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Atmospheric pollution in urban regions is highly influenced by oxidants due to their important role in the formation of secondary organic aerosol (SOA) and smog. These include the nitrate radical (NO3), which is typically considered a night-time oxidant, and the chlorine radical (Cl), an extremely potent oxidant that can be released in the morning in chloride-rich environments as a result of nocturnal build-up of nitryl chloride (ClNO2). Chloride makes up a higher percentage of particulate matter in Delhi than has been observed anywhere else in the world, which results in Cl having an unusually strong influence in this city. Here, we present observations and model results revealing that atmospheric chemistry in Delhi exhibits an unusual diel cycle, controlled by high concentrations of NO during the night. As a result of this, the formation of both NO3 and dinitrogen pentoxide (N2O5), a precursor of ClNO2 and thus Cl, are suppressed at night and increase to unusually high levels during the day. Our results indicate that a substantial reduction in night-time NO has the potential to increase both nocturnal oxidation via NO3 and the production of Cl during the day.

The lockdown due to COVID-19 created a rare opportunity to examine the nonlinear responses of secondary aerosols, which are formed through atmospheric oxidation of gaseous precursors, to intensive precursor emission reductions. Based on unique observational data sets from six supersites in eastern China during 2019-2021, we found that the lockdown caused considerable decreases (32-61%) in different secondary aerosol components in the study region because of similar-degree precursor reductions. However, due to insufficient combustion-related volatile organic compound (VOC) reduction, odd oxygen (Ox = O3 + NO2) concentration, an indicator of the extent of photochemical processing, showed little change and did not promote more decreases in secondary aerosols. We also found that the Chinese provinces and international cities that experienced reduced Ox during the lockdown usually gained a greater simultaneous PM2.5 decrease than other provinces and cities with an increased Ox. Therefore, we argue that strict VOC control in winter, which has been largely ignored so far, is critical in future policies to mitigate winter haze more efficiently by reducing Ox simultaneously.

Particulate matter (PM) has become a major concern in terms of human health and climate impact. In particular, the source apportionment (SA) of organic aerosols (OA) present in submicron particles (PM1) has gained relevance as an atmospheric research field due to the diversity and complexity of its primary sources and secondary formation processes. Moreover, relatively simple but robust instruments such as the Aerosol Chemical Speciation Monitor (ACSM) are now widely available for the near-real-time online determination of the composition of the non-refractory PM1. One of the most used tools for SA purposes is the source-receptor positive matrix factorisation (PMF) model. Even though the recently developed rolling PMF technique has already been used for OA SA on ACSM datasets, no study has assessed its added value compared to the more common seasonal PMF method using a practical approach yet. In this paper, both techniques were applied to a synthetic dataset and to nine European ACSM datasets in order to spot the main output discrepancies between methods. The main advantage of the synthetic dataset approach was that the methods' outputs could be compared to the expected "true"values, i.e. the original synthetic dataset values. This approach revealed similar apportionment results amongst methods, although the rolling PMF profile's adaptability feature proved to be advantageous, as it generated output profiles that moved nearer to the truth points. Nevertheless, these results highlighted the impact of the profile anchor on the solution, as the use of a different anchor with respect to the truth led to significantly different results in both methods. In the multi-site study, while differences were generally not significant when considering year-long periods, their importance grew towards shorter time spans, as in intra-month or intra-day cycles. As far as correlation with external measurements is concerned, rolling PMF performed better than seasonal PMF globally for the ambient datasets investigated here, especially in periods between seasons. The results of this multi-site comparison coincide with the synthetic dataset in terms of rolling-seasonal similarity and rolling PMF reporting moderate improvements. Altogether, the results of this study provide solid evidence of the robustness of both methods and of the overall efficiency of the recently proposed rolling PMF approach., Acknowledgements IDAEA-CSIC is a Centre of Excellence Severo Ochoa (Spanish Ministry of Science and Innovation, Project CEX2018-000794-S). The authors gratefully acknowledge the Romanian National Air Quality Monitoring Network (NAQMN, https://www.calitateaer.ro/public/home-page/?__locale=ro, last access: September 2022) for providing NOx data. Financial support This research has been supported by the Generalitat de Catalunya (grant no. AGAUR 2017 SGR41), the European Cooperation in Science and Technology (grant no. COST Action CA16109 COLOSSAL), the Ministerio de Ciencia, Innovación y Universidades (CAIAC, grant no. PID2019-108990RB-I00 and FEDER, grant no. EQC2018-004598-P.), the Horizon 2020, the Ministry of Education and Research, Romania (grant nos. PN-III-P1-1.1-TE-2019-0340 and 18PFE/30.12.2021, 18N/2019), the Agence Nationale de la Recherche (grant no. PIA, ANR-11_LABX-0005-01), the Conseil Régional Hauts-de-France (CLIMIBIO grant), the Ministère de l'Enseignement Supérieur et de la Recherche (CARA grant), the Environmental Protection Agency (AEROSOURCE, grant no. 2016-CCRP-MS-31), the Department of the Environment, Climate and Communications (AC3 network grant), and the Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung (SAMSAM, grant nos. IZCOZ9_177063 and PZPGP2_201992). We acknowledge support of the publication fee by the CSIC Open Access Publication Support Initiative through its Unit of Information Resources for Research (URICI).

The oxidative potential (OP) of ambient particulate matter (PM) is a metric commonly used to link the aerosol exposure to its adverse health effects. In this study, we report the first-ever real-ti...

