Real-Time Identification of Aerosol-Phase Carboxylic Acid Production Using Extractive Electrospray Ionization Mass Spectrometry.

Comprehensive identification of aerosol sources and their constituent organic compounds requires aerosol-phase molecular-level characterization with a high time resolution. While real-time chemical characterization of aerosols is becoming increasingly common, information about functionalization and structure is typically obtained from offline methods. This study presents a method for determining the presence of carboxylic acid functional groups in real time using extractive electrospray ionization mass spectrometry based on measurements of [M - H + 2Na]+ adducts. The method is validated and characterized using standard compounds. A proof-of-concept application to α-pinene secondary organic aerosol (SOA) shows the ability to identify carboxylic acids even in complex mixtures. The real-time capability of the method allows for the observation of the production of carboxylic acids, likely formed in the particle phase on short time scales (<120 min). Our research explains previous findings of carboxylic acids being a significant component of SOA and a quick decrease in peroxide functionalization following SOA formation. We show that the formation of these acids is commensurate with the increase of dimers in the particle phase. Our results imply that SOA is in constant evolution through condensed-phase processes, which lower the volatility of the aerosol components and increase the available condensed mass for SOA growth and, therefore, aerosol mass loading in the atmosphere. Further work could aim to quantify the effect of particle-phase acid formation on the aerosol volatility distributions.

Local incomplete combustion emissions define the PM2.5 oxidative potential in Northern India.

The oxidative potential (OP) of particulate matter (PM) is a major driver of PM-associated health effects. In India, the emission sources defining PM-OP, and their local/regional nature, are yet to be established. Here, to address this gap we determine the geographical origin, sources of PM, and its OP at five Indo-Gangetic Plain sites inside and outside Delhi. Our findings reveal that although uniformly high PM concentrations are recorded across the entire region, local emission sources and formation processes dominate PM pollution. Specifically, ammonium chloride, and organic aerosols (OA) from traffic exhaust, residential heating, and oxidation of unsaturated vapors from fossil fuels are the dominant PM sources inside Delhi. Ammonium sulfate and nitrate, and secondary OA from biomass burning vapors, are produced outside Delhi. Nevertheless, PM-OP is overwhelmingly driven by OA from incomplete combustion of biomass and fossil fuels, including traffic. These findings suggest that addressing local inefficient combustion processes can effectively mitigate PM health exposure in northern India.

Major source categories of PM2.5 oxidative potential in wintertime Beijing and surroundings based on online dithiothreitol-based field measurements.

Fine particulate matter (PM2.5) causes millions of premature deaths each year worldwide. Oxidative potential (OP) has been proposed as a better metric for aerosol health effects than PM2.5 mass concentration alone. In this study, we report for the first time online measurements of PM2.5 OP in wintertime Beijing and surroundings based on a dithiothreitol (DTT) assay. These measurements were combined with co-located PM chemical composition measurements to identify the main source categories of aerosol OP. In addition, we highlight the influence of two distinct pollution events on aerosol OP (spring festival celebrations including fireworks and a severe regional dust storm). Source apportionment coupled with multilinear regression revealed that primary PM and oxygenated organic aerosol (OOA) were both important sources of OP, accounting for 41 ± 12 % and 39 ± 10 % of the OPvDTT (OP normalized by the sampled air volume), respectively. The small remainder was attributed to fireworks and dust, mainly resulting from the two distinct pollution events. During the 3.5-day spring festival period, OPvDTT spiked to 4.9 nmol min-1 m-3 with slightly more contribution from OOA (42 ± 11 %) and less from primary PM (31 ± 15 %). During the dust storm, hourly-averaged PM2.5 peaked at a very high value of 548 µg m-3 due to the dominant presence of dust-laden particles (88 % of total PM2.5). In contrast, only mildly elevated OPvDTT values (up to 1.5 nmol min-1 m-3) were observed during this dust event. This observation indicates that variations in OPvDTT cannot be fully explained using PM2.5 alone; one must also consider the chemical composition of PM2.5 when studying aerosol health effects. Our study highlights the need for continued pollution control strategies to reduce primary PM emissions, and more in-depth investigations into the source origins of OOA, to minimize the health risks associated with PM exposure in Beijing.

