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To understand diurnal variations in PM2.5 composition and aerosol extract absorption, PM2.5 samples were collected at intervals of 2 hr from 8:00 to 20:00 and 6 hr from 20:00 to 8:00 (the next day) in northern Nanjing, China, during the winter and summer of 2019–2020 and analyzed for bulk components, organic tracers, and light absorption of water and methanol extracts—a proxy measure of brown carbon (BrC). Diurnal patterns of measured species reflected the influences of primary emissions and atmospheric processes. Light absorption coefficients of water (Abs365,w) and methanol extracts (Abs365,m) at 365 nm shared a similar diurnal profile peaking at 18:00–20:00, generally following changes in biomass burning tracers. However, Abs365,w, Abs365,m, and their normalizations to organic aerosols increased at 14:00–16:00, earlier than that of levoglucosan in the late afternoon, which was attributed to secondarily formed BrC. The methanol extracts showed a less drastic decrease in light absorption at night than the water extracts and elevated absorption efficiency during 2:00–8:00. This is due to the fact that the water‐insoluble OC has a longer lifetime and stronger light absorption than the water‐soluble OC. According to the source apportionment results solved by positive matrix factorization (PMF), biomass burning and secondary formation were the major BrC sources in northern Nanjing, with an average total relative contribution of about 90%. Compared to previous studies, diurnal source cycles were added to the PMF simulations in this work by using time‐resolved speciation data, which avoided misclassification of BrC sources. Plain Language Summary: Light‐absorbing organic carbon (OC), also known as "brown carbon", plays an important role in influencing the Earth's radiative balance. Filter samples of particulate matter with an aerodynamic diameter of less than 2.5 μm (PM2.5) were collected at a resolution of 2 hr from 8:00 to 20:00 and a resolution of 6 hr from 20:00 to 8:00 (the next day) in northern Nanjing, China, during the winter and summer of 2019 and 2020. To understand the diurnal variations of BrC and its sources, each sample was analyzed for bulk components (OC, elemental carbon, and water‐soluble ions), organic molecular markers, and light absorption by BrC, and a receptor model was used to identify potential BrC sources based on PM2.5 composition data. We found that diurnal variations of BrC generally followed changes in concentrations of levoglucosan‐a tracer of biomass burning; the increase in BrC absorption in the early afternoon was caused by secondary formation of BrC chromophores; biomass burning and secondary formation were the main sources of BrC. Time‐resolved measurements of PM2.5 components were rarely used to investigate the diurnal variations of BrC and its sources, which is very important for modeling the climate impact of BrC. Key Points: Diurnal variations in PM2.5 bulk components and organic tracers reflect diurnal cycles of sourcesLight absorption of water and methanol extracts of PM2.5 exhibited a similar diurnal profile that followed changes in levoglucosanShort‐term and high time‐resolved data of organic tracers should be used for source apportionment to avoid misclassification [ABSTRACT FROM AUTHOR]

• NO3- concentrations in coarse particles show elevations in warm seasons. • Size distributions of semi-volatile species have a dependency on ambient temperatures. • Relative humidity plays a role in driving seasonal changes of PM size distributions. • Heterogeneous formations of secondary salts contribute ∼20% of speciated coarse PM. Size-segregated ambient particulate matter (PM) samples were collected seasonally in suburban Nanjing of east China from 2016 to 2017 and chemically speciated. In both fine (< 2.1 µm, PM 2.1) and coarse (> 2.1 µm, PM >2.1) PM, organic carbon (OC) accounted for the highest fractions (26.9% ± 10.9% and 23.1% ± 9.35%) of all measured species, and NO 3 − lead in average concentrations of water-soluble inorganic ions (WSIIs). The size distributions of measured components were parameterized using geometric mean diameter (GMD). GMD values of NO 3 −, Cl−, OC, and PM for the whole size range varied from < 2.1 µm in winter to > 2.1 μm in warm seasons, which was due to the fact that the size distributions of semi-volatile components (e.g., NH 4 NO 3 , NH 4 Cl, and OC) had a dependency on the ambient temperature. Unlike OC, elemental carbon (EC), and elements, NH 4 +, NO 3 −, and SO 4 2− exhibited an increase trend in GMD values with relative humidity, indicating that the hygroscopic growth might also play a role in driving seasonal changes of PM size distributions. Positive matrix factorization was performed using compositional data of fine and coarse particles, respectively. The secondary formation of inorganic salts contributing to the majority (> 70%) of fine PM and 20.2% ± 19.9% of speciated coarse PM. The remaining coarse PM content was attributed to a variety of dust sources. Considering that coarse and fine PM had comparable mass concentrations, more attention should be paid to local dust emissions in future air quality plans. [Display omitted] [ABSTRACT FROM AUTHOR]