In recent years, the Indian capital city of Delhi has been impacted by very high levels of air pollution, especially during winters. Comprehensive knowledge of the composition and sources of the organic aerosol (OA), which constitutes a substantial fraction of total particulate mass (PM) in Delhi, is central to formulating effective public health policies. Previous source apportionment studies in Delhi identified key sources of primary OA (POA) and showed that secondary OA (SOA) played a major role, but were unable to resolve specific SOA sources. We address the latter through the first field deployment of an extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) in Delhi, together with a high-resolution aerosol mass spectrometer (AMS). Measurements were conducted during the winter of 2018/2019, and positive matrix factorization (PMF) was used separately on AMS and EESI-TOF datasets to apportion the sources of OA. AMS PMF analysis yielded three primary and two secondary factors which were attributed to hydrocarbon-like OA (HOA), biomass burning OA (BBOA-1 and 2), more oxidized oxygenated OA (MO-OOA), and less oxidized oxygenated OA (LO-OOA). On average, 40 % of the total OA mass was apportioned to the secondary factors. The SOA contribution to total OA mass varied greatly between daytime (76.8 %, 10:00–16:00 local time (LT)) and nighttime (31.0 %, 21:00–04:00 local time). The higher chemical resolution of EESI-TOF data allowed identification of individual SOA sources. The EESI-TOF PMF analysis in total yielded six factors, two of which were primary factors (primary biomass burning and cooking-related OA). The remaining four factors were predominantly of secondary origin: aromatic SOA, biogenic SOA, aged biomass burning SOA, and mixed urban SOA. Due to the uncertainties in the EESI-TOF ion sensitivities, mass concentrations of EESI-TOF SOA dominated factors were related to the total AMS SOA (i.e., MO-OOA + LO-OOA) by multi-linear regression (MLR). Aromatic SOA was the major SOA component during the day-time, with 55.2 % contribution to total SOA mass (42.4 % contribution to total OA). Its contribution to total SOA, however, decreased to 25.4 % (7.9 % of total OA) during night-time. This factor was attributed to the oxidation of light aromatic compounds emitted mostly from traffic. Biogenic SOA accounted for 18.4 % of total SOA mass (14.2 % of total OA) during day-time and 36.1 % of total SOA mass (11.2 % of total OA) during night-time. Aged biomass burning and mixed urban SOA accounted for 15.2 % and 11.0 % of total SOA mass ( 11.7 % and 8.5 % of total OA mass) during day-time respectively and 15.4 % and 22.9 % of total SOA mass (4.8 % and 7.1 % of total OA mass) during night-time, respectively. A simple dilution/partitioning model was applied on all EESI-TOF factors to estimate the fraction of observed day-time concentrations resulting from local photochemical production (SOA) or emissions (POA). Aromatic SOA, aged biomass burning, and mixed urban SOA were all found to be dominated by local photochemical production, likely from the oxidation of locally emitted VOCs. In contrast, biogenic SOA was related to the oxidation of diffuse regional emissions of isoprene and monoterpenes. The findings of this study show that in Delhi, the night-time high concentrations are caused by POA emissions led by traffic and biomass burning, and the daytime OA is dominated by SOA, with aromatic SOA accounting for the largest fraction. Because aromatic SOA is possibly more toxic than biogenic SOA and primary OA, its dominance during the day-time suggests an increased OA toxicity and health-related consequences for the general public.

Real-time, in situ molecular composition measurements of the organic fraction of fine particulate matter (PM2.5) remain challenging, hindering a full understanding of the climate impacts and health effects of PM2.5. In particular, the thermal decomposition and ionization-induced fragmentation affecting current techniques has limited a detailed investigation of secondary organic aerosol (SOA), which typically dominates OA. Here we deploy a novel extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF-MS) during winter 2017 in downtown Zurich, Switzerland, which overcomes these limitations, together with an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) and supporting instrumentation. Positive matrix factorization (PMF) implemented within the Multilinear Engine (ME-2) program was applied to the EESI-TOF-MS data to quantify the primary and secondary contributions to OA. An 11-factor solution was selected as the best representation of the data, including five primary and six secondary factors. Primary factors showed influence from cooking, cigarette smoke, biomass burning (two factors) and a special local unknown event occurred only during two nights. Secondary factors were affected by biomass burning (three factors, distinguished by temperature and/or wind direction), organonitrates, monoterpene oxidation, and undetermined regional processing, in particular the contributions of wood combustion. While the AMS attributed slightly over half the OA mass to SOA but did not identify its source, the EESI-TOF-MS showed that most (>70 %) of the SOA was derived from biomass burning. Together with significant contributions from less aged biomass burning factors identified by both AMS and EESI-TOF-MS, this firmly establishes biomass burning as the single most important contributor to OA mass at this site during winter. High correlation was obtained between EESI-TOF-MS and AMS PMF factors where specific analogues existed, as well as between total signal and POA–SOA apportionment. This suggests the EESI-TOF-MS apportionment in the current study can be approximately taken at face value, despite ion-by-ion differences in relative sensitivity. The apportionment of specific ions measured by the EESI-TOF-MS (e.g., levoglucosan, nitrocatechol, and selected organic acids) and utilization of a cluster analysis-based approach to identify key marker ions for the EESI-TOF-MS factors are investigated. The interpretability of the EESI-TOF-MS results and improved source separation relative to the AMS within this pilot campaign validate the EESI-TOF-MS as a promising approach to source apportionment and atmospheric composition research.

Smog chamber experiments were conducted to characterize the light absorption of brown carbon (BrC) from primary and photochemically aged coal combustion emissions. Light absorption was measured by the UV-visible spectrophotometric analysis of water and methanol extracts of filter samples. The single-scattering albedo at 450 nm was 0.73 ± 0.10 for primary emissions and 0.75 ± 0.13 for aged emissions. The light absorption coefficient at 365 nm of methanol extracts was higher than that of water extracts by a factor of 10 for primary emissions and a factor of 7 for aged emissions. This suggests that the majority of BrC is water-insoluble even after aging. The mass absorption efficiency of this BrC (MAE365) for primary OA (POA) was dependent on combustion conditions, with an average of 0.84 ± 0.54 m2 g-1, which was significantly higher than that for aged OA (0.24 ± 0.18 m2 g-1). Secondary OA (SOA) dominated aged OA and the decreased MAE365 after aging indicates that SOA is less light absorbing than POA and/or that BrC is bleached (oxidized) with aging. The estimated MAE365 of SOA (0.14 ± 0.08 m2 g-1) was much lower than that of POA. A comparison of MAE365 of residential coal combustion with other anthropogenic sources suggests that residential coal combustion emissions are among the strongest absorbing BrC organics.

