Biomass Burning Organic Aerosol Research Articles

Volatility of source apportioned wintertime organic aerosol in the city of Athens

The volatility distribution of ambient organic aerosol (OA) and its components was measured during the winter of 2013 in the city of Athens combining a thermodenuder (TD) and a High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). Positive Matrix Factorization (PMF) analysis of both the ambient and the thermodenuder AMS-spectra resulted in a four-factor solution for the OA, namely: hydrocarbon-like OA (HOA), biomass burning OA (BBOA), cooking OA (COA), and oxygenated OA (OOA). The thermograms of the four factors were analyzed and the corresponding volatility distributions were estimated using the volatility basis set (VBS). All four factors included compounds with a wide range of effective volatilities from 10 to less than 10−4 μg m−3 at 298 K. Almost 40% of the HOA consisted of low-volatility organic compounds (LVOCs) with the semi-volatile compounds (SVOCs) representing roughly 30%, while the remaining 30% consisted of extremely low volatility organic compounds (ELVOCs). BBOA was more volatile than the HOA factor on average, with 10% ELVOCs, 40% LVOCs, and 50% SVOCs. 10% of the COA consisted of ELVOCs, another 65% LVOCs, and 50% SVOCs. Finally, the OOA was the least volatile factor and included 40% ELVOCs, 25% LVOCs, and 35% SVOCs. Combining the volatility distributions and the O:C ratios of the various factors, we placed our results in the 2D-VBS analysis framework of Donahue et al. (2012). HOA and BBOA are in the expected region but also include an ELVOC component. COA is in similar range as HOA, but on average is half an order of magnitude more volatile. The OOA in these wintertime conditions had a moderate O:C ratio and included both semi-volatile and extremely low volatility components. The above results are sensitive to the assumed values of the effective vaporization enthalpy and the accommodation coefficient. A reduction of the accommodation coefficient by an order of magnitude or the reduction of the vaporization enthalpy by 20 kJ mol−1 results in the increase of the average volatility by half an order of magnitude.

Biomass burning and biogenic aerosols in northern Australia during the SAFIRED campaign

Abstract. There is a lack of knowledge of how biomass burning aerosols in the tropics age, including those in the fire-prone Northern Territory in Australia. This paper reports chemical characterization of fresh and aged aerosols monitored during the 1-month-long SAFIRED (Savannah Fires in the Early Dry Season) field study, with an emphasis on the chemical signature and aging of organic aerosols. The campaign took place in June 2014 during the early dry season when the surface measurement site, the Australian Tropical Atmospheric Research Station (ATARS), located in the Northern Territory, was heavily influenced by thousands of wild and prescribed bushfires. ATARS was equipped with a wide suite of instrumentation for gaseous and aerosol characterization. A compact time-of-flight aerosol mass spectrometer was deployed to monitor aerosol chemical composition. Approximately 90 % of submicron non-refractory mass was composed of organic material. Ozone enhancement in biomass burning plumes indicated increased air mass photochemistry. The diversity in biomass burning emissions was illustrated through variability in chemical signature (e.g. wide range in f44, from 0.06 to 0.18) for five intense fire events. The background particulate loading was characterized using positive matrix factorization (PMF). A PMF-resolved BBOA (biomass burning organic aerosol) factor comprised 24 % of the submicron non-refractory organic aerosol mass, confirming the significance of fire sources. A dominant PMF factor, OOA (oxygenated organic aerosol), made up 47 % of the sampled aerosol, illustrating the importance of aerosol aging in the Northern Territory. Biogenic isoprene-derived organic aerosol factor was the third significant fraction of the background aerosol (28 %).

Physical and chemical characterization of urban winter-time aerosols by mobile measurements in Helsinki, Finland

A two-week measurement campaign by a mobile laboratory van was performed in urban environments in the Helsinki metropolitan area, Finland, in winter 2012, to obtain a comprehensive view on aerosol properties and sources. The abundances and physico-chemical properties of particles varied strongly in time and space, depending on the main sources of aerosols. Four major types of winter aerosol were recognized: 1) clean background aerosol with low particle number (Ntot) and lung deposited surface area (LDSA) concentrations due to marine air flows from the Atlantic Ocean; 2) long-range transported (LRT) pollution aerosol due to air flows from eastern Europe where the particles were characterized by the high contribution of oxygenated organic aerosol (OOA) and inorganic species, particularly sulphate, but low BC contribution, and their size distribution possessed an additional accumulation mode; 3) fresh smoke plumes from residential wood combustion in suburban small houses, these particles were characterized by high biomass burning organic aerosol (BBOA) and black carbon (BC) concentrations; and 4) fresh emissions from traffic while driving on busy streets in the city centre and on the highways during morning rush hours. This aerosol was characterized by high concentration of Ntot, LDSA, small particles in the nucleation mode, as well as high hydrocarbon-like organic aerosol (HOA) and BC concentrations. In general, secondary components (OOA, NO3, NH4, and SO4) dominated the PM1 chemical composition during the LRT episode accounting for 70–80% of the PM1 mass, whereas fresh primary emissions (BC, HOA and BBOA) dominated the local traffic and wood burning emissions. The major individual particle types observed with electron microscopy analysis (TEM/EDX) were mainly related to residential wood combustion (K/S/C-rich, soot, other C-rich particles), traffic (soot, Si/Al-rich, Fe-rich), heavy fuel oil combustion in heat plants or ships (S with V-Ni-Fe), LRT pollutants (S/C-rich secondary particles) and sea salt (Na/Cl-rich). Tar balls from wood combustion were also observed, especially (∼5%) during the LRT pollution episode.