In this study, collocated filter samples of particulate matter with aerodynamic diameter less than 2.5 μm (PM2.5) from northern Nanjing were extracted using water and methanol, followed by analysis of light absorption. A backup quartz filter was used to correct sampling artifacts caused by adsorption of gaseous organics. The collocated precision of light‐absorbing properties of water‐soluble organic carbon (WSOC) and methanol‐extractable organic carbon (MEOC) were parameterized using correlation coefficient (r), coefficient of divergence (COD), and average relative percent difference (ARPD, %). In general, the light absorption of WSOC and MEOC showed good agreement (r > 0.80, COD < 0.20) between collocated samples. Performing artifact correction is necessary and will increase the heterogeneity between collocated measurements. The duplicate‐derived ARPD values of MEOC absorption were more than 60% higher than those of WSOC absorption. Then, it would be inappropriate to assume a uniform uncertainty fraction (e.g., ∼10%) for WSOC and MEOC absorption in future studies on their climate effects and source apportionment. To apportion artifact‐corrected absorption of aerosol extracts to specific emission sources or formation pathways, positive matrix factorization was performed by using concentration data of selected bulk species and organic molecular markers. Among the nine identified factor/sources, the biomass burning factor had the highest average contributions to the absorption of both WSOC (31.6%) and MEOC (48.0%), followed by dust resuspension and coal combustion factors. Unlike combustion‐related primary emissions, the factors containing influences from atmospheric processing (e.g., secondary nitrate) contributed more fractions of WSOC absorption than MEOC absorption. Key Points: Collocated measurements provide an approach to estimate uncertainties in light‐absorbing properties of solvent‐extractable organic carbonIgnoring the adsorption of gaseous organics onto filter medium will lead to significant overestimation of brown carbon absorptionAerosol sources influenced by aging processes contributed more fractions of aqueous extracts absorption than methanol extracts absorption [ABSTRACT FROM AUTHOR]

This study seeks to understand the ambient levels, gas/particle partitioning, and sources of nonpolar organic molecular makers (OMMs) at a suburban site in Nanjing, China. Particle‐ and gas‐phase OMMs were collected using a medium volume sampler equipped with two quartz filters in series and a polyurethane foam (PUF)/XAD‐4/PUF (PXP) adsorbent sandwich. More than 100 pairs of filter and PXP samples were collected diurnally from September 2018 to September 2019. The concentration profiles of total n‐alkanes and polycyclic aromatic hydrocarbons were peaking at n‐C12–n‐C17 homologs (9.98 ± 5.43–38.4 ± 17.7 ng m−3) and naphthalene (92.5 ± 56.7 ng m−3), respectively, followed by decreasing concentrations with further increases in molecular weight. Three artifact correction methods with different pre‐assumptions on relative contributions of evaporation loss to backup filter measurements were used to separate particle‐ and gas‐phase OMMs. The resulting particle‐phase fractions showed significant differences for OMMs with vapor pressure <10−9 atm at 298.15 K. Absorptive gas/particle partitioning coefficients of OMMs were empirically calculated based on measurements and theoretically predicted for comparison. The results obtained under the three artifact correction methods suggested growing importance of evaporation loss with decreased vapor pressure. Positive matrix factorization (PMF) was performed for source apportionment using total (PMFtotal) and particle‐phase (PMFparticle) OMMs data, respectively. Besides eliminating the influence of gas/particle partitioning, the involvements of more volatile species and gaseous OMMs data improved the identification of specific emission sources, supporting the usage of total OMMs data over a wide vapor pressure range for PMF source apportionment. Key Points: The particulate fractions of organic molecular markers attained their minima in summer, when the total concentrations increasedEvaporation loss might be the main sampling artifact of particulate organics when the vapor pressure is lower than 10−10 atmTotal concentrations of organic molecular markers over a wide vapor pressure range should be used for positive matrix factorization analysis [ABSTRACT FROM AUTHOR]