Krakow is routinely affected by very high air pollution levels, especially during the winter months. Although a lot of effort has been done on characterization of ambient aerosols, there is a lack of online and long-term measurements of non-refractory aerosols. Our measurements at AGH University provide online long-term chemical composition of ambient submicron particulate matter (PM1) between January 2018 and April 2019. Here we report the chemical characterization of non-refractory submicron aerosols and source apportionment of the organic fraction by positive matrix factorization (PMF). In contrast to other long-term source apportionment studies, we let a small PMF window roll over the dataset instead of performing PMF over the full dataset or on separate seasons. In this way, the seasonal variation of the source profiles can be captured. The uncertainties of the PMF solutions are addressed by the bootstrap resampling strategy and the random a-value approach for constrained factors.We observe clear seasonal patterns in concentration and composition of PM1, with high concentrations during the winter months and lower concentrations during the summer months. Organics are the dominant species throughout the campaign. Five organic aerosol (OA) factors are resolved, of which three are of primary nature (hydrocarbon-like OA (HOA), biomass burning OA (BBOA) and coal combustion OA (CCOA)) and two are of secondary nature (more oxidized oxygenated OA (MO-OOA) and less oxidized oxygenated OA (LO-OOA)). While HOA contributes on average 8.6 % ± 2.3 % throughout the campaign, the solid fuel combustion related BBOA and CCOA show a clear seasonal trend with average contributions of 10.4 % ± 2.7 % and 14.1 %, ± 2.1 % respectively. The highest contributions are observed during wintertime as a result of residential heating. Throughout the campaign, the OOA can be separated into MO-OOA and LO-OOA with average contribution of 38.4 % ± 8.4 % and 28.5 % ± 11.2 %, respectively.

Characteristics and sources of volatile organic compounds (VOCs) were investigated with highly time-resolved measurements by a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) at an urban site in Beijing in winter 2017. During the measurement period, high mixing ratios of VOCs (48.9 ppbv) and trace gases were observed, with alternating episodes of strong haze pollution and clean air. Ten VOC families showed clear dependence on the VOC concentration. Aromatics increased the most during haze, with significantly elevated benzene concentration at high VOC concentration, while CxHyO3 and CxHy increased the least. The positive matrix factorization (PMF) receptor model was applied to the VOC mass spectra, yielding four major VOC factors: traffic emissions (21.0%), solid fuel combustion (SFC, 24.4%), and two oxygenated VOC (OVOC) factors (32.3% and 22.3%). Traffic and solid fuel combustion were dominant during the periods of high total VOC concentration, while the OVOC1 fraction was reduced. Comparisons with organic aerosol (OA) sources showed increased oxygenated organic aerosol (OOA) concentration during high VOC concentration periods, indicating the importance of OVOCs to secondary organic aerosol formation. Furthermore, trajectory analysis showed that most of the clean days were associated with northerly winds with high ratios of OVOC1. In contrast, the haze periods were not only due to high primary emissions under stagnant conditions, but also influenced by air masses from a more regional scale.

Aerosol particles negatively affect human health while also having climatic relevance due to, for example, their ability to act as cloud condensation nuclei. Ultrafine particles (diameter Dp < 100 nm) typically comprise the largest fraction of the total number concentration, however, their chemical characterization is difficult because of their low mass. Using an extractive electrospray time-of-flight mass spectrometer (EESI-TOF), we characterize the molecular composition of freshly nucleated particles from naphthalene and β-caryophyllene oxidation products at the CLOUD chamber at CERN. We perform a detailed intercomparison of the organic aerosol chemical composition measured by the EESI-TOF and an iodide adduct chemical ionization mass spectrometer equipped with a filter inlet for gases and aerosols (FIGAERO-I-CIMS). We also use an aerosol growth model based on the condensation of organic vapors to show that the chemical composition measured by the EESI-TOF is consistent with the expected condensed oxidation products. This agreement could be further improved by constraining the EESI-TOF compound-specific sensitivity or considering condensed-phase processes. Our results show that the EESI-TOF can obtain the chemical composition of particles as small as 20 nm in diameter with mass loadings as low as hundreds of ng m−3 in real time. This was until now difficult to achieve, as other online instruments are often limited by size cutoffs, ionization/thermal fragmentation and/or semi-continuous sampling. Using real-time simultaneous gas- and particle-phase data, we discuss the condensation of naphthalene oxidation products on a molecular level., Using real-time simultaneous gas- and particle-phase data, the condensation of naphthalene and β-caryophyllene oxidation products on a molecular level is discussed.

Despite the fact that atmospheric particulate organic nitrogen (ON) can significantly affect human health, ecosystems and the earth's climate system, qualitative and quantitative chemical characterization of ON remains limited due to its chemical complexity. In this study, the Aerodyne soot particle - high-resolution time-of-flight aerosol mass spectrometer (SP-AMS) was deployed for ambient measurements in Nanjing, China. Positive matrix factorization (PMF) was applied to the ON data to quantify the sources of ON in submicron aerosols. The averaged ON concentration was 1.24 μg m-3, while the averaged total nitrogen (TN) in the aerosol was 20.26 μg m-3. From the PMF ON analysis, a 5-factor solution was selected as the most representative and interpretable solution for the investigated dataset, including oxygenated OA (OOAON), amine-related OAON (AMOAON), hydrocarbon-like OA (HOAON), industry OA (IOAON), and local primary OA (POAON) factors. The quantified ON ions were separated into families, including CxHN, CxHyNO, C3H

