Water-soluble Organic Aerosol Research Articles

Anthropogenic sources and liquid water drive secondary organic aerosol formation over the eastern Himalaya

Atmospheric aerosols have a serious impact on altering the radiation balance of the vulnerable Himalayan atmosphere. Organic aerosol (OA), one of the least resolved aerosol fractions in the Himalayas, constrain our competence to assess their climate impacts on the region. Here we investigate water-soluble OA molecules in PM10 samples collected from March to May 2019 at Lachung (27.4°N and 88.4°E), a high-altitude location (2700 m a.s.l.) in the eastern Himalaya, to elucidate their origin and formation process. The dominance of oxalic acid (C2) reveals that water-soluble OA in the eastern Himalaya are atmospherically processed. Backward air mass trajectories and mass concentration ratios of organic tracers as well as relationships with inorganic species (K+, SO42−, NH4+) suggest an anthropogenic origin of water-soluble OA with significant atmospheric processing during long-range transport to the eastern Himalayan region. We used the thermodynamic prediction of aerosol liquid water (ALW) to examine the formation mechanism of secondary OA (SOA) such as oxalic acid. Correlations of ALW with SO42− and water-soluble organic matter show that ALW is sensitive to both anthropogenic sulfate and water-soluble organic compounds in Himalayan aerosols. A strong positive relationship of C2 acid with predicted ALW provides evidence of extensive SOA formation from precursors via aqueous phase photochemical processes. This inference is supported by positive correlations of C2 acid relative abundance with diagnostic mass concentration ratios of C2 acid to precursor molecules. Our findings underscore the importance of anthropogenic sources and ALW in SOA formation through aqueous phase processes in the eastern Himalaya.

Compositions and sources of fluorescent water-soluble and water-insoluble organic aerosols

Brown carbon (BrC), the light-absorbing component of organic aerosols, plays a significant role in climate change and atmospheric photochemistry. However, the water-insoluble fractions of BrC have not been extensively studied, limiting the assessment of the overall climate effects of BrC. In this study, water-soluble and -insoluble organic carbon (i.e., WSOC and WIOC) in wintertime aerosols in Hefei were subsequently fractionated, and their fluorescence properties were comparatively investigated with the excitation–emission matrix method. WIOC contributing 57.1 % was the major component of organic carbon. WSOC with the largest contribution from humic-like regions exhibited a redshift compared to WIOC. Three humic-like substances (HULIS) with different oxidation degrees and one protein-like substances (PRLIS) were identified as the major fluorescent components by the parallel factor analysis. WSOC had more highly oxygenated HULIS, whereas low-oxygenated HULIS dominated WIOC. Nighttime WIOC contained more less-oxygenated species. The positive matrix factorization analysis suggested that biomass burning (43 %) was the largest source of both fluorescent WSOC and WIOC. Coal combustion contributed much more to fluorescent WIOC (40 %), whereas secondary formation contributed more to fluorescent WSOC (12 %). During aerosol pollution episodes, the increase in fluorescence efficiency was much greater for WIOC (25 %) than for WSOC (12 %), and WSOC and WIOC experienced a redshift and blueshift in emission wavelength, respectively. WSOC had more highly oxygenated HULIS, while WIOC had more less-oxygenated HULIS in aerosol episodes than the non-episodic periods. In addition, aerosol pollution was accompanied by the increased contributions of biomass burning and coal combustion to both fluorescent WSOC and WIOC, while the decreased relative contribution of secondary formation to fluorescent WSOC. Our findings highlighted the different fluorescence properties, compositions and sources of fluorescent WSOC and WIOC, providing a comprehensive view of BrC aerosols.

Seasonal characterization of chemical and optical properties of water-soluble organic aerosol in Beijing

Water-soluble organic aerosol (WSOA) plays a crucial role in altering radiative forcing and impacting human health. However, our understanding of the seasonal variations of WSOA in Chinese megacities after the three-year clean air action plan is limited. In this study, we analyzed PM2.5 filter samples collected over one year (2020−2021) in Beijing to characterize the seasonal changes in the chemical and optical properties of WSOA using an offline aerosol mass spectrometer along with spectroscopy techniques. The mean mass concentration of WSOA during the observation period was 8.84 ± 7.12 μg m−3, constituting approximately 64–67 % of OA. Our results indicate the contribution of secondary OA (SOA) increased by 13–28 % due to a substantial reduction in primary emissions after the clean air action plan. The composition of WSOA exhibited pronounced seasonal variations, with a predominant contribution from less oxidized SOA in summer (61 %) and primary OA originating from coal combustion and biomass burning during the heating season (34 %). The mass absorption efficiency of WSOA at 365 nm in winter was nearly twice that in summer, suggesting that WSOA from primary emissions possesses a stronger light-absorbing capability than SOA. On average, water-soluble brown carbon accounted for 33–48 % of total brown carbon absorption. Fluorescence analysis revealed humic-like substances as the most significant fluorescence component of WSOA, constituting 82 %. Furthermore, both absorption and fluorescence chromophores were associated with nitrogen-containing compounds, highlighting the role of nitrogen-containing species in influencing the optical properties of WSOA. The results are important for chemical transport models to accurately simulate the WSOA and its climate effects.