Chemical composition, sources and secondary processes of aerosols in Baoji city of northwest China

Particulate air pollution is a severe environmental problem in China, affecting visibility, air quality, climate and human health. However, previous studies focus mainly on large cities such as Beijing, Shanghai, and Guangzhou. In this study, an Aerodyne Aerosol Chemical Speciation Monitor was deployed in Baoji, a middle size inland city in northwest China from 26 February to 27 March 2014. The non-refractory submicron aerosol (NR-PM1) was dominated by organics (55%), followed by sulfate (16%), nitrate (15%), ammonium (11%) and chloride (3%). A source apportionment of the organic aerosol (OA) was performed with the Sofi (Source Finder) interface of ME-2 (Multilinear Engine), and six main sources/factors were identified and classified as hydrocarbon-like OA (HOA), cooking OA (COA), biomass burning OA (BBOA), coal combustion OA (CCOA), less oxidized oxygenated OA (LO-OOA) and more oxidized oxygenated OA (MO-OOA), which contributed 20%, 14%, 13%, 9%, 23% and 21% of total OA, respectively. The contribution of secondary components shows increasing trends from clean days to polluted days, indicating the importance of secondary aerosol formation processes in driving particulate air pollution. The formation of LO-OOA and MO-OOA is mainly driven by photochemical reactions, but significantly influenced by aqueous-phase chemistry during periods of low atmospheric oxidative capacity.

Regional influence of wildfires on aerosol chemistry in the western US and insights into atmospheric aging of biomass burning organic aerosol

Abstract. Biomass burning (BB) is one of the most important contributors to atmospheric aerosols on a global scale, and wildfires are a large source of emissions that impact regional air quality and global climate. As part of the Biomass Burning Observation Project (BBOP) field campaign in summer 2013, we deployed a high-resolution time-of-flight aerosol mass spectrometer (HR-AMS) coupled with a thermodenuder at the Mt. Bachelor Observatory (MBO, ∼ 2.8 km above sea level) to characterize the impact of wildfire emissions on aerosol loading and properties in the Pacific Northwest region of the United States. MBO represents a remote background site in the western US, and it is frequently influenced by transported wildfire plumes during summer. Very clean conditions were observed at this site during periods without BB influence where the 5 min average (±1σ) concentration of non-refractory submicron aerosols (NR-PM1) was 3.7 ± 4.2 µg m−3. Aerosol concentration increased substantially (reaching up to 210 µg m−3 of NR-PM1) for periods impacted by transported BB plumes, and aerosol composition was overwhelmingly organic. Based on positive matrix factorization (PMF) of the HR-AMS data, three types of BB organic aerosol (BBOA) were identified, including a fresh, semivolatile BBOA-1 (O ∕ C = 0.35; 20 % of OA mass) that correlated well with ammonium nitrate; an intermediately oxidized BBOA-2 (O ∕ C = 0.60; 17 % of OA mass); and a highly oxidized BBOA-3 (O ∕ C = 1.06; 31 % of OA mass) that showed very low volatility with only ∼ 40 % mass loss at 200 °C. The remaining 32 % of the OA mass was attributed to a boundary layer (BL) oxygenated OA (BL-OOA; O ∕ C = 0.69) representing OA influenced by BL dynamics and a low-volatility oxygenated OA (LV-OOA; O ∕ C = 1.09) representing regional aerosols in the free troposphere. The mass spectrum of BBOA-3 resembled that of LV-OOA and had negligible contributions from the HR-AMS BB tracer ions – C2H4O2+ (m∕z = 60.021) and C3H5O2+ (m∕z = 73.029); nevertheless, it was unambiguously related to wildfire emissions. This finding highlights the possibility that the influence of BB emission could be underestimated in regional air masses where highly oxidized BBOA (e.g., BBOA-3) might be a significant aerosol component but where primary BBOA tracers, such as levoglucosan, are depleted. We also examined OA chemical evolution for persistent BB plume events originating from a single fire source and found that longer solar radiation led to higher mass fraction of the chemically aged BBOA-2 and BBOA-3 and more oxidized aerosol. However, an analysis of the enhancement ratios of OA relative to CO (ΔOA ∕ΔCO) showed little difference between BB plumes transported primarily at night versus during the day, despite evidence of substantial chemical transformation in OA induced by photooxidation. These results indicate negligible net OA production in photochemically aged wildfire plumes observed in this study, for which a possible reason is that SOA formation was almost entirely balanced by BBOA volatilization. Nevertheless, the formation and chemical transformation of BBOA during atmospheric transport can significantly influence downwind sites with important implications for health and climate.