Source attribution of carbonaceous fraction of particulate matter in the urban atmosphere based on chemical and carbon isotope composition.

Air quality is of large concern in the city of Krakow, southern Poland. A comprehensive study was launched by us in which two PM fractions (PM1 and PM10) were sampled during 1-year campaign, lasting from April 21, 2018 to March 19, 2019. A suite of modern analytical methods was used to characterize the chemical composition of the collected samples. The contents of 14 sugars, sugar alcohols and anhydrosugars, 16 polycyclic aromatic hydrocarbons, selected metals and non-metals and ions were analyzed, in addition to organic and elemental carbon content. The carbon isotope composition in both analysed PM fractions, combined with an isotope-mass balance method, allowed to distinguish three main components of carbonaceous emissions in the city: (1) emissions related to combustion of hard coal, (2) emissions related to road transport, and (3) biogenic emissions. The heating season emissions from coal combustion had the biggest contribution to the reservoir of carbonaceous aerosols in the PM10 fraction (44%) and, together with the biogenic emission, they were the biggest contributors to the PM1 fraction (41% and 44%, respectively). In the non-heating season, the dominant source of carbon in PM10 and PM1 fraction were the biogenic emissions (48 and 54%, respectively).

Uncovering the dominant contribution of intermediate volatility compounds in secondary organic aerosol formation from biomass-burning emissions.

Organic vapors from biomass burning are a major source of secondary organic aerosols (SOAs). Previous smog chamber studies found that the SOA contributors in biomass-burning emissions are mainly volatile organic compounds (VOCs). While intermediate volatility organic compounds (IVOCs) are efficient SOA precursors and contribute a considerable fraction of biomass-burning emissions, their contribution to SOA formation has not been directly observed. Here, by deploying a newly-developed oxidation flow reactor to study SOA formation from wood burning, we find that IVOCs can contribute ∼70% of the formed SOA, i.e. >2 times more than VOCs. This previously missing SOA fraction is interpreted to be due to the high wall losses of semi-volatile oxidation products of IVOCs in smog chambers. The finding in this study reveals that SOA production from biomass burning is much higher than previously thought, and highlights the urgent need for more research on the IVOCs from biomass burning and potentially other emission sources.

Sensitivity Constraints of Extractive Electrospray for a Model System and Secondary Organic Aerosol.

The quantification of an aerosol chemical composition is complicated by the uncertainty in the sensitivity of each species detected. Soft-ionization response factors can vary widely from molecule to molecule. Here, we have employed a method to separate molecules by their volatility through systematic evaporation with a thermal denuder (TD). The fraction remaining after evaporation is compared between an extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) and a scanning mobility particle sizer (SMPS), which provides a comparison between a quantified mass loss by the SMPS and the signal loss in the EESI-TOF. The sensitivity of the EESI-TOF is determined for both a simplified complex mixture (PEG-300) and also for a complex mixture of α-pinene secondary organic aerosol (SOA). For PEG-300, separation is possible on a molecule-by-molecule level with the TD and provides insights into the molecule-dependent sensitivity of the EESI-TOF, showing a higher sensitivity toward the most volatile molecule. For α-pinene SOA, sensitivity determination for specific classes is possible because of the number of molecular formula observed by the EESI-TOF. These classes are separated by their volatility and are broken down into monomers (O3-5,6-7,8+), dimers (O4-7,8+), and higher order oligomers (e.g., trimers and tetramers). Here, we show that the EESI-TOF initially measures 60.1% monomers, 32.7% dimers, and 7.2% trimers and tetramers in α-pinene SOA, but after sensitivity correction, the distribution of SOA is 37.4% monomers, 56.1% dimers, and 6.4% trimers and tetramers. These results provide a path forward for the quantification of aerosol components with the EESI-TOF in other applications and potentially for atmospheric measurements.