Reactive oxygen species generation from winter water-soluble organic aerosols in Delhi's PM2.5

In this study, we evaluate the relative redox activity of various water-soluble organic aerosol (WSOA) sources in Delhi's winter PM2.5, focusing on their capacity to generate reactive oxygen species (ROS). Using offline-aerosol mass spectrometry (AMS) and positive matrix factorization (PMF), we identified two oxidized factors—more oxidized oxygenated organic aerosol (MO-OOA) and less oxidized oxygenated organic aerosol (LO-OOA)—and three primary factors, namely nitrogen-enriched hydrocarbon-like organic aerosol (NHOA), biomass-burning organic aerosol (BBOA), and solid-fuel combustion organic aerosol (SFC-OA). The ROS-generating capability of PM2.5 was assessed using a real-time oxidative potential (OP) measurement system based on the dithiothreitol (DTT) assay. We employed multivariate linear regression technique (MLR) to explore the association between the DTT activity of water-soluble PM2.5 and these identified factors. We found BBOA, SFCOA, and MO-OOA significantly contributed to volume-normalized OP, with intrinsic water-soluble activities of 39 ± 11, 106 ± 31 and 160 ± 43 pmol/min/μg, respectively. MO-OOA, primarily from non-fossil precursors, serves as a proxy for aged biomass burning, which intensifies during winter and significantly influences the DTT activity. Additionally, OP is significantly influenced by WSOA derived from local incomplete solid fuel combustion sources, including coal and wood burning for household cooking and heating, burning of leaves, biodegradable waste, and garbage along the roadside. Interestingly, water-soluble metals (Mn, Cu, and Fe) showed no discernible contribution to the OP. These findings highlight the need for targeted mitigation strategies addressing local combustion processes and unregulated biomass burning to effectively reduce PM health exposure in Delhi.

Contribution of fossil and biomass-derived secondary organic carbon to winter water-soluble organic aerosols in Delhi, India

Delhi, among the world's most polluted megacities, is a hotspot of particulate matter emissions, with high contribution from organic aerosol (OA), affecting health and climate in the entire northern India. While the primary organic aerosol (POA) sources can be effectively identified, an incomplete source apportionment of secondary organic aerosol (SOA) causes significant ambiguity in the management of air quality and the assessment of climate change. Present study uses positive matrix factorization analysis on the water-soluble organic aerosol (WSOA) data from the offline-aerosol mass spectrometry (AMS). It revealed POA as the dominant source of WSOA, with biomass-burning OA (31–34 %) and solid fuel combustion OA (∼21 %) being two major contributors. Here we use water-solubility fingerprints to track the SOA precursors, such as oxalates or organic nitrates, instead of identifying them based on their O:C ratio. Non-fossil precursors dominate in more oxidized oxygenated organic carbon (MO-OOC) (∼90 %), a proxy for aged secondary organic carbon (SOC), by coupling offline-AMS with 14C measurements. On the contrary, the oxidation of fossil fuel emissions produces a large quantity of fresh fossil SOC, which accounts for ∼75 % of less oxidized oxygenated organic carbon (LO-OOC). Our study reveals that apart from major POA contributions, large fractions of fossil (10–14 %) and biomass-derived SOA (23–30 %) contribute significantly to the total WSOA load, having impact on climate and air quality of the Delhi megacity. Our study reveals that large-scale unregulated biomass burning was not only found to dominate in POA but was also observed to be a significant contributor to SOA with implications on human health, highlighting the need for effective control strategies.