Elemental concentrations of ambient aerosols are commonly sampled over 12–24 h, and the low time resolution puts a great limit on current understanding about the temporal variations and source apportionment based on receptor models. In this work, hourly-resolved concentrations of eighteen elements in PM 2.5 at an urban site in Nanjing, a megacity in Yangtze River Delta of east China, were obtained by using a Xact 625 ambient metals monitor from 12/12/2016 to 12/31/2017. The influence of traffic activities was clearly reflected by the spikes of crustal elements (e.g., Fe, Ca, and Si) in the morning rush hour, and the firework burning and sandstorm events during the sampling periods were tracked by sharp enrichment of Ba, K and Fe, Ca, Si, Ti in PM 2.5 , respectively. To evaluate the advantage of hourly-resolved elements data in identifying impacts from specific emission sources, positive matrix factorization (PMF) analysis was performed with the 1-h data set (PMF 1-h) and 23-h averaged data (PMF 23-h), respectively. The 4- and 6-factor PMF 23-h solutions had similar factor profiles and consistent factor contributions as the corresponding PMF 1-h solutions. However, due to the limit in inter-sample variability, PMF analysis with 23-h average data misclassified some major (e.g., K, Fe, Zn, Ca, and Si) and trace (e.g., Pb) elements in factor profiles, resulting in different absolute factor contributions between PMF 23-h and PMF 1-h solutions. These results suggested the use of high time-resolved data to obtain valid and robust source apportionment results. Image 1 • PM 2.5 elements were measured with 1-h resolution at an urban site in Nanjing city. • Specific local emissions were reflected by the diurnal variations of PM 2.5 elements. • Two pollution episodes were tracked by sharp enrichment of distinct elements. • The 1-h measurements data were preferred over 23-h averages for source apportionment. This study suggests using high time-resolved measurements of PM 2.5 elements for receptor-based source apportionment to obtain robust results. [ABSTRACT FROM AUTHOR]

Abstract Light-absorbing organic carbon (OC), also referred to as "brown carbon" (BrC), has been intensively investigated in atmospheres impacted by biomass burning. However, other BrC sources (e.g., secondary formation in the atmosphere) are rarely studied in ambient aerosols. In the current work, forty-five PM 2.5 filter samples were collected in Research Triangle Park (RTP), NC, USA from June 1st to July 15th, 2013. The bulk carbonaceous components, including OC, elemental carbon (EC), water soluble OC (WSOC), and an array of organic molecular markers were measured; an ultraviolet/visible spectrometer was used to measure the light absorption of methanol extractable OC and WSOC. The average light absorption per OC and WSOC mass of PM 2.5 samples in summer RTP are 0.36 ± 0.16 m2 gC−1 and 0.29 ± 0.13 m2 gC−1, respectively, lower than the ambient aerosol samples impacted by biomass burning and/or fossil fuel combustion (0.7–1.6 m2 gC−1) from other places. Less than 1% of the aqueous extracts absorption is attributed to the light-absorbing chromophores (nitroaromatic compounds) identified in this work. To identify the major sources of BrC absorption in RTP in the summer, Positive Matrix Factorization (PMF) was applied to a dataset containing optical properties and chemical compositions of carbonaceous components in PM 2.5. The results suggest that the formation of biogenic secondary organic aerosol (SOA) containing organosulfates is an important BrC source, contributing up to half of the BrC absorption in RTP during the summertime. Graphical abstract Image 1 Highlights • BrC absorption in summer at RTP, NC is similar to other Southeastern US locations. • Less than 1% of BrC absorption is attributed to identified nitroaromatic compounds. • Biomass burning is not the dominant source for BrC absorption in summer at RTP, NC. • Biogenic secondary organic aerosol formation is a major BrC source in this work. This study identified a linkage between atmospheric BrC and biogenic SOA formation when biomass burning is not significant in Research Triangle Park, NC during the summer. [ABSTRACT FROM AUTHOR]

