Dominant contribution of oxygenated organic aerosol to haze particles from real-time observation in Singapore during an Indonesian wildfire event in 2015

Recurring transboundary haze from Indonesian wildfires in previous decades significantly elevated particulate matter (PM) concentrations in Southeast Asia. During that event on October 10 to 31, 2015, we conducted a real-time observation of non-refractory submicron PM (NR-PM1) in Singapore using an Aerodyne aerosol mass spectrometer. Simultaneously, we characterized carbonaceous components and organic aerosol (OA) tracers from fine PM (PM2.5) samples to support source apportionment of the online measurements. The real-time analysis demonstrated that OA accounted for approximately 80 % of NR-PM1 mass during the wildfire haze period. Source apportionment analysis applied to the OA mass spectra using multilinear-engine (ME-2) approach resulted in four factors: hydrocarbon-like OA (HOA), biomass burning OA (BBOA), peat burning OA (PBOA), and oxygenated OA (OOA). The OOA can be considered as a surrogate of both secondary organic aerosol (SOA) and oxidized primary organic aerosol (OPOA), while the other factors are considered as surrogates of primary organic aerosol (POA). The OOA accounted for approximately 50 % of the total OA mass in NR-PM1, while POA subtypes from wildfires (BBOA and PBOA) contributed to approximately 30 % of the total OA mass. Our findings highlight the importance of atmospheric chemical processes, which likely include POA oxidation and SOA formation from oxidation of gaseous precursors, to the OOA concentration. As this research could not separately quantify the POA oxidation and SOA formation processes, further studies should attempt to investigate the contribution of gaseous precursors oxidation and POA aging to the OOA formation in wildfire plumes.

Improved source apportionment of organic aerosols in complex urban air pollution using the multilinear engine (ME-2)

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

Improved source apportionment of organic aerosols in complex urban air pollution using the multilinear engine (ME-2)

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

The role of traffic emissions in particulate organics and nitrate at a downwind site in the periphery of Guangzhou, China

Particulate matter (PM) pollution on the peripheries of rapidly expanding megacities in China can be as serious as in the cities due to direct emission and transport of primary PM from cities and effective formation of secondary PM. To investigate the emission and formation of PM on the periphery of Guangzhou (a megacity in southern China), a suite of real-time instruments were deployed at Panyu, downwind of Guangzhou, for PM measurements from November to December 2014. Dominated by organics, PM1 (particles with diameter less than 1 μm) concentrations in Panyu were higher (average ~ 55.4 μg/m3) than those in nearby cities such as Hong Kong and Shenzhen. Five sources for organic aerosols (OA) were resolved by positive matrix factorization (PMF) analysis with the multilinear engine (ME-2). These sources are hydrocarbon-like organic aerosol (HOA), cooking organic aerosol (COA), biomass burning related organic aerosol (BBOA), as well as semi-volatile oxygenated organic aerosol (SVOOA) and low-volatile oxygenated organic aerosol (LVOOA). The use of the COA mass spectrum obtained in our earlier study at a urban site in Hong Kong as a constraining factor in ME-2 produced the most interpretable results for the Panyu dataset. Freshly emitted HOA contributed 40 % to the high concentrations of organics at night. The mass concentration of SOA (SVOOA + LVOOA) continuously increased as odd oxygen (Ox = O3 + NO2) increased during daytime, attributable to the secondary production of PM facilitated by photochemistry. The SOA-to-Ox ratio was higher than those reported in previous studies in North America (covering the period from spring to summer), indicating efficient photochemical production of SOA even in late autumn and early winter at this subtropical downwind site. The efficient SOA formation during daytime was likely fueled by the sufficient SOA precursors in the atmosphere. The large input of NOx, which tracked well with HOA from automobile emissions, resulted in the significant formation of nitrate in both daytime and nighttime. Strong correlations between particulate nitrate and excess ammonium ([NH4+]/[SO42−] − 1.5) × [SO42−]) were observed. Higher partitioning of nitrate into the gas phase was found in November than in December, likely due to the lower temperatures in December. Results from this study suggest that there is much room to mitigate the PM pollution in urbanized areas such as Guangzhou, as well as their peripheries, by reductions in traffic-related pollutants.