Characterizing water-soluble brown carbon in fine particles in four typical cities in northwestern China during wintertime: integrating optical properties with chemical processes

Abstract. Brown carbon (BrC) aerosol could impact atmospheric radiative forcing and play a crucial role in atmospheric photochemistry. In this study, fine particulate matter (PM2.5) filter samples were collected synchronously in four major cities in northwestern China during the winter season (December 2019–January 2020): Lanzhou (LZ), Xining (XN), Yinchuan (YC), and Ürümqi (UR), which are represented as energy-producing and heavy manufacturing cities in China. The primary aim of the study is to explore the optical properties, sources, and chemical processes of water-soluble BrC (WS-BrC). The average mass absorption efficiency at 365 nm (MAE365) of WS-BrC at these four cities was 1.24 ± 0.19 m2 g−1 (XN), 1.19 ± 0.12 m2 g−1 (LZ), 1.07 ± 0.23 m2 g−1 (YC), and 0.78 ± 0.16 m2 g−1 (UR). The properties of WS-BrC were further investigated by an acid–base titration experiment. The results showed that the MAE365 values in all cities increased with higher pH values (2–11), while the fluorescence intensities of water extracts fluctuated with pH values, being stronger under both highly acidic and basic conditions. The sensitivity to pH variation was most pronounced in the WS-BrC samples from YC and LZ, indicating the important contribution of acid or base functional group compounds in these locations. Additionally, the study revealed significant photo-enhancement (LZ) or photo-bleaching (YC and UR) phenomena of WS-BrC in different cities. These results suggest that the sources and/or chemical processes of WS-BrC varied among the cities. The sources and chemical processes of WS-BrC were further explored by a combination of parallel factor analysis (PARAFAC) on excitation–emission matrix (EEM) spectra of WS-BrC and positive matrix factorization analysis (PMF) on high-resolution mass spectra of water-soluble organic aerosol (WSOA). Six PARAFAC components were identified, including three humic-like substances (HULIS; two less oxygenated (LO) HULIS and one highly oxygenated (HO) HULIS), two protein-like or phenol-like substances (PLS), and one undefined substance. Four PMF factors were identified, including a water-soluble primary OA (WS-POA), a less oxidized oxygenated OA associated with coal combustion-induced WSOA (LO-OOA), and two highly oxidized oxygenated OAs resulting from photochemical oxidation and aqueous-phase oxidation transformations (HO-OOA1 and HO-OOA2). WS-POA was determined to be the most significant source of light absorption, accounting for 30 %–60 % based on multiple linear regression models, and it showed a significant correlation with PLS and LO-HULIS components. The loss of light absorption of WS-POA was found to occur through its conversion to LO-OOA and HO-OOAs through photochemical or aqueous reactions, with HO-OOAs being significantly correlated with the HO-HULIS component. These processes can be clearly illustrated by integrating optical properties and chemical composition using a Van Krevelen diagram and an EEM plot.

Characterizing the sources of ambient PM10 organic aerosol in urban and rural Catalonia, Spain

Organic aerosols (OA) have recently been shown to be the dominant contributor to the oxidative potential of airborne particulate matter in northeastern Spain. We collected PM10 filter samples every fourth day from January 2017 to March 2018 at two sampling stations located in Barcelona city and Montseny Natural Park, representing urban and rural areas, respectively. The chemical composition of PM10 was analyzed offline using a broad set of analytical instruments, including high-resolution time-of-flight mass spectrometry (HR-ToF-AMS), a total organic carbon analyzer (TCA), inductively coupled plasma atomic emission spectrometry (ICP-AES), inductively coupled plasma mass spectrometry (ICP-MS), ion chromatography (IC), and thermal-optical carbon analyzer. Source apportionment analysis of the water-soluble organic content of the samples measured via HR-ToF-AMS revealed two primary and two secondary sources of OA, which included biomass-burning OA (BBOA), sulfur-containing OA (SCOA), as well as summer- and winter‑oxygenated OA (SOOA and WOOA). The presence of hydrocarbon-like water-insoluble OA was also identified based on concentration trends in black carbon and nitrogen oxides. The results from the source apportionment analysis of the inorganic composition were correlated with different OA factors to assess potential source contributors. Barcelona showed significantly higher average water-soluble OA concentrations (5.63 ± 0.56 μg m-3) than Montseny (3.27 ± 0.37 μg m-3) over the sampling period. WOOA accounted for nearly 27 % of the averaged OA in Barcelona compared to only 7 % in Montseny. In contrast, SOOA had a greater contribution to OA in Montseny (47 %) than in Barcelona (24 %). SCOA and BBOA were responsible for 15–28 % of the OA at both sites. There were also seasonal variations in the relative contributions of different OA sources. Our overall results showed that local anthropogenic sources were primarily responsible for up to 70 % of ambient soluble OA in Barcelona, and regulating local-scale emissions could significantly improve air quality in urban Spain.