We have collected one year of aerosol chemical speciation monitor (ACSM) data in Magadino, a village located in the south of the Swiss Alpine region, which is one of the most polluted areas in Switzerland. We analysed the mass spectra of organic aerosol (OA) by positive matrix factorization (PMF) using Source Finder Professional (SoFi Pro) to retrieve the origins of OA. Therein, we deployed the rolling algorithm to account for the temporal changes of the source profiles, which is closer to the real world. As the first ever application of rolling PMF analysis for a rural cite, we resolved two primary OA factors (traffic-related hydrocarbon-like OA (HOA) and biomass burning OA (BBOA)), one local OA (LOA) factor, a less oxidized oxygenated OA (LO-OOA) factor, and a more oxidized oxygenated OA (MO-OOA) factor. HOA showed stable contributions to the total OA through the whole year ranging from 8.1–10.1 %, while the contribution of BBOA showed a clear seasonal variation with a range of 8.3–27.4 % (highest during winter, lowest during summer) and a yearly average of 17.1 %. The OOA was represented by two factors (LO-OOA and MO-OOA) throughout the year. OOA contributed 71.6 % of the OA mass, varying from 62.5 % (in winter) to 78 % (in spring and summer). The uncertainties (σ) for the modelled OA factors (i.e., rotational uncertainty and statistical variability of the sources) varied from ±4 % (LOA) to a maximum of ±40 % (LO-OOA). Considering the fact that BBOA and LO-OOA (showing influences of biomass burning in winter) had significant contributions to the total OA mass, we suggest a reduction and control of the residential heating as a mitigation strategy for better air quality and lower PM levels in this region. In Appendix A, we conducted a head-to-head comparison between the conventional seasonal PMF analysis and the rolling mechanism. It showed similar or slightly improved results in terms of mass concentrations, correlations with external tracers and factor profiles of the constrained POA factors. The rolling results show smaller scaled residuals and enhanced correlations between OOA factors and corresponding inorganic salts than those of the seasonal solutions, was most likely because the rolling PMF analysis can capture the temporal variations of the oxidation processes for OOA sources. Specifically, the time dependent factor profiles of MO-OOA and LO-OOA can well explain the temporal viabilities of two main ions for OOA factors, m/z 44 (CO2+) and m/z 43 (mostly C2H3O+). This rolling PMF analysis therefore provides a more realistic source apportionment (SA) solution, with time-dependent OA sources. The rolling results show also good agreement with offline Aerodyne aerosol mass spectrometer (AMS) SA results from filter samples, except for winter. This is likely because the online measurement is capable of capturing the fast oxidation processes of biomass burning sources. This study demonstrates the strengths of the rolling mechanism and provides a comprehensive criterion list for ACSM users to obtain reproducible SA results and is a role model for similar analyses of such world-wide available data.

Characteristics and sources of ambient particle elements in urban Beijing were studied by hourly observations in two size fractions (PM

We present highly time-resolved (30 to 120 min) measurements of size-fractionated (PM10 and PM2.5) elements in two cities in Asia (Delhi and Beijing) and Europe (Krakow and London). For most elements, the mean concentrations in PM10 and PM2.5 are higher in Asian cities (up to 24 and 28 times, respectively) than in Krakow, and often higher in Delhi than in Beijing. Among European cities, Krakow shows higher elemental concentrations (up to 20 and 27 times, respectively) than London. The enrichment factor of an element together with the size distribution allows for a rough classification of elements by major sources. We define five groups: (1) dust-related, (2) non-exhaust traffic emissions, (3) solid fuel combustion, (4) mixed traffic/industrial emissions, and (5) industrial/coal/waste burning emissions, with the last group exhibiting the most site-to-site variability. Hourly maximum concentrations of Pb and Zn reach up to 1 µg m−3 in Delhi, substantially higher than at the other sites. We demonstrate that the high time resolution and size-segregated elemental dataset can be a powerful tool to assess aerosol composition and sources in urban environments. Our results highlight the need to consider the size distributions of toxic elements, diurnal patterns of targeted emissions, and local vs. regional effects in formulating effective environmental policies to protect public health.

National Capital Region (NCR) encompassing New Delhi is one of the most polluted urban metropolitan areas in the world. Real-time chemical characterization of fine particulate matter (PM1 and PM2.5) was carried out using three aerosol mass spectrometers, two aethalometers, and one single particle soot photometer (SP2) at two sites in Delhi (urban) and one site located ~40 km downwind of Delhi, during January–March 2018. The campaign mean PM2.5 (NR-PM2.5 + BC) concentrations at the two urban sites were 153.8 ± 109.4 μg.m−3 and 127.8 ± 83.2 μg.m−3, respectively, whereas PM1 (NR-PM1 + BC) was 72.3 ± 44.0 μg.m−3 at the downwind site. PM2.5 particles were composed mostly of organics (43–44)% followed by chloride (14–17)%, ammonium (9–11)%, nitrate (9%), sulfate (8–10)%, and black carbon (11–16)%, whereas PM1 particles were composed of 47% organics, 13% sulfate as well as ammonium, 11% nitrate as well as chloride, and 5% black carbon. Organic aerosol (OA) source apportionment was done using positive matrix factorization (PMF), solved using an advanced multi-linear engine (ME-2) model. Highly mass-resolved OA mass spectra at one urban and downwind site were factorized into three primary organic aerosol (POA) factors including one traffic-related and two solid-fuel combustion (SFC), and three oxidized OA (OOA) factors. Whereas unit mass resolution OA at the other urban site was factorized into two POA factors related to traffic and SFC, and one OOA factor. OOA constituted a majority of the total OA mass (45–55)% with maximum contribution during afternoon hours ~(70–80)%. Significant differences in the absolute OOA concentration between the two urban sites indicated the influence of local emissions on the oxidized OA formation. Similar PM chemical composition, diurnal and temporal variations at the three sites suggest similar type of sources affecting the particulate pollution in Delhi and adjoining cities, but variability in mass concentration suggest more local influence than regional.