Time-Resolved Molecular Characterization of Secondary Organic Aerosol Formed from OH and NO3 Radical Initiated Oxidation of a Mixture of Aromatic Precursors.

Aromatic hydrocarbons (ArHCs) and oxygenated aromatic hydrocarbons (ArHC-OHs) are emitted from a variety of anthropogenic activities and are important precursors of secondary organic aerosol (SOA) in urban areas. Here, we analyzed and compared the composition of SOA formed from the oxidation of a mixture of aromatic VOCs by OH and NO3 radicals. The VOC mixture was composed of toluene (C7H8), p-xylene + ethylbenzene (C8H10), 1,3,5-trimethylbenzene (C9H12), phenol (C6H6O), cresol (C7H8O), 2,6-dimethylphenol (C8H10O), and 2,4,6-trimethylphenol (C9H12O) in a proportion where the aromatic VOCs were chosen to approximate day-time traffic-related emissions in Delhi, and the aromatic alcohols make up 20% of the mixture. These VOCs are prominent in other cities as well, including those influenced by biomass combustion. In the NO3 experiments, large contributions from CxHyOzN dimers (C15-C18) were observed, corresponding to fast SOA formation within 15-20 min after the start of chemistry. Additionally, the dimers were a mixture of different combinations of the initial VOCs, highlighting the importance of exploring SOAs from mixed VOC systems. In contrast, the experiments with OH radicals yielded gradual SOA mass formation, with CxHyOz monomers (C6-C9) being the dominant constituents. The evolution of SOA composition with time was tracked and a fast degradation of dimers was observed in the NO3 experiments, with concurrent formation of monomer species. The rates of dimer decomposition in NO3 SOA were ∼2-3 times higher compared to those previously determined for α-pinene + O3 SOA, highlighting the dependence of particle-phase reactions on VOC precursors and oxidants. In contrast, the SOA produced in the OH experiments did not dramatically change over the same time frame. No measurable effects of humidity were observed on the composition and evolution of SOA.

Effect of OH scavengers on the chemical composition of α-pinene secondary organic aerosol.

OH scavengers are extensively used in studies of secondary organic aerosol (SOA) because they create an idealized environment where only a single oxidation pathway is occurring. Here, we present a detailed molecular characterization of SOA produced from α-pinene + O3 with a variety of OH scavengers using the extractive electrospray time-of-flight mass spectrometer in our atmospheric simulation chamber, which is complemented by characterizing the gas phase composition in flow reactor experiments. Under our experimental conditions, radical chemistry largely controls the composition of SOA. Besides playing their desired role in suppressing the reaction of α-pinene with OH, OH scavengers alter the reaction pathways of radicals produced from α-pinene + O3. This involves changing the HO2 : RO2 ratio, the identity of the RO2 radicals present, and the RO2 major sinks. As a result, the use of the OH scavengers has significant effects on the composition of SOA, including inclusions of scavenger molecules in SOA, the promotion of fragmentation reactions, and depletion of dimers formed via α-pinene RO2-RO2 reactions. To date fragmentation reactions and inclusion of OH scavenger products into secondary organic aerosol have not been reported in atmospheric simulation chamber studies. Therefore, care should be considered if and when to use an OH scavenger during experiments.

Real-Time Source Apportionment of Organic Aerosols in Three European Cities.

97% of the urban population in the EU in 2019 were exposed to an annual fine particulate matter level higher than the World Health Organization (WHO) guidelines (5 µg/m3). Organic aerosol (OA) is one of the major air pollutants, and the knowledge of its sources is crucial for designing cost-effective mitigation strategies. Positive matrix factorization (PMF) on aerosol mass spectrometer (AMS) or aerosol chemical speciation monitor (ACSM) data is the most common method for source apportionment (SA) analysis on ambient OA. However, conventional PMF requires extensive human labor, preventing the implementation of SA for routine monitoring applications. This study proposes the source finder real-time (SoFi RT, Datalystica Ltd.) approach for efficient retrieval of OA sources. The results generated by SoFi RT agree remarkably well with the conventional rolling PMF results regarding factor profiles, time series, diurnal patterns, and yearly relative contributions of OA factor on three year-long ACSM data sets collected in Athens, Paris, and Zurich. Although the initialization of SoFi RT requires a priori knowledge of OA sources (i.e., the approximate number of factors and relevant factor profiles) for the sampling site, this technique minimizes user interactions. Eventually, it could provide up-to-date trustable information on timescales useful to policymakers and air quality modelers.