Sources and atmospheric processing of winter aerosols in Seoul, Korea: insights from real-time measurements using a high-resolution aerosol mass spectrometer

Abstract. Highly time-resolved chemical characterization of nonrefractory submicrometer particulate matter (NR-PM1) was conducted in Seoul, the capital and largest metropolis of Korea, using an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). The measurements were performed during winter, when elevated particulate matter (PM) pollution events are often observed. This is the first time that detailed real-time aerosol measurement results have been reported from Seoul, Korea, and they reveal valuable insights into the sources and atmospheric processes that contribute to PM pollution in this region. The average concentration of submicron aerosol (PM1 = NR-PM1+ black carbon (BC)) was 27.5 µg m−3, and the total mass was dominated by organics (44 %), followed by nitrate (24 %) and sulfate (10 %). The average atomic ratios of oxygen to carbon (O / C), hydrogen to carbon (H / C), and nitrogen to carbon (N / C) of organic aerosols (OA) were 0.37, 1.79, and 0.018, respectively, which result in an average organic mass-to-carbon (OM / OC) ratio of 1.67. The concentrations (2.6–90.7 µg m−3) and composition of PM1 varied dynamically during the measurement period due to the influences of different meteorological conditions, emission sources, and air mass origins. Five distinct sources of OA were identified via positive matrix factorization (PMF) analysis of the HR-ToF-AMS data: vehicle emissions represented by a hydrocarbon-like OA factor (HOA, O / C = 0.06), cooking activities represented by a cooking OA factor (COA, O / C = 0.14), wood combustion represented by a biomass burning OA factor (BBOA, O / C = 0.34), and secondary organic aerosol (SOA) represented by a semivolatile oxygenated OA factor (SV-OOA, O / C = 0.56) and a low-volatility oxygenated OA factor (LV-OOA, O / C = 0.68). On average, primary OA (POA = HOA + COA + BBOA) accounted for 59 % the OA mass, whereas SV-OOA and LV-OOA contributed 15 and 26 %, respectively. Our results indicate that air quality in Seoul during winter is influenced strongly by secondary aerosol formation, with sulfate, nitrate, ammonium, SV-OOA, and LV-OOA together accounting for 64 % of the PM1 mass during this study. However, aerosol sources and composition were found to be significantly different between clean and polluted periods. During stagnant periods with low wind speed (WS) and high relative humidity (RH), PM concentration was generally high (average ±1σ = 43.6 ± 12.4 µg m−3) with enhanced fractions of nitrate (27 %) and SV-OOA (8 %), which suggested a strong influence from local production of secondary aerosol. Low-PM loading periods (12.6 ± 7.1 µg m−3) tended to occur under higher-WS and lower-RH conditions and appeared to be more strongly influenced by regional air masses, as indicated by higher mass fractions of sulfate (12 %) and LV-OOA (20 %) in PM1. Overall, our results indicate that PM pollutants in urban Korea originate from complex emission sources and atmospheric processes and that their concentrations and composition are controlled by various factors, including meteorological conditions, local anthropogenic emissions, and upwind sources.

Chemical characterization of submicron aerosol particles during wintertime in a northwest city of China using an Aerodyne aerosol mass spectrometry

An Aerodyne quadrupole aerosol mass spectrometry (Q-AMS) was utilized to measure the size-resolved chemical composition of non-refractory submicron particles (NR-PM1) from October 27 to December 3, 2014 at an urban site in Lanzhou, northwest China. The average NR-PM1 mass concentration was 37.3 μg m−3 (ranging from 2.9 to 128.2 μg m−3) under an AMS collection efficiency of unity and was composed of organics (48.4%), sulfate (17.8%), nitrate (14.6%), ammonium (13.7%), and chloride (5.7%). Positive matrix factorization (PMF) with the multi-linear engine (ME-2) solver identified six organic aerosol (OA) factors, including hydrocarbon-like OA (HOA), coal combustion OA (CCOA), cooking-related OA (COA), biomass burning OA (BBOA) and two oxygenated OA (OOA1 and OOA2), which accounted for 8.5%, 20.2%, 18.6%, 12.4%, 17.8% and 22.5% of the total organics mass on average, respectively. Primary emissions were the major sources of fine particulate matter (PM) and played an important role in causing high chemically resolved PM pollution during wintertime in Lanzhou. Back trajectory analysis indicated that the long-range regional transport air mass from the westerly was the key factor that led to severe submicron aerosol pollution during wintertime in Lanzhou.

Argon offline-AMS source apportionment of organic aerosol over yearly cycles for an urban, rural, and marine site in northern Europe