Particulate chloride is an important component of fine particulate matter in marine air masses. Recent field studies also report elevated concentrations of gas-phase reactive chlorine species and particulate chloride related to anthropogenic activities. This work focuses on particulate chloride detection and quantification issues observed for some quadrupole aerosol chemical speciation monitors (Q-ACSMs) which are designed for the long-term measurement of ambient aerosol composition. The ACSM reports particle concentrations based on the difference between measurements of ambient air (sample mode) and particle-free ambient air (filter mode). For our long-term campaign in Krakow, Poland, the Q-ACSM reports apparent negative total chloride concentration for most of the campaign when analyzed with the default fragmentation table. This is the result of the difference signal from m∕z 35 (35Cl+) being negative, which dominates over the positive difference signal from m∕z 36 (H35Cl+). Highly time-resolved experiments with NH4Cl, NaCl and KCl particles show that the signal response of m∕z 35 is non-ideal when the signal builds up and decreases slowly for all three salts, leading to a negative difference measurement. In contrast, the m∕z 36 signal exhibits a near step-change response for NH4Cl during the sampling and filter period, resulting in a positive difference signal. The response of m∕z 36 for NaCl and KCl is not as prompt as for NH4Cl but still fast enough to have a positive difference signal. Furthermore, it is shown that this behavior is mostly independent of vaporizer temperature. Based on these observations, this work presents an approach to correct the chloride concentration time series by adapting the standard fragmentation table coupled with a calibration of NH4Cl to obtain a relative ionization efficiency (RIE) based on the signal at m∕z 36 (H35Cl+). This correction can be applied to measurements in environments where chloride is dominated by NH4Cl. Caution should be exercised when other chloride salts dominate the ambient particulate chloride.

Delhi is one of the most polluted cities worldwide and a comprehensive understanding and deeper insight into the air pollution and its sources is of high importance. We report 5 months of highly time-resolved measurements of non-refractory PM

Megacities worldwide are suffering from elevated air pollution due, e.g., to continuously increasing urbanization, and a sizeable amount of the population in such areas is exposed to particulate matter (PM) concentrations exceeding the WHO limits. Huge efforts are therefore undertaken to characterize the air pollution situation and to reduce or mitigate the impact on the population and the environment. Modern instrumentation allows for a quantitative determination of aerosol concentration and composition with high time resolution (minutes to hours), and subsequent source apportionment.We collected PM10 and PM2.5 aerosols alternatingly with an online X-ray fluorescence (XRF) spectrometer in the cities of New Delhi (India) in 2019, Beijing (China) in 2017, and Krakow (Poland) in 2018, with time resolutions from 30 to 120 min, and in London (UK) in 2012 with 3-stage rotating drum impactors and subsequent offline SR-XRF analysis. Campaigns lasted for two to seven weeks in fall and winter. Elements from Al to Bi were analyzed in near-real time, except for London.Our results show that some of the cities experience episodic extreme events, whereas extremely high elemental concentrations are chronic in others. Toxic metals are shown to be strongly location-dependent, and may occur in extreme plumes. Meteorological conditions also play an important role and will be discussed. The regional influence of fine PM, in comparison to the more local origin of coarse PM will be evaluated. The differences among the four cities, with substantially higher concentrations in the Asian cities than the European ones will be discussed. Highly time-resolved size-segregated sampling allowed for a rough classification of elements into five groups and will be described in detail. We demonstrate that the use of size information on toxic elements, diurnal patterns of targeted emissions, and local vs. regional effects are advantageous for formulating effective environmental policies to protect public health.

Size resolved data of chemical species carries a lot of latent information about the sources and atmospheric processes which lead to their formation and growth. Source apportionment techniques on organic or inorganic aerosols provide a fair amount of information about the sources but this analysis only provides a partial picture owing to the complicated nature of the ambient aerosols which may contain both, organic as well as inorganic particulate matter. Traditionally, potential emission sources are distinguished by either the organic or inorganic tracers present in ambient aerosol, but recently several studies have performed PMF on both the species (Sun et al, 2012). However, it tells more about the final transformed products which could be formed from different pathways but not much about the transformation pathways. Insights about the source and the atmospheric processes involved can be derived from the analysis of size-resolved data of the ambient aerosol. PMF on Size-resolved information helps us to narrow down the possible pathways of the transformed products.However, there is very limited literature available to help us understand more about size-resolved bulk particulate matter. In this manuscript, a novel approach to perform Positive Matrix Factorization (PMF) on real-time size-resolved Unit Mass Resolution (UMR) data from Aerosol Mass Spectrometer (AMS) is presented. Both size- and time-resolved PMF is performed on non-refractory particle composition (organic & inorganic) on the UMR PTOF data of two sites in one of the most polluted cities in the world. The sampling through Long Time of flight mass spectrometer (LToF-AMS) was carried out at Indian Institute of Technology, Delhi which is located in Hauz Khaz area, at the heart of Delhi NCR, whereas parallel sampling through High-resolution Time of flight aerosol mass spectrometer (HR-ToF-AMS) was carried out at Manav Rachna University which is located in Faridabad within Delhi NCR at a downwind location. PMF was performed on the data by using Multi-linear Engine (ME-2) on PMF model by SoFi (Source Finder) tool. A seven-factor solution was chosen based on the factor profiles, time series, diurnals and correlation with the external factors obtained by supplementary instruments. The size-resolved spectra of the species at an individual site was studied and the difference between the sites was compared.

Atmospheric particulate matter has adverse effects on human health, and causes over 4 million deaths per year globally. New Delhi was ranked as world’s most polluted megacity with annual average PM2.5 concentration of ~140 ug.m-3. Thus, real time chemical characterization of fine particulate matter and identification of its sources is important for developing cost effective mitigation policies.Highly time resolved real-time chemical composition of PM2.5 was measured using Long-Time of Flight-Aerosol Mass Spectrometer (L-ToF-AMS) at Indian Institute of Technology Delhi and Time of Flight-Aerosol Chemical Speciation Monitor (ToF-ACSM) at Indian Institute of Tropical Meteorology, Delhi, and PM1 using High Resolution-Time of Flight-Aerosol Mass Spectrometer (HR-ToF-AMS) at Manav Rachna International University, Faridabad, Haryana located ~40 km downwind of Delhi during Jan-March, 2018. Black carbon concentration was measured using Aethalometer at all three sites. Unit mass resolution (UMR) and high resolution (HR) data analysis were performed on AMS and ACSM mass spectra to calculate organics, nitrate, sulfate and chloride concentrations. Positive Matrix Factorization (PMF) (Paatero and Tapper, 1994) of organic mass spectra was performed by applying multilinear engine (ME-2) algorithm using Sofi (Source finder) for identifying sources of OA.