Source identification and characterization of organic nitrogen in atmospheric aerosols at a suburban site in China.

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<6N, CxH2x+2N, CxH2xN and Others, consistent with their contribution to each factor. The CxHyNO family mainly contributed to the OOAON factor and suggested the presence of amides or amino acids. The CxH2x+2N family likely mostly originated from amines only contributing to the AMOAON and HOAON factors. The IOAON and POAON factors were resolved due to significant tracers in the mass spectra. Further, compared with regular organic PMF analysis, PMF ON analysis gave more insights due to improved source separation and interpretability of the OA components, which could be a role model for further atmospheric ON research.

Molecular characterization of ultrafine particles using extractive electrospray time-of-flight mass spectrometry.

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 D p < 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 ß-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.

Critical Role of Simultaneous Reduction of Atmospheric Odd Oxygen for Winter Haze Mitigation.

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.

Diurnal variability in the spectral characteristics and sources of water-soluble brown carbon aerosols over Delhi.

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.

Photodegradation of α-Pinene Secondary Organic Aerosol Dominated by Moderately Oxidized Molecules.

Atmospheric secondary organic aerosol (SOA) undergoes chemical and physical changes when exposed to UV radiation, affecting the atmospheric lifetime of the involved molecules. However, these photolytic processes remain poorly constrained. Here, we present a study aimed at characterizing, at a molecular level and in real time, the chemical composition of α-pinene SOA exposed to UV-A light at 50% relative humidity in an atmospheric simulation chamber. Significant SOA mass loss is observed at high loadings (∼100 µg m-3), whereas the effect is less prevalent at lower loadings (∼20 µg m-3). For the vast majority of molecules measured by the extractive electrospray time-of-flight mass spectrometer, there is a fraction that is photoactive and decays when exposed to UV-A radiation and a fraction that appears photorecalcitrant. The molecules that are most photoactive contain between 4 and 6 oxygen atoms, while the more highly oxygenated compounds and dimers do not exhibit significant decay. Overall, photolysis results in a reduction of the volatility of SOA, which cannot be explained by simple evaporative losses but requires either a change in volatility related to changes in functional groups or a change in physical parameters (i.e., viscosity).

Brown Carbon in Primary and Aged Coal Combustion Emission.

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.

Real-time characterization and source apportionment of fine particulate matter in the Delhi megacity area during late winter.

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.

Characteristics and sources of hourly elements in PM10 and PM2.5 during wintertime in Beijing.

Characteristics and sources of ambient particle elements in urban Beijing were studied by hourly observations in two size fractions (PM10 and PM2.5) during November and December 2017 using an online multi-element analyzer. The reconstructed oxide concentrations of 24 elements (from Al to Pb) comprise an appreciable fraction of PM10 and PM2.5, accounting for 37% and 17%, respectively on average. We demonstrate the benefit of using high-time-resolution chemical speciation data in achieving robust source apportionment of the total elemental PM10 (PM10el) and elemental PM2.5 (PM2.5el) mass using positive matrix factorization (PMF). Biomass burning, coal combustion, secondary sulfate, industry, non-exhaust traffic and dust were identified in both size fractions (with varying relative concentrations), which accounted on average for 4%, 12%, 5%, 2%, 14%, and 63%, respectively to the total PM10el, and 14%, 35%, 21%, 6%, 12% and 12%, respectively to the total PM2.5el. Biomass burning and coal combustion exhibited higher concentrations during haze episodes of the heating season. In contrast, secondary sulfate and industry contributed more to haze episodes during the non-heating season. The fractional contribution of dust was mostly high during clean days, while the fractional non-exhaust traffic emission contribution was similar throughout the measurement period. The non-exhaust traffic emissions contributed locally, while the remaining sources were dominated by neighboring areas. Furthermore, trajectory analysis showed that the origin of the industrial sources roughly agreed with the locations of the main point sources. Overall, this work provides detailed information on the characteristics of the elements during different haze events during heating and non-heating seasons.