Abstract. The widespread use of Aerodyne aerosol mass spectrometers (AMS) has greatly improved real-time organic aerosol (OA) monitoring, providing mass spectra that contain sufficient information for source apportionment. However, AMS field deployments remain expensive and demanding, limiting the acquisition of long-term datasets at many sampling sites. The offline application of aerosol mass spectrometry entailing the analysis of nebulized water extracted filter samples (offline-AMS) increases the spatial coverage accessible to AMS measurements, being filters routinely collected at many stations worldwide. PM1 (particulate matter with an aerodynamic diameter < 1 µm) filter samples were collected during an entire year in Lithuania at three different locations representative of three typical environments of the southeast Baltic region: Vilnius (urban background), Rūgšteliškis (rural terrestrial), and Preila (rural coastal). Aqueous filter extracts were nebulized in Ar, yielding the first AMS measurements of water-soluble atmospheric organic aerosol (WSOA) without interference from air fragments. This enables direct measurement of the CO+ fragment contribution, whose intensity is typically assumed to be equal to that of CO2+. Offline-AMS spectra reveal that the water-soluble CO2+ : CO+ ratio not only shows values systematically > 1 but is also dependent on season, with lower values in winter than in summer. AMS WSOA spectra were analyzed using positive matrix factorization (PMF), which yielded four factors. These factors included biomass burning OA (BBOA), local OA (LOA) contributing significantly only in Vilnius, and two oxygenated OA (OOA) factors, summer OOA (S-OOA) and background OOA (B-OOA), distinguished by their seasonal variability. The contribution of traffic exhaust OA (TEOA) was not resolved by PMF due to both low concentrations and low water solubility. Therefore, the TEOA concentration was estimated using a chemical mass balance approach, based on the concentrations of hopanes, specific markers of traffic emissions. AMS-PMF source apportionment results were consistent with those obtained from PMF applied to marker concentrations (i.e., major inorganic ions, OC / EC, and organic markers including polycyclic aromatic hydrocarbons and their derivatives, hopanes, long-chain alkanes, monosaccharides, anhydrous sugars, and lignin fragmentation products). OA was the largest fraction of PM1 and was dominated by BBOA during winter with an average concentration of 2 µg m−3 (53 % of OM), while S-OOA, probably related to biogenic emissions, was the prevalent OA component during summer with an average concentration of 1.2 µg m−3 (45 % of OM). PMF ascribed a large part of the CO+ explained variability (97 %) to the OOA and BBOA factors. Accordingly, we discuss a new CO+ parameterization as a function of CO2+ and C2H4O2+ fragments, which were selected to describe the variability of the OOA and BBOA factors.

Chemical Characterization of Water-Soluble Organic Aerosol in Contrasting Rural and Urban Environments in the Southeastern United States.

We developed a novel system for direct and online characterization of water-solubility of organic aerosol (OA) by coupling a Particle Into Liquid Sampler (PILS) to a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). We showed that approximately 88% and 77% of OA are water-soluble in rural Centreville, Alabama and urban Atlanta, Georgia, respectively. The water-solubility of OA factors, resolved with Positive Matrix Factorization analysis of AMS data, is directly investigated for the first time. Above 80% of isoprene-derived OA is water-soluble and its water-soluble fraction has the least variability among all OA factors. This is consistent with that the majority of this factor represents OA formed through the aqueous-phase reaction of isoprene epoxydiols. More-oxidized oxygenated OA is dominantly water-soluble, consistent with this factor representing highly oxidized compounds. Less-oxidized oxygenated OA has the lowest water-solubility among all secondary OA factors, which agrees with the hypothesis that this factor in the southeastern U.S. includes contributions from organic nitrates. While hydrocarbon-like OA is largely water-insoluble, biomass burning OA and cooking OA have the largest range of water-soluble fraction. This study on the water-solubility of OA factors provides insights for interpretation of OA factors and improves understanding of the complex OA sources in the atmosphere.

Organic aerosol source apportionment in London 2013 with ME-2: exploring the solution space with annual and seasonal analysis

Abstract. The multilinear engine (ME-2) factorization tool is being widely used following the recent development of the Source Finder (SoFi) interface at the Paul Scherrer Institute. However, the success of this tool, when using the a value approach, largely depends on the inputs (i.e. target profiles) applied as well as the experience of the user. A strategy to explore the solution space is proposed, in which the solution that best describes the organic aerosol (OA) sources is determined according to the systematic application of predefined statistical tests. This includes trilinear regression, which proves to be a useful tool for comparing different ME-2 solutions. Aerosol Chemical Speciation Monitor (ACSM) measurements were carried out at the urban background site of North Kensington, London from March to December 2013, where for the first time the behaviour of OA sources and their possible environmental implications were studied using an ACSM. Five OA sources were identified: biomass burning OA (BBOA), hydrocarbon-like OA (HOA), cooking OA (COA), semivolatile oxygenated OA (SVOOA) and low-volatility oxygenated OA (LVOOA). ME-2 analysis of the seasonal data sets (spring, summer and autumn) showed a higher variability in the OA sources that was not detected in the combined March–December data set; this variability was explored with the triangle plots f44 : f43 f44 : f60, in which a high variation of SVOOA relative to LVOOA was observed in the f44 : f43 analysis. Hence, it was possible to conclude that, when performing source apportionment to long-term measurements, important information may be lost and this analysis should be done to short periods of time, such as seasonally. Further analysis on the atmospheric implications of these OA sources was carried out, identifying evidence of the possible contribution of heavy-duty diesel vehicles to air pollution during weekdays compared to those fuelled by petrol.

Atmospheric aerosols in Rome, Italy: sources, dynamics and spatial variations during two seasons