Delhi is one of the world’s most polluted city and experiences very high levels of particulate matter throughout the year. It significantly affects radiative forcing, increases mortality, and causes other deleterious effects on human health. Generally, there is a lack of consensus on the dominant sources of organic aerosol driving these high aerosol concentrations. In particular, there is a need to elucidate the relative importance of primary vs. secondary sources and formation mechanisms of secondary aerosols. In order to answer questions pertaining to the sources, formation mechanisms, and atmospheric transformations of organic aerosol, we deployed for the first time in Delhi, the recently developed extractive electrospray ionization long-time-of-flight mass spectrometer (EESI-TOF) in Delhi. This was deployed along with a high-resolution long-time-of-flight aerosol mass spectrometer (AMS), and a Chemical Ionisation Mass Spectrometer fitted with a Filter Inlet for Gases and AEROsols (FIGAERO-CIMS). These measurements were further supported by measurements of black carbon and gaseous species such as CO, NOx etc.The EESI-TOF provides in real-time information on the chemical composition at the near-molecular level without thermal desorption and fragmentation (Lopez-Hilfiker et al., 2019). It was operated in Delhi from December to February 2019. Measurements by the AMS showed persisting high levels of particulate matter. We attributed the relative contributions of different sources to total non-refractory PM mass by performing source apportionment analysis by means of positive matrix factorization (PMF). A strong day-night variability was clearly seen in all the AMS species. High levels of secondary sources during daytime e.g., low-volatility oxygenated organic aerosol (LVOOA) and an increase of factors associated with primary sources i.e., hydrocarbon-like organic aerosol (HOA) and aerosol from solid fuel combustion (SFC) during morning and evening hours was observed. A similar trend as for the primary aerosol was seen for the semi-volatile oxygenated organic aerosol (SVOOA) mainly due to increased temperature during daytime which may leads to evaporation of semi-volatile species. A unique feature observed was a significant contribution of chloride to the non-refractory (NR) PM2.5 mass. On average, chloride contributed 18-20% to total NR-mass. Similar trends have also been seen in a recent study (Gani et al., 2018). The effect of these high chlorine concentrations during the night and early morning on atmospheric chemistry as well as on secondary organic aerosol formation will be presented.

Characteristics and sources of volatile organic compounds (VOCs) were investigated with highly time-resolved simultaneous measurements by two proton-transfer-reaction time-of-flight mass spectrometers (PTR-ToF-MS) at an urban and a suburban site in New Delhi, India from January to March 2018. During the measurement period, high mixing ratios of VOCs and trace gases were observed, with high nocturnal mixing ratios and strong day-night variations. The positive matrix factorization (PMF) receptor model was applied separately to the two sites, and six major factors of VOCs were identified at both sites, i.e., two factors related to traffic emissions, two to solid fuel combustion, and two secondary factors. At the urban IITD site, traffic-related emissions comprising mostly mono-aromatic compounds were the dominant sources, contributing 56.6 % of the total mixing ratio, compared to 36.0 % at the suburban MRIU site. Emissions from various solid fuel combustion processes, particularly in the night, were identified as a significant source of aromatics, phenols and furans at both sites. The secondary factors accounted for 15.9 % of the total VOC concentration at IITD and for 33.6 % at MRIU. They were dominated by oxygenated VOCs and exhibited substantially higher contributions during daytime.

The aerosol mass spectrometer (AMS), combined with statistical methods such as positive matrix factorization (PMF), has greatly advanced the quantification of primary organic aerosol (POA) sources and total secondary organic aerosol (SOA) mass. However, the use of thermal vaporization and electron ionization yields extensive thermal decomposition and ionization-induced fragmentation, which destroy chemical information needed for SOA source apportionment. The recently developed extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) provides mass spectra of the organic aerosol fraction with a linear response to mass and no thermal decomposition or ionization-induced fragmentation. However, the costs and operational requirements of online instruments make their use impractical for long-term or spatially dense monitoring applications. This challenge was overcome for AMS measurements by measuring re-nebulized water extracts from ambient filter samples. Here, we apply the same strategy for EESI-TOF measurements of 1 year of 24-hour filter samples collected approximately every 4th day throughout 2013 at the NABEL monitoring station at Zurich-Kaserne, an urban site. The nebulized water extracts were measured simultaneously with an AMS. The application of positive matrix factorization (PMF) to EESI-TOF spectra resolved seven factors, which describe water-soluble OA: less and more aged biomass burning aerosol (LABBEESI and MABBEESI, respectively), cigarette smoke-related organic aerosol (CS-OAEESI), primary biological organic aerosol (PBOAEESI), biogenic secondary organic aerosol (BSOAEESI), and a summer mixed oxygenated organic aerosol (SMOAEESI) factor. Seasonal trends and relative contributions of the EESI-TOF OA sources were compared with AMS source apportionment factors, measured water-soluble ions, cellulose, and meteorological data. Cluster analysis was utilized to identify key factor-specific ions based on PMF. Both LABB and MABB contribute strongly during winter. LABB is distinguished by very high signals from C6H10O5 (levoglucosan and isomers) and C8H12O6, whereas MABB is characterized by a large number of CxHyOz and CxHyOzN species two distinct populations: one with low H : C and high O : C, and the other with high H : C and low O : C. Two oxygenated summertime SOA sources were attributed to terpene-derived biogenic SOA, a major summertime aerosol source in Central Europe. Furthermore, a primary biological organic aerosol factor was identified, which was dominated by plant-derived fatty acids and correlated with free cellulose. The CS-OA factor contained a high contribution of nicotine and high abundance of organic nitrate ions with low m/z.

Delhi, the capital of India, suffers from heavy local emissions as well as regional transport of air pollutants, resulting in severe aerosol loadings. To determine the sources of these pollutants, we have quantified the mass concentrations of 26 elements in airborne particles, measured by an online X-ray fluorescence spectrometer with time resolution between 30 min and 1 h. Measurements of PM10 and PM2.5 (particulate matter

Real-time investigation of the intraparticle reactions in secondary organic aerosol., Highly oxygenated organic molecules (HOMs) are formed from the oxidation of biogenic and anthropogenic gases and affect Earth’s climate and air quality by their key role in particle formation and growth. While the formation of these molecules in the gas phase has been extensively studied, the complexity of organic aerosol (OA) and lack of suitable measurement techniques have hindered the investigation of their fate post-condensation, although further reactions have been proposed. We report here novel real-time measurements of these species in the particle phase, achieved using our recently developed extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF). Our results reveal that condensed-phase reactions rapidly alter OA composition and the contribution of HOMs to the particle mass. In consequence, the atmospheric fate of HOMs cannot be described solely in terms of volatility, but particle-phase reactions must be considered to describe HOM effects on the overall particle life cycle and global carbon budget.