Chemical characterization of submicron regional background aerosols in the western Mediterranean using an Aerosol Chemical Speciation Monitor

An Aerosol Chemical Speciation Monitor (ACSM, Aerodyne Research Inc.) was deployed at the Montseny (MSY; 41° 46'46" N, 02° 21'29" E, 720 m a.s.l.) regional background site in the western Mediterranean, Spain, from June 2012 to July 2013 to measure real-time inorganic (nitrate, sulfate, ammonium and chloride) and organic submicron aerosol concentrations. Co-located measurements, including real-time submicron particulate matter (PM1) and black carbon (BC) concentrations, and off-line PM1 chemical analysis were also carried out. This is one of the few studies that compare ACSM data with off-line PM1 measurements, avoiding the tail of the coarse mode included in the PM2.5 fraction. The ACSM + BC concentrations agreed with the PM1 measurements, and a strong correlation was found between the concentrations of ACSM species and the off-line measurements, although some discrepancies remain unexplained. Results point to a current underestimation of the relative ionization efficiency (RIE) established for organic aerosol (OA), which should be revised in the future. The OA was the major component of submicron aerosol (53% of PM1), with a higher contribution in summer (58% of PM1) than in winter (45% of PM1). Source apportionment of OA was carried out by applying positive matrix factorization (PMF), using the multilinear engine (ME-2) to the organic mass spectral data matrix. Three sources were identified in summer: hydrocarbon-like OA (HOA), low-volatile oxygenated OA (LV-OOA), and semi-volatile oxygenated OA (SV-OOA). The secondary OA (SOA; 4.8 μg m−3, sum of LV-OOA and SV-OOA) accounted for 85% of the total OA, and its formation during daytime (mainly SV-OOA) was estimated to be 1.1 μg m−3. In winter, HOA was also identified (12% of OA), a contribution from biomass burning OA (BBOA) was included and it was not possible to differentiate between two different SOA factors, but a single oxygenated OA (OOA) factor was resolved. The OOA contribution represented 60% of the total OA, with a degree of oxidation higher than both OOA summer factors. An intense wildfire episode was studied, obtaining a region-specific BBOA profile.

Chemical characterization of submicron regional background aerosols in the Western Mediterranean using an Aerosol Chemical Speciation Monitor

An Aerosol Chemical Speciation Monitor (ACSM, Aerodyne Research Inc.) was deployed at Montseny (MSY, 720 m a.s.l.) regional background site in the Western Mediterranean from June 2012 to July 2013 to measure real-time inorganic (nitrate, sulphate, ammonium and chloride) and organic submicron aerosol concentrations. Co-located measurements were also carried out including real-time submicron particulate matter (PM1) and black carbon (BC) concentrations, and off-line PM1 chemical analysis. This is one of the few studies that compare ACSM data with off-line PM1 measurements, avoiding the tail of the coarse mode included in the PM2.5 fraction. The ACSM + BC concentrations agreed with the PM1 measurements, and strong correlation was found between the concentrations of ACSM species and the off-line measurements, although some discrepancies remain unexplained. Results point to a current underestimation of the relative ionization efficiency (RIE) established for organic aerosol (OA), which should be revised in the future. The OA was the major component of submicron aerosol (53% of PM1), with a higher contribution in summer (58% of PM1) than in winter (45% of PM1). Source apportionment of OA was carried out by applying Positive Matrix Factorization (PMF) using the Multilinear Engine (ME-2) to the organic mass spectral data matrix. Three sources were identified in summer: hydrocarbon-like OA (HOA), low-volatile oxygenated OA (LV-OOA), and semi-volatile oxygenated OA (SV-OOA). The secondary OA (SOA, 4.7 μg m−3, sum of LV-OOA and SV-OOA) accounted for 85% of the total OA and its formation during daytime (mainly SV-OOA) was estimated to be 1.1 μg m−3. In winter, HOA was also identified (12% of OA), a contribution from biomass burning OA was included, and it was not possible to differentiate two different SOA factors but a single OOA factor was resolved. The OOA contribution represented the 60% of the total OA, with a degree of oxidation higher than both OOA summer factors. An intense wildfire episode was studied obtaining a region-specific BBOA profile.