Abstract. Investigations on atmospheric aerosols and their sources were carried out in October/November 2013 and May/June 2014 consecutively in a suburban area of Rome (Tor Vergata) and in central Rome (near St Peter's Basilica). During both years a Saharan dust advection event temporarily increased PM10 concentrations at ground level by about 12–17 µg m−3. Generally, in October/November the ambient aerosol was more strongly influenced by primary emissions, whereas higher relative contributions of secondary particles (sulfate, aged organic aerosol) were found in May/June. Absolute concentrations of anthropogenic emission tracers (e.g. NOx, CO2, particulate polycyclic aromatic hydrocarbons, traffic-related organic aerosol) were generally higher at the urban location. Positive matrix factorization was applied to the PM1 organic aerosol (OA) fraction of aerosol mass spectrometer (HR-ToF-AMS) data to identify different sources of primary OA (POA): traffic, cooking, biomass burning and (local) cigarette smoking. While biomass burning OA was only found at the suburban site, where it accounted for the major fraction of POA (18–24 % of total OA), traffic and cooking were more dominant sources at the urban site. A particle type associated with cigarette smoke emissions, which is associated with a potential characteristic marker peak (m∕z 84, C5H10N+, a nicotine fragment) in the mass spectrum, was only found in central Rome, where it was emitted in close vicinity to the measurement location. Regarding secondary OA, in October/November, only a very aged, regionally advected oxygenated OA was found, which contributed 42–53 % to the total OA. In May/June total oxygenated OA accounted for 56–76 % of the OA. Here a fraction (18–26 % of total OA) of a fresher, less oxygenated OA of more local origin was also observed. New particle formation events were identified from measured particle number concentrations and size distributions in May/June 2014 at both sites. While they were observed every day at the urban location, at the suburban location they were only found under favourable meteorological conditions, but were independent of advection of the Rome emission plume. Particles from sources in the metropolitan area of Rome and particles advected from outside Rome contributed 42–70 and 30–58 % to the total measured PM1, respectively. Apart from the general aerosol characteristics, in this study the properties (e.g. emission strength) and dynamics (e.g. temporal behaviour) of each identified aerosol type is investigated in detail to provide a better understanding of the observed seasonal and spatial differences.

Wintertime organic and inorganic aerosols in Lanzhou, China: sources, processes, and comparison with the results during summer

Abstract. Lanzhou, which is located in a steep alpine valley in western China, is one of the most polluted cities in China during the wintertime. In this study, an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), a seven-wavelength aethalometer, and a scanning mobility particle sizer (SMPS) were deployed during 10 January to 4 February 2014 to study the mass concentrations, chemical processes, and sources of submicrometer particulate matter (PM1). The average PM1 concentration during this study was 57.3 µg m−3 (ranging from 2.1 to 229.7 µg m−3 for hourly averages), with organic aerosol (OA) accounting for 51.2 %, followed by nitrate (16.5 %), sulfate (12.5 %), ammonium (10.3 %), black carbon (BC, 6.4 %), and chloride (3.0 %). The mass concentration of PM1 during winter was more than twice the average value observed at the same site in summer 2012 (24.5 µg m−3), but the mass fraction of OA was similar in the two seasons. Nitrate contributed a significantly higher fraction to the PM1 mass in winter than summer (16.5 % vs. 10 %), largely due to more favored partitioning to the particle phase at low air temperature. The mass fractions of both OA and nitrate increased by ∼ 5 % (47 to 52 for OA and 13 to 18 % for nitrate) with the increase of the total PM1 mass loading, while the average sulfate fraction decreased by 6 % (17 to 11 %), indicating the importance of OA and nitrate for the heavy air pollution events in Lanzhou. The size distributions of OA, nitrate, sulfate, ammonium, and chloride all peaked at ∼ 500 nm, with OA being slightly broader, suggesting that aerosol particles were internally mixed during winter, likely due to frequently calm and stagnant air conditions during wintertime in Lanzhou (average wind speed: 0.82 m s−1).The average mass spectrum of OA showed a medium oxidation degree (average O ∕ C ratio of 0.28), which was lower than that during summer 2012 (O ∕ C = 0.33). This is consistent with weaker photochemical processing during winter. Positive matrix factorization (PMF) with the multi-linear engine (ME-2) solver identified six OA sources, i.e., a hydrocarbon-like OA (HOA), a biomass burning OA (BBOA), a cooking-emitted OA (COA), a coal combustion OA (CCOA), and two oxygenated OA (OOA) factors. One of the OOAs was less oxidized (LO-OOA), and the other one more oxidized (MO-OOA). LO-OOA was the most abundant OA component (22.3 % of OA mass), followed by CCOA (22.0 %), COA (20.2 %), MO-OOA (14.9 %), BBOA (10.8 %), and HOA (9.8 %). The mass fraction of primary OA ( = HOA + BBOA + COA + CCOA) increased during high PM pollution periods, indicating that local primary emissions were a main reason for the formation of air pollution events in Lanzhou during winter. Radiocarbon (14C) measurement was conducted on four PM2.5 filter samples from this study, which allowed for a quantitative source apportionment of organic carbon (OC). The non-fossil sources on average accounted for 55 ± 3 % of OC, which could be mainly from biomass burning and cooking activities, suggesting the importance of non-fossil sources for the PM pollution in Lanzhou. Together with the PMF results, we also found that a large fraction (66 ± 10 %) of the secondary OC was from non-fossil OC.