Water-soluble organic aerosols over South Asia – Seasonal changes and source characteristics

Water-soluble organic carbon (WSOC) has been identified as a key component in atmospheric aerosols due to its ability to act as cloud condensation nuclei (CCN) owing to their highly hygroscopic nature. This paper discusses about the spatio-temporal variability in WSOC mass concentration, sources (primary and secondary contributions), the role of long-range air-mass transport in modulating their abundance, at distinct sectors over South Asia. We found from our observations that, photochemical ageing of primary organic aerosols that are derived from biomass emissions, significantly contribute to the total WSOC budget over South Asia. The wide range of water-soluble compounds released by biomass burning can contribute directly to the WSOC fraction or undergo further atmospheric processing, such as oxidation or ageing, leading to the formation of additional WSOC. WSOC/OC (organic carbon) ratio and the correlation between the WSOC and secondary organic carbon (SOC) are used for assessing the contribution from secondary sources. The three different ratios are used to delineate different source processes; OC/EC (elemental carbon) for source identification, WSOC/OC for long-range atmospheric transport (ageing) and WSOC/SOC to understand the primary and secondary contribution of WSOC. The present investigation revealed that, the primary OC that have undergone significant chemical processing as a result of long-range transport have a substantial influence on WSOC formation over South Asia, especially in Indo Gangetic Plain outflow regions such as southern peninsular and adjacent marine regions. Overall, oxidation and ageing of primary organic aerosols emitted from biomass burning was found to serve as an important source of WSOC over South Asia.

Mist cannon trucks can exacerbate the formation of water-soluble organic aerosol and PM2.5 pollution in the road environment

Abstract. Mist cannon trucks have been widely applied in megacities in China to reduce the road dust, since they are considered to be more water saving and efficient than the traditional sprinkling trucks. However, their effect on the formation of water-soluble organic compounds and the pollution control of fine particles (PM2.5) remains unknown. We characterized the variations of chemical compositions in PM2.5 collected on the road sides during the simulated operations of mist cannon truck and traditional sprinkling truck via Fourier transform ion cyclotron resonance mass spectrometry and ion chromatography. The mass concentrations of water-soluble organic carbon in PM2.5 showed a significant increase (62 %–70 %) after air spraying. Furthermore, we found that water-soluble organic compounds, particularly organic nitrates, increased significantly via the interactions of reactive gas-phase organics, atmospheric oxidants and aerosol liquid water after air spraying, although the air spraying had a better effect on suppressing road dust than the ground aspersion. Moreover, the formation of PM2.5 on the road segment where the mist cannon truck passed by was promoted, with an increase of up to 13 % in mass concentration after 25–35 min, on average. Thus, the application of mist cannon trucks potentially worsens the road atmospheric environment through the increase in PM2.5 levels and the production of a large number of water-soluble organic compounds in PM2.5. The overall results provide not only valuable insights to the formation processes of water-soluble organic compounds associated with aerosol liquid water in the road environment but also management strategies to regulate the operation of mist cannon trucks in China.

Chemical and Light-Absorption Properties of Water-Soluble Organic Aerosols in Northern California and Photooxidant Production by Brown Carbon Components.

Atmospheric brown carbon (BrC) can impact the radiative balance of the earth and form photooxidants. However, the light absorption and photochemical properties of BrC from different sources remain poorly understood. To address this gap, dilute water extracts of particulate matter (PM) samples collected at Davis, CA over one year were analyzed using high resolution aerosol mass spectrometry (HR-AMS) and UV-vis spectroscopy. Positive matrix factorization (PMF) on combined AMS and UV-vis data resolved five water-soluble organic aerosol (WSOA) factors with distinct mass spectra and UV-vis spectra: a fresh and an aged water-soluble biomass burning OA (WSBBOAfresh and WSBBOAaged) and three oxygenated OA (WSOOAs). WSBBOAfresh is the most light-absorbing, with a mass absorption coefficient (MAC365nm) of 1.1 m2 g-1, while the WSOOAs are the least (MAC365nm = 0.01-0.1 m2 g-1). These results, together with the high abundance of WSBBOAs (∼52% of the WSOA mass), indicate that biomass burning activities such as residential wood burning and wildfires are an important source of BrC in northern California. The concentrations of aqueous-phase photooxidants, i.e., hydroxyl radical (·OH), singlet molecular oxygen (1O2*), and oxidizing triplet excited states of organic carbon (3C*), were also measured in the PM extracts during illumination. Oxidant production potentials (PPOX) of the five WSOA factors were explored. The photoexcitation of BrC chromophores from BB emissions and in OOAs is a significant source of 1O2* and 3C*. By applying our PPOX values to archived AMS data at dozens of sites, we found that oxygenated organic species play an important role in photooxidant formation in atmospheric waters.