Real-time measurement and source apportionment of elements in Delhi's atmosphere.

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 <10 µm and < 2.5 µm) were conducted during two consecutive winters (2018 and 2019) in Delhi. On average, 26 elements from Al to Pb made up ~25% and ~19% of the total PM10 mass (271 µg m-3 and 300 µg m-3) in 2018 and 2019, respectively. Nine different aerosol sources were identified during both winters using positive matrix factorization (PMF), including dust, non-exhaust, an S-rich factor, two solid fuel combustion (SFC) factors and four industrial/combustion factors related to plume events (Cr-Ni-Mn, Cu-Cd-Pb, Pb-Sn-Se and Cl-Br-Se). All factors were resolved in both size ranges (but varying relative concentrations), comprising the following contributions to the elemental PM10 mass (in % average for 2018 and 2019): Cl-Br-Se (41.5%, 36.9%), dust (27.6%, 28.7%), non-exhaust (16.2%, 13.7%), S-rich (6.9%, 9.2%), SFC1 + SFC2 (4%, 7%), Pb-Sn-Se (2.3%, 1.66%), Cu-Cd-Pb (0.67%, 2.2%) and Cr-Ni-Mn (0.57%, 0.47%). Most of these sources had the highest relative contributions during late night (22:00 local time (LT)) and early morning hours (between 03:00 to 08:00 LT), which is consistent with enhanced emissions into a shallow boundary layer. Modelling of airmass source geography revealed that the Pb-Sn-Se, Cl-Br-Se and SFC2 factors prevailed for northwest winds (Pakistan, Punjab, Haryana and Delhi), while the Cu-Cd-Pb and S-rich factors originated from east (Nepal and Uttar Pradesh) and the Cr-Ni-Mn factor from northeast (Uttar Pradesh). In contrast, SFC1, dust and non-exhaust were not associated with any specific wind direction.

Chemical characterization of PM2.5 and source apportionment of organic aerosol in New Delhi, India.

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 PM2.5 and black carbon (BC). Additionally, source apportionment based on positive matrix factorization (PMF) of the organic aerosol (OA) fraction is presented. The highest pollution levels are observed during winter in December/January. During that time, also uniquely high chloride concentrations are measured, which are sometimes even the most dominant NR-species in the morning hours. With increasing temperature, the total PM2.5 concentration decreases steadily, whereas the chloride concentrations decrease sharply. The concentrations measured in May are roughly 6 times lower than in December/January. PMF analysis resolves two primary factors, namely hydrocarbon-like (traffic-related) OA (HOA) and solid fuel combustion OA (SFC-OA), and one or two secondary factors depending on the season. The uncertainties of the PMF analysis are assessed by combining the random a-value approach and the bootstrap resampling technique of the PMF input. The uncertainties for the resolved factors range from ±18% to ±19% for HOA, ±7% to ±19% for SFC-OA and ±6 % to ±11% for the OOAs. The average correlation of HOA with equivalent black carbon from traffic (eBCtr) is R2 = 0.40, while SFC-OA has a correlation of R2 = 0.78 with equivalent black carbon from solid fuel combustion (eBCsf). Anthracene (m/z 178) and pyrene (m/z 202) (PAHs) are mostly explained by SFC-OA and follow its diurnal trend (R2 = 0.98 and R2 = 0.97). The secondary oxygenated aerosols are dominant during daytime. The average contribution during the afternoon hours (1 pm-5 pm) is 59% to the total OA mass, with contributions up to 96% in May. In contrast, the primary sources are more important during nighttime: the mean nightly contribution (22 pm-3 am) to the total OA mass is 48%, with contributions up to 88% during some episodes in April.