Characterization of submicron aerosols influenced by biomass burning at a site in the Sichuan Basin, southwestern China

Abstract. Severe air pollution in Asia is often the consequence of a combination of large anthropogenic emissions and adverse synoptic conditions. However, limited studies on aerosols have been conducted under high emission intensity and under unique geographical and meteorological conditions. In this study, an Aerodyne high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS) and other state-of-the-art instruments were utilized at a suburban site, Ziyang, in the Sichuan Basin during December 2012 to January 2013. The chemical compositions of atmospheric submicron aerosols (PM1) were determined, the sources of organic aerosols (OA) were apportioned, and the aerosol secondary formation and aging process were explored as well. Due to high humidity and static air, PM1 maintained a relatively stable level during the whole campaign, with the mean concentration of 59.7 ± 24.1 µg m−3. OA was the most abundant component (36 %) in PM1, characterized by a relatively high oxidation state. Positive matrix factorization analysis was applied to the high-resolution organic mass spectral matrix, which deconvolved OA mass spectra into four factors: low-volatility (LV-OOA) and semivolatile oxygenated OA (SV-OOA), biomass burning (BBOA) and hydrocarbon-like OA (HOA). OOA (sum of LV-OOA and SV-OOA) dominated OA as high as 71 %. In total, secondary inorganic and organic formation contributed 76 % of PM1. Secondary inorganic species correlated well (Pearson r = 0.415–0.555, p < 0.01) with relative humidity (RH), suggesting the humid air can favor the formation of secondary inorganic aerosols. As the photochemical age of OA increased with higher oxidation state, secondary organic aerosol formation contributed more to OA. The slope of OOA against Ox( = O3+NO2) steepened with the increase of RH, implying that, besides the photochemical transformation, the aqueous-phase oxidation was also an important pathway of the OOA formation. Primary emissions, especially biomass burning, resulted in high concentration and proportion of black carbon (BC) in PM1. During the episode obviously influenced by primary emissions, the contributions of BBOA to OA (26 %) and PM1 (11 %) were much higher than those (10–17 %, 4–7 %) in the clean and other polluted episodes, highlighting the significant influence of biomass burning.

Molecular Characterization of Brown Carbon in Biomass Burning Aerosol Particles.

Emissions from biomass burning are a significant source of brown carbon (BrC) in the atmosphere. In this study, we investigate the molecular composition of freshly emitted biomass burning organic aerosol (BBOA) samples collected during test burns of sawgrass, peat, ponderosa pine, and black spruce. We demonstrate that both the BrC absorption and the chemical composition of light-absorbing compounds depend significantly on the type of biomass fuels. Common BrC chromophores in the selected BBOA samples include nitro-aromatics, polycyclic aromatic hydrocarbon derivatives, and polyphenols spanning a wide range of molecular weights, structures, and light absorption properties. A number of biofuel-specific BrC chromophores are observed, indicating that some of them may be used as source-specific markers of BrC. On average, ∼50% of the light absorption in the solvent-extractable fraction of BBOA can be attributed to a limited number of strong BrC chromophores. The absorption coefficients of BBOA are affected by solar photolysis. Specifically, under typical atmospheric conditions, the 300 nm absorbance decays with a half-life of ∼16 h. A "molecular corridor" analysis of the BBOA volatility distribution suggests that many BrC compounds in the fresh BBOA have low saturation mass concentration (<1 μg m-3) and will be retained in the particle phase under atmospherically relevant conditions.

Variations in the chemical composition of the submicron aerosol and in the sources of the organic fraction at a regional background site of the Po Valley (Italy)

Abstract. Fine particulate matter (PM) levels and resulting impacts on human health are in the Po Valley (Italy) among the highest in Europe. To build effective PM abatement strategies, it is necessary to characterize fine PM chemical composition, sources and atmospheric processes on long timescales (&gt; months), with short time resolution (&lt; day), and with particular emphasis on the predominant organic fraction. Although previous studies have been conducted in this region, none of them addressed all these aspects together. For the first time in the Po Valley, we investigate the chemical composition of nonrefractory submicron PM (NR-PM1) with a time resolution of 30 min at the regional background site of Ispra during 1 full year, using the Aerodyne Aerosol Chemical Speciation Monitor (ACSM) under the most up-to-date and stringent quality assurance protocol. The identification of the main components of the organic fraction is made using the Multilinear-Engine 2 algorithm implemented within the latest version of the SoFi toolkit. In addition, with the aim of a potential implementation of ACSM measurements in European air quality networks as a replacement of traditional filter-based techniques, parallel multiple offline analyses were carried out to assess the performance of the ACSM in the determination of PM chemical species regulated by air quality directives. The annual NR-PM1 level monitored at the study site (14.2 µg m−3) is among the highest in Europe and is even comparable to levels reported in urban areas like New York City and Tokyo. On the annual basis, submicron particles are primarily composed of organic aerosol (OA, 58 % of NR-PM1). This fraction was apportioned into oxygenated OA (OOA, 66 %), hydrocarbon-like OA (HOA, 11 % of OA) and biomass burning OA (BBOA, 23 %). Among the primary sources of OA, biomass burning (23 %) is thus bigger than fossil fuel combustion (11 %). Significant contributions of aged secondary organic aerosol (OOA) are observed throughout the year. The unexpectedly high degree of oxygenation estimated during wintertime is probably due to the contribution of secondary BBOA and the enhancement of aqueous-phase production of OOA during cold months. BBOA and nitrate are the only components of which contributions increase with the NR-PM1 levels. Therefore, biomass burning and NOx emission reductions would be particularly efficient in limiting submicron aerosol pollution events. Abatement strategies conducted during cold seasons appear to be more efficient than annual-based policies. In a broader context, further studies using high-time-resolution analytical techniques on a long-term basis for the characterization of fine aerosol should help better shape our future air quality policies, which constantly need refinement.