Characterization of water−soluble brown carbon in atmospheric fine particles over Xi'an, China: Implication of aqueous brown carbon formation from biomass burning

Brown carbon (BrC) aerosols can affect not only the climate but also human health, however, the light absorption, chemical compositions, and formation mechanisms of BrC are still uncertain, which leads to uncertainties in the accurate estimation of its climate and health impacts. In this study, highly time − resolved brown carbon (BrC) in fine particles was investigated in Xi'an using offline aerosol mass spectrometer analysis. The light absorption coefficient (babs365) and mass absorption efficiency (MAE365) at 365 nm of water−soluble organic aerosol (WSOA) generally increased with oxygen−to−carbon (O/C) ratios, indicating that oxidized OA could have more impacts on BrC light absorption. Meanwhile, the light absorption appeared to increase generally with the increases of nitrogen−to−carbon (N/C) ratios and water−soluble organic nitrogen; strong correlations (R of 0.76 for CxHyNp+ and R of 0.78 for CxHyOzNp+) between babs365 and the N − containing organic ion families were observed, suggesting that the N − containing compounds are the effective BrC chromophores. babs365 correlated relatively well with BBOA (r of 0.74) and OOA (R of 0.57), but weakly correlated with CCOA (R of 0.33), indicating that BrC in Xi'an was likely to be associated with biomass burning and secondary sources. A multiple linear regression model was applied to apportion babs365 to contributions of different factors resolved from positive matrix factorization on water-soluble organic aerosols (OA) and obtained MAE365 values of different OA factors. We found that biomass-burning organic aerosol (BBOA) dominated the babs365 (48.3 %), followed by oxidized organic aerosol (OOA, 33.6 %) and coal combustion organic aerosol (CCOA, 18.1 %). We further observed that nitrogen−containing organic matter (i.e., CxHyNp+ and CxHyOzNp+) increased with the increase of OOA/WSOA and the decrease of BBOA/WSOA, especially under high ALWC conditions. Our work offered proper observation evidence that BBOA is oxidized through the aqueous formation to produce BrC in Xi'an, China.

Fluorescence of solvent-extractable organics in sub-micrometer forest aerosols in Hokkaido, Japan

Excitation–emission matrix (EEM) fluorescence spectroscopy is an analytical method for obtaining the properties, components, and sources of chromophores of atmospheric organic aerosols (OA). Most studies have been limited to water-soluble OA; the chemical structures of OA associated with chromophores and the sources of chromophores are still not well understood. In this study, the fluorescence properties of solvent-extractable organic components, fractionated based on their polarity in sub-micrometer forest aerosols in Hokkaido, Japan, were characterized on the basis of their EEMs in combination with chemical structural characterization from offline aerosol mass spectrometry. The fluorescence volume normalized by the mass concentration (NFV) and the fluorescence volume (FV) corresponding to the atmospheric abundance for water-insoluble organic matter (WISOM) were higher than those of other OA fractions and highest in the winter. Correlation analyses between the NFVs and the relative intensities of ion groups from the mass spectra from a high-resolution aerosol mass spectrometer suggest that organic compounds containing O and N contributed to the fluorescence of the OA fractions. Although the fluorescence indices used to characterize aquatic dissolved organic matter exhibited comparable values for water-soluble organic matter (WSOM) in this study and in previous studies, they are not applicable in explaining the types or sources of other OA fractions. A parallel factor (PARAFAC) analysis for EEM profiles identified five components. Four components had fluorescence characteristics similar to those associated with humic-like substances (HULIS), and one had fluorescence characteristics associated with protein-like compounds (PLOM). The chromophores commonly associated with HULIS with oxygenated structures contributed significantly to respective OA fractions; this implies that for fluorescence measurements, such as the detection of primary biological aerosol particles (PBAP), contributions from oxygenated organics should be considered in the forest region.