Gasoline direct injection (GDI) vehicles have recently been identified as a significant source of carbonaceous aerosol, of both primary and secondary origin. Here we investigated primary emissions and secondary organic aerosol (SOA) from four GDI vehicles, two of which were also retrofitted with a prototype gasoline particulate filter (GPF). We studied two driving test cycles under cold- and hot-engine conditions. Emissions were characterized by proton transfer reaction time-of-flight mass spectrometry (gaseous non-methane organic compounds, NMOCs), aerosol mass spectrometry (sub-micron non-refractory particles) and light attenuation measurements (equivalent black carbon (eBC) determination using Aethalometers) together with supporting instrumentation. Atmospheric processing was simulated using the PSI mobile smog chamber (SC) and the potential aerosol mass oxidation flow reactor (OFR). Overall, primary and secondary particulate matter (PM) and NMOC emissions were dominated by the engine cold start, i.e., before thermal activation of the catalytic after-treatment system. Trends in the SOA oxygen to carbon ratio (O : C) for OFR and SC were related to different OH exposures, but divergences in the H : C remained unexplained. SOA yields agreed within experimental variability between the two systems, with a tendency for higher values in the OFR than in the SC (or, vice versa, lower values in the SC). A few aromatic compounds dominated the NMOC emissions, primarily benzene, toluene, xylene isomers/ethylbenzene and C3-benzene. A significant fraction of the SOA was explained by those compounds, based on comparison of effective SOA yield curves with those of toluene, o-xylene and 1,2,4-trimethylbenzene determined in our OFR, as well as others from literature. Remaining discrepancies, which were smaller in the SC and larger in the OFR, were up to a factor of 2 and may have resulted from diverse reasons including unaccounted precursors and matrix effects. GPF retrofitting significantly reduced primary PM through removal of refractory eBC and partially removed the minor POA fraction. At cold-started conditions it did not affect hydrocarbon emission factors, relative chemical composition of NMOCs or SOA formation, and likewise SOA yields and bulk composition remained unaffected. GPF-induced effects at hot-engine conditions deserve attention in further studies.

Organic aerosols (OAs), which consist of thousands of complex compounds emitted from various sources, constitute one of the major components of fine particulate matter. The traditional positive matrix factorization (PMF) method often apportions aerosol mass spectrometer (AMS) organic datasets into less meaningful or mixed factors, especially in complex urban cases. In this study, an improved source apportionment method using a bilinear model of the multilinear engine (ME-2) was applied to OAs collected during the heavily polluted season from two Chinese megacities located in the north and south with an Aerodyne high-resolution aerosol mass spectrometer (HR-ToF-AMS). We applied a rather novel procedure for utilization of prior information and selecting optimal solutions, which does not necessarily depend on other studies. Ultimately, six reasonable factors were clearly resolved and quantified for both sites by constraining one or more factors: hydrocarbon-like OA (HOA), cooking-related OA (COA), biomass burning OA (BBOA), coal combustion (CCOA), less-oxidized oxygenated OA (LO-OOA) and more-oxidized oxygenated OA (MO-OOA). In comparison, the traditional PMF method could not effectively resolve the appropriate factors, e.g., BBOA and CCOA, in the solutions. Moreover, coal combustion and traffic emissions were determined to be primarily responsible for the concentrations of PAHs and BC, respectively, through the regression analyses of the ME-2 results.

Ambient ammonia (NH3) measurements were performed with a mobile platform in three European cities: Zurich (Switzerland), Tartu (Estonia) and Tallinn (Estonia) deploying an NH3 analyzer based on cavity ring-down spectroscopy. A heated inlet line along with an auxiliary flow was used to minimize NH3 adsorption onto the inlet walls. In addition, a detailed characterization of the response and recovery times of the measurement system was used to deconvolve the true NH3 signal from the remaining adsorption-induced hysteresis. Parallel measurements with an aerosol mass spectrometer were used to correct the observed NH3 for the contribution of ammonium nitrate, which completely evaporated in the heated line at the chosen temperature, in contrast to ammonium sulfate. In this way a quantitative measurement of ambient gaseous NH3 was achieved with sufficient time resolution to enable measurement of NH3 point sources with a mobile sampling platform. The NH3 analyzer and the aerosol mass spectrometer were complemented by an aethalometer and various gas-phase analyzers to enable a complete characterization of the sources of air pollution, including the spatial distributions and the regional background concentrations and urban increments of all measured components. Although at all three locations similar increment levels of organic aerosols were attributed to biomass burning and traffic, traffic emissions clearly dominated the city enhancements of NH3, equivalent black carbon (eBC) and carbon dioxide (CO2). Urban increments of 3.4, 1.8 and 3.0 ppb of NH3 were measured in the traffic areas in Zurich, Tartu and Tallinn, respectively, representing an enhancement of 36.6, 38.3 and 93.8% over the average background concentrations. Measurements in areas strongly influenced by traffic emissions (including tunnel drives) were used to estimate emission factors (EF) for the traffic-related pollutants. The obtained median EFs range between 136.8-415.1 mg kg−1 fuel for NH3, 157.1–734.8 mg kg−1 fuel for eBC and 39.9–324.3 mg kg−1 fuel for HOA. Significant differences were found between the EFs of certain components in the three cities, which were partially linked to an older vehicle fleet in Estonia compared to Switzerland. Using the determined EFs we show that traffic can fully explain the NH3 enhancements in the three cities and also presents a non-negligible fraction of the background concentrations, which are mostly related to agricultural activities. Moreover, the estimated total contribution of traffic to NH3 at all three locations is in good agreement with the available emission inventories.