Detection of Saharan dust and biomass burning events using near-real-time intensive aerosol optical properties in the north-western Mediterranean

Abstract. The study of Saharan dust events (SDEs) and biomass burning (BB) emissions are both topics of great scientific interest since they are frequent and important polluting scenarios affecting air quality and climate. The main aim of this work is evaluating the feasibility of using near-real-time in situ aerosol optical measurements for the detection of these atmospheric events in the western Mediterranean Basin (WMB). With this aim, intensive aerosol optical properties (SAE: scattering Ångström exponent, AAE: absorption Ångström exponent, SSAAE: single scattering albedo Ångström exponent and g: asymmetry parameter) were derived from multi-wavelength aerosol light scattering, hemispheric backscattering and absorption measurements performed at regional (Montseny; MSY, 720 m a.s.l.) and continental (Montsec; MSA, 1570 m a.s.l.) background sites in the WMB. A sensitivity study aiming at calibrating the measured intensive optical properties for SDEs and BB detection is presented and discussed. The detection of SDEs by means of the SSAAE parameter and Ångström matrix (made up by SAE and AAE) depended on the altitude of the measurement station and on SDE intensity. At MSA (mountain-top site) SSAAE detected around 85 % of SDEs compared with 50 % at the MSY station, where pollution episodes dominated by fine anthropogenic particles frequently masked the effect of mineral dust on optical properties during less intense SDEs. Furthermore, an interesting feature of SSAAE was its capability to detect the presence of mineral dust after the end of SDEs. Thus, resuspension processes driven by summer regional atmospheric circulations and dry conditions after SDEs favoured the accumulation of mineral dust at regional level having important consequences for air quality. On average, SAE, AAE and g ranged between −0.7 and 1, 1.3 and 2.5 and 0.5 and 0.75 respectively during SDEs. Based on the aethalometer model, BB contribution to equivalent black carbon (BC) accounted for 36 and 40 % at MSY and MSA respectively. Linear relationships were found between AAE and %BCbb, with AAE values reaching around 1.5 when %BCbb was higher than 50 %. BB contribution to organic matter (OM) at MSY was around 30 %. Thus fossil fuel (FF) combustion sources showed important contributions to both BC and OM in the region under study. Results for OM source apportionment showed good agreement with simultaneous biomass burning organic aerosol (BBOA) and hydrocarbon-like organic aerosol (HOA) obtained by applying a positive matrix factorization model (PMF) to simultaneous Aerosol Chemical Speciation Monitor (ACSM) measurements. A wildfire episode was identified at MSY, showing AAE values up to 2 when daily BB contributions to BC and OM were 73 and 78 % respectively.

Regional Influence of Aerosol Emissions from Wildfires Driven by Combustion Efficiency: Insights from the BBOP Campaign

Wildfires are important contributors to atmospheric aerosols and a large source of emissions that impact regional air quality and global climate. In this study, the regional and nearfield influences of wildfire emissions on ambient aerosol concentration and chemical properties in the Pacific Northwest region of the United States were studied using real-time measurements from a fixed ground site located in Central Oregon at the Mt. Bachelor Observatory (∼2700 m a.s.l.) as well as near their sources using an aircraft. The regional characteristics of biomass burning aerosols were found to depend strongly on the modified combustion efficiency (MCE), an index of the combustion processes of a fire. Organic aerosol emissions had negative correlations with MCE, whereas the oxidation state of organic aerosol increased with MCE and plume aging. The relationships between the aerosol properties and MCE were consistent between fresh emissions (∼1 h old) and emissions sampled after atmospheric transport (6-45 h), suggesting that biomass burning organic aerosol concentration and chemical properties were strongly influenced by combustion processes at the source and conserved to a significant extent during regional transport. These results suggest that MCE can be a useful metric for describing aerosol properties of wildfire emissions and their impacts on regional air quality and global climate.

Deriving aerosol hygroscopic mixing state from size-resolved CCN activity and HR-ToF-AMS measurements

The ability of a particle to uptake water and form a cloud droplet depends on its hygroscopicity. To understand its impact on cloud properties and ultimately radiative forcing, knowledge of chemically-resolved mixing state information or the one based on hygroscopic growth is crucial. Typically, global models assume either pure internal or external mixing state which might not be true for all conditions and sampling locations. To investigate into this, the current study employed an indirect approach to infer the probable mixing state. The hygroscopic parameters derived from κ-Kohler theory using size-resolved CCN measurements (κCCN) and bulk/size-resolved aerosol mass spectrometer (AMS) measurements (κAMS) were compared. The accumulation mode particles were found to be more hygroscopic (κCCN = 0.24) than Aitken mode (κCCN = 0.13), perhaps due to increased ratio of inorganic to organic mass fraction. The activation diameter calculated from size-resolved CCN activity measurements at 5 different supersaturation (SS) levels varied in the range of 115 nm–42 nm with κCCN = 0.13–0.23 (avg = 0.18 ± 0.10 (±1σ)). Further, κAMS>κCCN was observed possibly due to the fact that organic and inorganic mass present in the Aitken mode was not correctly represented by bulk chemical composition and size-resolved fractional contribution of oxidized OA was not accurately accounted. Better correlation of organic fraction (forg) and κCCN at lower SS explained this behaviour. The decrease in κCCN with the time of the day was more pronounced at lower SS because of the relative mass reduction of soluble inorganic species by ∼17%.Despite the large differences between κ measured from two approaches, less over-prediction (up to 18%) between measured and predicted CCN concentration suggested lower impact of chemical composition and mixing state at higher SS. However, at lower SS, presences of externally mixed CCN-inactive aerosols lead to CCN over-prediction reflecting the significance of aerosol mixing state information. Further examination of the effect of biomass burning aerosols (∼35% in least oxidized biomass burning organic aerosol (BBOA-2 fraction) on hygroscopicity and CCN activity showed increase in the concentration of all AMS measured species (except NH4+ and SO42−), less O:C ratio, and organic mass fraction (forg) peak shift to lower diameter range caused ∼13% change in critical diameter (Da) and ∼40% change in κCCN. Increased deviation of ∼100% between κCCN and κAMS due to sudden influx of internally mixed BBOA caused suppressed hygroscopic growth. This study finally suggests the assumption of pure internally mixed aerosol does not completely hold true for this anthropogenically polluted site.