Marine nitrogen fixation as a possible source of atmospheric water-soluble organic nitrogen aerosols in the subtropical North Pacific

Abstract. Water-soluble organic nitrogen (WSON) in marine atmospheric aerosols affect the water solubility, acidity, and light-absorbing properties of aerosol particles, which are important parameters in assessing both the climate impact and the biogeochemical cycling of bioelements. Size-segregated aerosol and surface seawater (SSW) samples were simultaneously collected over the subtropical North Pacific to investigate the origin of WSON in the marine atmosphere. The fine-mode WSON concentration (7.5 ± 6.6 ngN m−3) at 200–240∘ E along 23∘ N, defined as the eastern North Pacific (ENP), was significantly higher than that (2.4 ± 1.9 ngN m−3) at 135–200∘ E, defined as the western North Pacific (WNP). Analysis of the stable carbon isotope ratio of water-soluble organic carbon (WSOC; δ13CWSOC) together with backward trajectory indicated that most of the observed WSON in the fine particles in the ENP originated from the ocean surface. We found positive relations among nitrogen-fixation rate, dissolved organic nitrogen (DON) in SSW, and the WSON concentrations. The result suggests that reactive nitrogen (DON and ammonium), produced and exuded by nitrogen-fixing microorganisms in SSW, contributed to the formation of WSON aerosols. This study provides new insights into the role of ocean-derived reactive nitrogen aerosols associated with marine microbial activity.

Environmental factors driving the formation of water-soluble organic aerosols: A comparative study under contrasting atmospheric conditions

Water-soluble organic carbon (WSOC), as major fractions of atmospheric aerosols, have gained attention due to their light-absorption properties. To illustrate the sources and key environmental factors driving WSOC formation under different atmospheric conditions, a comparative study was conducted by summarizing the results obtained from five field campaigns at inland (urban, suburban or regional) sites and a coastal site during different seasons. Organic carbon concentrations varied from 8.5 μg/m3 at the summer regional site to 17.5 μg/m3 at the winter urban site, with 46 %- 89 % of the mass as WSOC. Based on correlation analysis, primary combustion emissions were more important in winter than in summer, and secondary formation was an important source of WSOC during winter, summer and autumn. Atmospheric oxidants (NO2, O3), aerosol liquid water (ALW) and ambient RH were important factors influencing the WSOC formation, while their roles varied in different atmospheres. We observed a seasonal transition of atmospheric oxidants dominating the WSOC formation from O3 and NO2-driven conditions in summer to NO2-driven conditions in winter. Elevated ALW or ambient RH generally favor the WSOC formation, while the WSOC dependence of ALW varied among different ALW ranges. As the increasing of ALW or ambient RH, a transition of WSOC formation from “RH/ALW-limited regime” under low-ALW conditions, to “RH/ALW and precursor-driven regime” under medium-ALW/RH, and to “precursor-limited (RH/ALW-excess) regime” were observed for the inland atmospheric conditions. Under the high-RH and ALW conditions in coastal areas, ALW or ambient RH was generally not a limiting factor for WSOC formation.

Light absorption potential of water-soluble organic aerosols in the two polluted urban locations in the central Indo-Gangetic Plain

PM2.5 (particulate matter having aerodynamic diameter ≤2.5 μm) samples were collected during wintertime from two polluted urban sites (Allahabad and Kanpur) in the central Indo-Gangetic Plain (IGP) to comprehend the sources and atmospheric transformations of light-absorbing water-soluble organic aerosol (WSOA). The aqueous extract of each filter was atomized and analyzed in a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Water-soluble organic carbon (WSOC) and WSOA concentrations at Kanpur were ∼1.2 and ∼1.5 times higher than that at Allahabad. The fractions of WSOC and secondary organic carbon (SOC) to total organic carbon (OC) were also significantly higher ∼53% and 38%, respectively at Kanpur compared to Allahabad. This indicates a higher abundance of oxidized WSOA at Kanpur. The absorption coefficient (babs-365) of light-absorbing WSOA measured at 365 nm was 46.5 ± 15.5 Mm−1 and 73.2 ± 21.6 Mm−1 in Allahabad and Kanpur, respectively, indicating the dominance of more light-absorbing fractions in WSOC at Kanpur. The absorption properties such as mass absorption efficiency (MAE365) and imaginary component of refractive index (kabs-365) at 365 nm at Kanpur were also comparatively higher than Allahabad. The absorption forcing efficiency (Abs SFE; indicates warming effect) of WSOA at Kanpur was ∼1.4 times higher than Allahabad. Enhancement in light absorption capacity was observed with the increase in f44/f43 (fraction of m/z 44 (f44) to 43 (f43) in organic mass spectra) and O/C (oxygen to carbon) ratio of WSOA at Kanpur while no such trend was observed for the Allahabad site. Moreover, the correlation between carbon fractions and light absorption properties suggested the influence of low-volatile organic compounds (OC3 + OC4 fraction obtained from thermal/optical carbon analyzer) in increasing the light absorption capacity of WSOA in Kanpur.