Owing to the potential influence of light-absorbing organic carbon (OC), also termed "brown carbon" (BrC), on the planetary radiation budget, many studies have focused on its absorption in single-sized ranges of particulate matter (PM). However, the size distribution and organic tracer-based source apportionment of BrC absorption have not been extensively investigated. In this study, size-resolved PM samples were collected using multi-stage impactors from eastern Nanjing during each season in 2017. The light absorption of methanol-extractable OC at 365 nm (Abs 365 , Mm−1) was determined using spectrophotometry, and a series of organic molecular markers (OMMs) was measured using a gas chromatography-mass spectrometer. Fine PM with an aerodynamic diameter <2.1 μm (PM 2.1) dominated Abs 365 (79.8 ± 10.4%) of the total size ranges with maxima and minima in winter and summer, respectively. The distributions of Abs 365 shifted to larger PM sizes from winter to spring and summer due to lower primary emissions and increased BrC chromophores in dust. Except for low-volatility (p o,* L < 10−10 atm) polycyclic aromatic hydrocarbons (PAHs), the non-polar OMMs, including n- alkanes, PAHs, oxygenated PAHs, and steranes, showed a bimodal distribution pattern. Secondary products of biogenic precursors and biomass burning tracers presented a unimodal distribution peaking at 0.4–0.7 μm, while sugar alcohols and saccharides were enriched in coarse PM. Their seasonal variations in average concentrations reflected intense photochemical reactions in summer, more biomass burning emissions in winter, and stronger microbial activity in spring and summer. Positive matrix factorization was used for the source apportionment of Abs 365 in fine and coarse PM samples. Biomass burning contributed an average of 53.9% to the Abs 365 of PM 2.1 extracts. The Abs 365 of coarse PM extracts was associated with various dust-related sources where the aging processes of aerosol organics could occur. [Display omitted] • Fine particles dominated the light absorption of methanol extracts of total PM. • Low-volatile n- alkanes and steranes in coarse PM increased during warm periods. • Biomass burning contributed more than 50% to BrC absorption in fine PM. • Aging processes of organics in coarse particles could lead to BrC formation. [ABSTRACT FROM AUTHOR]

Abstract: This study presents source apportionment results for PM2.5 from applying positive matrix factorization (PMF) to a 32-month series of daily PM2.5 compositional data from Denver, CO, including concentrations of sulfate, nitrate, bulk elemental carbon (EC) and organic carbon (OC), and 51 organic molecular markers (OMMs). An optimum 8-factor solution was determined primarily based on the interpretability of the PMF results and rate of matching factors from bootstrapped PMF solutions with those from the base case solution. These eight factors were identified as inorganic ion, n-alkane, EC/sterane, light n-alkane/polycyclic aromatic hydrocarbon (PAH), medium alkane/alkanoic acid, PAH, winter/methoxyphenol and summer/odd n-alkane. The inorganic ion factor dominated the reconstructed PM2.5 mass (sulfate + nitrate + EC + OC) in cold periods (daily average temperature <10 °C; 43.7% of reconstructed PM2.5 mass) whereas the summer/odd n-alkane factor dominated in hot periods (>20 °C; 53.1%). The two factors had comparable relative contributions of 26.5% and 27.1% in warm periods with temperatures between 10 °C and 20 °C. Each of the seven factors resolved in a previous study (Dutton et al., 2010b) using a 1-year data set from the same location matches one factor from the current work based on comparing factor profiles. Six out of the seven matched pairs of factors are linked to similar source classes as suggested by the strong correlations between factor contributions (r = 0.89–0.98). Temperature-stratified source apportionment was conducted for three subsets of the data in the current study, corresponding to the cold, warm and hot periods mentioned above. The cold period (7-factor) solution exhibited a similar distribution of reconstructed PM2.5 mass as the full data set solution. The factor contributions of the warm period (7-factor) solution were well correlated with those from the full data set solution (r = 0.76–0.99). However, the reconstructed PM2.5 mass was distributed more to inorganic ion, n-alkane and medium alkane/alkanoic acid factors in the warm period solution than in the full data set solution. For the hot period (6-factor) solution, PM2.5 mass distribution was quite different from that of the full data set solution, as illustrated by regression slopes as low as 0.2 and as high as 4.8 of each matched pair of factors across the two solutions. [Copyright &y& Elsevier]

