistency with co-located instruments

As part of the European ACTRIS project, the first large Quadrupole Aerosol Chemical Speciation Monitor (Q-ACSM) intercomparison study was conducted in the region of Paris for 3 weeks during the late-fall – early-winter period (November–December 2013). The first week was dedicated to the tuning and calibration of each instrument, whereas the second and third were dedicated to side-by-side comparison in ambient conditions with co-located instruments providing independent information on submicron aerosol optical, physical, and chemical properties. Near real-time measurements of the major chemical species (organic matter, sulfate, nitrate, ammonium, and chloride) in the non-refractory submicron aerosols (NR-PM1) were obtained here from 13 Q-ACSM. The results show that these instruments can produce highly comparable and robust measurements of the NR-PM1 total mass and its major components. Taking the median of the 13 Q-ACSM as a reference for this study, strong correlations (r2 > 0.9) were observed systematically for each individual Q-ACSM across all chemical families except for chloride for which three Q-ACSMs showing weak correlations partly due to the very low concentrations during the study. Reproducibility expanded uncertainties of Q-ACSM concentration measurements were determined using appropriate methodologies defined by the International Standard Organization (ISO 17025, 1999) and were found to be 9, 15, 19, 28, and 36 % for NR-PM1, nitrate, organic matter, sulfate, and ammonium, respectively. However, discrepancies were observed in the relative concentrations of the constituent mass fragments for each chemical component. In particular, significant differences were observed for the organic fragment at mass-to-charge ratio 44, which is a key parameter describing the oxidation state of organic aerosol. Following this first major intercomparison exercise of a large number of Q-ACSMs, detailed intercomparison results are presented, along with a discussion of some recommendations about best calibration practices, standardized data processing, and data treatment.JRC.H.2-Air and Climat