Organic aerosol sources in Krakow, Poland, before implementation of a solid fuel residential heating ban

Krakow is a pollution hot-spot in Europe which is thought to be caused mainly by a high use of coal combustion (power plants, residential heating). Here, we quantify the impact of coal burning on air quality in the city of Krakow before the use of solid fuels for residential heating was banned within the city of Krakow. The particulate matter (PM) was collected on 126 24-hour filter samples (January to September, both PM1 and PM10, i.e., with an aerodynamic diameter smaller than 1 μm and 10 μm, respectively) and analyzed with an aerosol mass spectrometer and the sources of the organic aerosol (OA) quantified. Secondary OA (SOA) likely from residential heating was the main contributor to winter-time OA (78 % in PM1, 57 % in PM10) and was composed of equal parts of fossil and non-fossil emissions. Additionally, fresh solid fuel combustion emissions from residential heating contributed to OA during winter (coal combustion OA (CCOA): 12 %, biomass burning OA (BBOA): 3 %). While BBOA contributed substantially to water-soluble OA, COOA was found to be water-insoluble and thus not identified as part of water-soluble OA. Together with the fairly low water-solubility of winter oxygenated OA (WOOA, 29 %), this leads to a low overall water-solubility of organic carbon during winter (35 %). In contrast, spring and summer were characterized by more soluble organic carbon (71 % in PM1, 55 % in PM10) which was dominated by biogenic sources (non-fossil), i.e., fine biogenic secondary oxygenated OA (summer oxygenated OA (SOOA): 35 % in PM1) and coarse primary biological OA (PBOA: 54 % in PM10). Overall, here we provide information on OA's sources needed to evaluate the success of mentioned efforts to improve air quality in Krakow in future studies.

Large contribution of fossil-derived components to aqueous secondary organic aerosols in China

Incomplete understanding of the sources of secondary organic aerosol (SOA) leads to large uncertainty in both air quality management and in climate change assessment. Chemical reactions occurring in the atmospheric aqueous phase represent an important source of SOA mass, yet, the effects of anthropogenic emissions on the aqueous SOA (aqSOA) are not well constrained. Here we use compound-specific dual-carbon isotopic fingerprints (δ13C and Δ14C) of dominant aqSOA molecules, such as oxalic acid, to track the precursor sources and formation mechanisms of aqSOA. Substantial stable carbon isotope fractionation of aqSOA molecules provides robust evidence for extensive aqueous-phase processing. Contrary to the paradigm that these aqSOA compounds are largely biogenic, radiocarbon-based source apportionments show that fossil precursors produced over one-half of the aqSOA molecules. Large fractions of fossil-derived aqSOA contribute substantially to the total water-soluble organic aerosol load and hence impact projections of both air quality and anthropogenic radiative forcing. Our findings reveal the importance of fossil emissions for aqSOA with effects on climate and air quality.

Optical properties and potential sources of water-soluble and methanol-soluble organic aerosols in Taipei, Taiwan

The optical properties and sources of brown carbon (BrC) have been poorly constrained in climate models due to the variability of spatiotemporal characteristics, impeding the accurate understanding of its impact on air quality and climate. In this study, daily PM2.5 samples, which were collected from January to November 2021 in urban Taipei, Taiwan, and seasonal variations of optical properties of water-soluble and methanol-soluble organic carbon (WSOC and MSOC) were evaluated. The light absorption coefficients at 365 nm (Abs365) of both extracts, which strongly correlated with WSOC and MSOC mass concentrations, displayed distinct seasonal variations with the highest in winter and the lowest in summer. The Absorption Ångström Exponent of WSOC and MSOC ranged from 4.16 to 7.75 and 4.03–6.83, with averages of 6.05 ± 0.56 and 5.29 ± 0.61, respectively. The mass absorption efficiency (MAE365), which normalizes the Abs365 of both extracts to the mass of WSOC and MSOC, showed significant seasonal difference with the high MAE365, WSOC of 0.96 ± 0.29 m2 g−1 in winter and the lowest in summer of 0.49 ± 0.07 m2 g−1, whereas contrasting with the largest MAE365, MSOC of 0.99 ± 0.46 m2 g−1 in summer and the lowest in winter of 0.66 ± 0.28 m2 g−1, respectively. Fossil fuel combustion, such as traffic emission, and biomass burning, such as crematorium, were identified to be important contributors to light-absorbing substances. The estimated fractional radiative forcing by WSOC and MSOC to elemental carbon was most significant during winter (8.15 ± 3.77%) and spring (13.90 ± 4.38%), respectively, which may greatly affect the atmospheric photochemistry and climate. This study suggests that the impact of BrC in Taiwan on the local and regional air quality and climate is non-negligible.