Abstract: To identify the sources of PM2.5 – bound carbonaceous species and examine the spatial variability of source contributions in the Denver metropolitan area, positive matrix factorization (PMF) was applied to one year of every sixth day ambient PM2.5 compositional data, including elemental carbon (EC), organic carbon (OC), and 32 organic molecular markers, from four sites (two residential and two near-traffic). Statistics (median, inner quantiles and 5th – 95th percentiles range) of factor contributions, expressed as reconstructed carbonaceous mass (EC + OC), were estimated from PMF solutions of replicate datasets generated by using a stationary block bootstrap technique. A seven-factor solution was resolved for a set of data pooled across the four sites, as it gave the most interpretable results and had the highest rate of neural network factor matching (76.9%). Identified factors were primarily associated with high plant wax, summertime emission, diesel vehicle emission, fossil fuel combustion, motor vehicle emission, lubricating oil combustion and wood burning. Pearson correlation coefficients (r) and coefficients of divergence (COD) were used to assess spatial variability of factor contributions. The summertime emission factor exhibited the highest spatial correlation (r = 0.74 – 0.88) and lowest CODs (0.32 – 0.38) among all resolved factors; while the three traffic dominated factors (diesel vehicle emission, motor vehicle emission and lubricating oil combustion) showed lower correlations (r = 0.47 – 0.55) and higher CODs (0.41 – 0.53) on average. Average total EC and OC mass were apportioned to each factor and showed a similar distribution across the four sites. Modeling uncertainties were defined as the 5th – 95th percentile range of the factor contributions derived from valid bootstrap PMF solutions, and were highly correlated with the median factor contribution in each factor (r = 0.77 – 0.98). Source apportionment was also performed on site specific datasets; the results exhibited similar factor profiles and temporal variation in factor contribution as those obtained for the pooled dataset, indicating that the four sites are primarily influenced by similar types of sources. On the other hand, differences were observed in absolute factor contributions between PMF solutions for the pooled versus site-specific datasets, likely due to the large uncertainties in EC and OC factor profiles derived from the site specific datasets with limited numbers of observations. [Copyright &y& Elsevier]

In this study, hourly concentrations of PM 2.5 water-soluble inorganic ions, bulk organic carbon (OC), and elemental carbon (EC) were monitored from 1/1/2017 to 12/31/2017 and validated using filter-based offline analysis at an urban site in Nanjing, China. Compared with 2013 or before, the annual average of PM 2.5 concentration (36.5 ± 32.9 μg m−3) in 2017 decreased by more than 40%, NO 3 − (12.8 ± 11.4 μg m−3) became the most abundant water-soluble ion instead of SO 4 2− (9.29 ± 6.07 μg m−3), and the relative contribution of OC (5.92 ± 3.40 μg m−3) and EC (2.95 ± 1.53 μg m−3) to bulk PM 2.5 (24.9 ± 9.31%) increased substantially, indicating the effectiveness of the control policy for reducing gaseous precursor emissions. Based on the diurnal variations of water-soluble ions and gaseous pollutants, NH 4 +, SO 4 2−, and NO 3 − were secondarily formed and NH 4 NO 3 dominated the composition of ammonium salts in PM 2.5. The diurnal changes of OC, EC, and OC/EC ratios reflected prominent influences from local traffic patterns. Positive matrix factorization was performed using hourly data of PM 2.5 components (PMF 1-h), of which the results were justified by comparing to those using 23-h averaged data (PMF 23-h). Given that the secondary ion formation was still the dominant source (68.2%) of PM 2.5 , and the average PM 2.5 concentration in urban Nanjing remained higher than Tier II limit (35 μg m−3) of the Chinese National Ambient Air Quality Standard, controlling emissions of PM 2.5 precursor gases should be continued after the completion of Air Pollution Prevention and Control Action Plan in 2017. Image 1 • NH 4 NO 3 dominated the composition of ammonium salts in PM 2.5 in urban Nanjing. • Diurnal variations of OC and EC reflected influences from local traffic patterns. • Using hourly measurement data for PMF analysis can achieve more robust results. • Gaseous precursors should be continuously controlled to attain air quality standards. [ABSTRACT FROM AUTHOR]