This study presents the first multi-site evolution analysis of fine Organic Aerosols (OA) and inorganics in the Delhi megacity (National Capital Region (NCR)) using high-resolution-particle time of flight (HR-PToF) size distribution obtained from Aerodyne HR-ToF-AMS. It provides a comprehensive view of the atmospheric dynamic processes responsible for the aerosol size and composition transformation. The measurements were performed at two different sampling sites (1) Indian Institute of Technology, Delhi (IITD), and (2) Manav Rachna International University, Faridabad (MRIU) during a late winter period (February to March 2018). Among organics, primary OA (POA) showed particle growth, whereas it was absent in secondary OA proxies. IITD was observed to have a distinct growth pattern as compared to MRIU because of high vehicular density and heterogeneity, and the presence of growth-promoting factors such as acidity and RH conditions. IITD aerosols were observed to be more acidic (ANR∼ 0.75) compared to MRIU (ANR∼1) and showed a distinct diurnal bin-wise increase during the photochemically active period (PAP). Such high acidic conditions are responsible for promoting acid-catalyzed SOA productions over the broader size bins, especially during the PAPs. Primary OA (POA) such as HOA and BBOA proxies show a diurnal growth from ∼440 to 970 nm and from ∼370 to 550 nm, at IITD and from ∼270 to 400 nm and ∼430–470 nm, at MRIU respectively. Further, OA families (amines and hydrocarbons), and inorganics such as chloride and nitrate also showed distinct concurrent diurnal growth patterns at IITD (from an MMDs of ∼380–520 nm to 650–960 nm). We have also observed a positive correlation between OA and inorganics growth and the mass fraction (MF = SOA/OA) of SOA at both sites of NCR. For 0.1 (MF) increase in SOA, the sizes of HOA, chloride, primary CH family and amines (CHN family), and secondary amines (CHON family) are increased by ∼93, 80, 64, 66, and 47 nm at IITD and ∼14, 35, 8, 11, and 16 nm at MRIU respectively. The concurrent growth of these species with the increase in the SOA concentration indicates the existence of a similar size evolution mechanism at both NCR sites, further promoting the formation of internally mixed aerosols during some phase of their evolution. This suggests that condensation is significantly governing the growth mechanism in NCR. Our study indicates the inclusion of such dynamic growth patterns arising from local prevailing conditions into the models for a better understanding of atmospheric aerosol evolution and estimation of fine particulate matter budget.

It is well established that light-absorbing organic aerosols (commonly known as brown carbon, BrC) impact climate. However, uncertainties remain as their contributions to absorption at different wavelengths are often ignored in climate models. Further, BrC exhibits differences in absorption at different wavelengths due to the variable composition including varying sources and meteorological conditions. However, diurnal variability in the spectral characteristics of water-soluble BrC (hereafter BrC) is not yet reported. This study presents unique measurement hitherto lacking in the literature. Online measurements of BrC were performed using an assembled system including a particle-into-liquid sampler, portable UV–Visible spectrophotometer with liquid waveguid capillary cell, and total carbon analyzer (PILS-LWCC-TOC). This system measured the absorption of ambient aerosol extracts at the wavelengths ranging from 300 to 600 nm with 2 min integration time and water-soluble organic carbon (WSOC) with 4 min integration time over a polluted megacity, New Delhi. Black carbon, carbon monoxide (CO), nitrogen oxides (NOx), and the chemical composition of non-refractory submicron aerosols were also measured in parallel. Diurnal variability in absorption coefficient (0.05 to 65 Mm−1), mass absorption efficiency (0.01 to 3.4 m−2 gC−1) at 365 nm, and absorption angstrom exponent (AAE) of BrC for different wavelength range (AAE300–400: 4.2–5.8; AAE400–600: 5.5–8.0; and AAE300–600: 5.3–7.3) is discussed. BrC chromophores absorbing at any wavelength showed minimum absorption during afternoon hours, suggesting the effects of boundary layer expansion and their photo-sensitive/volatile nature. On certain days, a considerable presence of BrC absorbing at 490 nm was observed during nighttime that disappears during the daytime. It appeared to be associated with secondary BrC. Observations also infer that BrC species emitted from the biomass and coal burning are more absorbing among all sources. A fraction of BrC is likely associated with trash burning, as inferred from the spectral characteristics of Factor-3 from the PMF analysis of BrC spectra. Such studies are essential in understanding the BrC characteristics and their further utilization in climate models.

To reduce the influence of biomass burning on air quality, consumers are encouraged to replace their old woodstove with new and cleaner appliances. While their primary emissions have been extensively investigated, the impact of atmospheric aging on these emissions, including secondary organic aerosol (SOA) formation, remains unknown. Here, using an atmospheric smog chamber, we aim at understanding the chemical nature and quantify the emission factors of the primary organic aerosols (POA) from three types of appliances for residential heating, and to assess the influence of aging thereon. Two, old and modern, logwood stoves and one pellet burner were operated under typical conditions. Emissions from an entire burning cycle (past the start-up operation) were injected, including the smoldering and flaming phases, resulting in highly variable emission factors. The stoves emitted a significant fraction of POA (up to 80%) and black carbon. After ageing, the total mass concentration of organic aerosol (OA) increased on average by a factor of 5. For the pellet stove, flaming conditions were maintained throughout the combustion. The aerosol was dominated by black carbon (over 90% of the primary emission) and amounted to the same quantity of primary aerosol emitted by the old logwood stove. However, after ageing, the OA mass was increased by a factor of 1.7 only, thus rendering OA emissions by the pellet stove almost negligible compared to the other two stoves tested. Therefore, the pellet stove was the most reliable and least polluting appliance out of the three stoves tested. The spectral signatures of the POA and aged emissions by a High Resolution – Time of Flight – Aerosol Mass Spectrometer (Electron Ionization (EI) at 70 eV) were also investigated. The m/z 44 (CO2+) and high molecular weight fragments (m/z 115 (C9H7+), 137 (C8H9O2+), 167 (C9H11O3+) and 181 (C9H9O4+, C14H13+)) correlate with the modified combustion efficiency (MCE) allowing us to discriminate further between emissions generated from smoldering vs flaming conditions.