Sources and processes of water-soluble and water-insoluble organic aerosol in cold season in Beijing, China

Abstract. Water-soluble and water-insoluble organic aerosol (WSOA and WIOA) constitute a large fraction of fine particles in winter in northern China, yet our understanding of their sources and processes are still limited. Here we have a comprehensive characterization of WSOA in cold season in Beijing. Particularly, we present the first mass spectral characterization of WIOA by integrating online and offline organic aerosol measurements from high-resolution aerosol mass spectrometer. Our results showed that WSOA on average accounted for 59 % of the total OA and comprised dominantly secondary OA (SOA, 69 %). The WSOA composition showed significant changes during the transition season from autumn to winter. While the photochemical-related SOA dominated WSOA (51 %) in early November, the oxidized SOA from biomass burning increased substantially from 8 % to 29 % during the heating season. Comparatively, local primary OA dominantly from cooking aerosol contributed the major fraction of WSOA during clean periods. WIOA showed largely different spectral patterns from WSOA which were characterized by prominent hydrocarbon ions series and low oxygen-to-carbon (O/C = 0.19) and organic mass-to-organic carbon (OM/OC = 1.39) ratios. The nighttime WIOA showed less oxidized properties (O/C = 0.16 vs. 0.24) with more pronounced polycyclic aromatic hydrocarbons (PAHs) signals than daytime, indicating the impacts of enhanced coal combustion emissions on WIOA. The evolution process of WSOA and WIOA was further demonstrated by the triangle plot of f44 (fraction of m/z 44 in OA) vs. f43, f44 vs. f60, and the Van Krevelen diagram (H/C vs. O/C). We also found more oxidized WSOA and an increased contribution of SOA in WSOA compared with previous winter studies in Beijing, indicating that the changes in OA composition due to clean air act have affected the sources and properties of WSOA.

Oxidative potential and hydroxyl radical generation capacity of ambient PM2.5 over a high-altitude site in northeastern Himalaya: Role of long-range transport

This study investigates the dithiothreitol (DTT)-based oxidative potential (OP) and corresponding hydroxyl radical (•OH) generations capacity of PM2.5 (particulate matter with aerodynamic diameter ≤ 2.5 μm) over a high-altitude site, Shillong (25.7 °N, 91.9 °E; 1064 m above mean sea level), located in the northeastern Himalaya. Measured OP and •OH are reported in two units: per m3 of filtered air (OPV and OHV) or per unit mass of PM2.5 in μg (OPM and OHM). Based on the characteristic ratios of chemical species in different sources, PM2.5 were classified into three source categories: Biomass Burning (BB) (N = 10), Secondary Organic Aerosols (SOA) (N = 12), and Mixed (N = 12). Consistently higher OP and •OH generation per m3 of air (OPV: 6.2 ± 1.0 (average ± SD, 1σ) nmol DTT min−1 m−3, and OHV: 1.2 ± 0.31 nmol •OH m−3) in all BB-dominated PM2.5 samples indicate relatively hazardous exposure dose from BB emissions among all sources. Characteristic OC/EC, WSOC/OC, and nss-K+/EC ratios evoked that SOA from biogenic precursors was a significant source for the observed OP and •OH in SOA-categorized samples. Distinctly different chemical composition of PM2.5 over Shillong (about 55% composed of organic matter) makes it relatively more (2–4 times) intrinsically redox-active compare to a reported study over another high-altitude site in a semi-arid region of India. Despite ∼1.7 times lower PM2.5 mass over Shillong (characterized by more aged PM2.5) compare to Patiala (30.3°N, 76.4°E; 250m amsl, a semi-urban city, characterized by fresher PM2.5 from mixed sources), the observed OPV over Shillong was about 1.2 times higher, and the OPM was about 2 times higher. It is attributed to the effect of atmospheric processing on particle's redox-activity. While examining the relationship of OPV and OHV with chemical species, it was observed that •OH generation capacity was more influenced by WSOC species' origin (primary or secondary) compare to DTT consumption. Such an observation restricts the practicality of particle-induced OP to be considered as the only metric for aerosol particle toxicity, and suggests also to consider simultaneous measurements of •OH generations. For the BB-dominated category, OC-normalized OP (OPOC) was correlated strongly with the fractions of N-containing water-soluble organic aerosols (i.e., a fraction of WSON and a fraction of familyCHO1N). Corresponding OC/EC, nss-K+/EC and nss-SO42−/EC ratios hint that coal combustion, in addition to BB, could be a significant source of redox-active WSON species in these samples. Such studies are important for identifying redox-active aerosol species and developing appropriate mitigation policies for healthy air.