Biomass-burning impact on CCN number, hygroscopicity and cloud formation during summertime in the eastern Mediterranean

Abstract. This study investigates the concentration, cloud condensation nuclei (CCN) activity and hygroscopic properties of particles influenced by biomass burning in the eastern Mediterranean and their impacts on cloud droplet formation. Air masses sampled were subject to a range of atmospheric processing (several hours up to 3 days). Values of the hygroscopicity parameter, κ, were derived from CCN measurements and a Hygroscopic Tandem Differential Mobility Analyzer (HTDMA). An Aerosol Chemical Speciation Monitor (ACSM) was also used to determine the chemical composition and mass concentration of non-refractory components of the submicron aerosol fraction. During fire events, the increased organic content (and lower inorganic fraction) of the aerosol decreases the values of κ, for all particle sizes. Particle sizes smaller than 80 nm exhibited considerable chemical dispersion (where hygroscopicity varied up to 100 % for particles of same size); larger particles, however, exhibited considerably less dispersion owing to the effects of condensational growth and cloud processing. ACSM measurements indicate that the bulk composition reflects the hygroscopicity and chemical nature of the largest particles (having a diameter of ∼ 100 nm at dry conditions) sampled. Based on positive matrix factorization (PMF) analysis of the organic ACSM spectra, CCN concentrations follow a similar trend as the biomass-burning organic aerosol (BBOA) component, with the former being enhanced between 65 and 150 % (for supersaturations ranging between 0.2 and 0.7 %) with the arrival of the smoke plumes. Using multilinear regression of the PMF factors (BBOA, OOA-BB and OOA) and the observed hygroscopicity parameter, the inferred hygroscopicity of the oxygenated organic aerosol components is determined. We find that the transformation of freshly emitted biomass burning (BBOA) to more oxidized organic aerosol (OOA-BB) can result in a 2-fold increase of the inferred organic hygroscopicity; about 10 % of the total aerosol hygroscopicity is related to the two biomass-burning components (BBOA and OOA-BB), which in turn contribute almost 35 % to the fine-particle organic water of the aerosol. Observation-derived calculations of the cloud droplet concentrations that develop for typical boundary layer cloud conditions suggest that biomass burning increases droplet number, on average by 8.5 %. The strongly sublinear response of clouds to biomass-burning (BB) influences is a result of strong competition of CCN for water vapor, which results in very low maximum supersaturation (0.08 % on average). Attributing droplet number variations to the total aerosol number and the chemical composition variations shows that the importance of chemical composition increases with distance, contributing up to 25 % of the total droplet variability. Therefore, although BB may strongly elevate CCN numbers, the impact on droplet number is limited by water vapor availability and depends on the aerosol particle concentration levels associated with the background.

Urban increments of gaseous and aerosol pollutants and their sources using mobile aerosol mass spectrometry measurements

Abstract. Air pollution is one of the main environmental concerns in urban areas, where anthropogenic emissions strongly affect air quality. This work presents the first spatially resolved detailed characterization of PM2.5 (particulate matter with aerodynamic equivalent diameter daero ≤ 2.5 µm) in two major Estonian cities, Tallinn and Tartu. The measurements were performed in March 2014 using a mobile platform. In both cities, the non-refractory (NR)-PM2.5 was characterized by a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) using a recently developed lens which increases the transmission of super-micron particles. Equivalent black carbon (eBC) and several trace gases including carbon monoxide (CO), carbon dioxide (CO2), and methane (CH4) were also measured. The chemical composition of PM2.5 was found to be very similar in the two cities. Organic aerosol (OA) constituted the largest fraction, explaining on average about 52 to 60 % of the PM2.5 mass. Four sources of OA were identified using positive matrix factorization (PMF): hydrocarbon-like OA (HOA, from traffic emissions), biomass burning OA (BBOA, from biomass combustion), residential influenced OA (RIOA, probably mostly from cooking processes with possible contributions from waste and coal burning), and oxygenated OA (OOA, related to secondary aerosol formation). OOA was the major OA source during nighttime, explaining on average half of the OA mass, while during daytime mobile measurements the OA was affected by point sources and dominated by the primary fraction. A strong increase in the secondary organic and inorganic components was observed during periods with transport of air masses from northern Germany, while the primary local emissions accumulated during periods with temperature inversions. Mobile measurements offered the identification of different source regions within the urban areas and the assessment of the extent to which pollutants concentrations exceeded regional background levels (urban increments). HOA, eBC, CO2, and CO showed stronger enhancements on busy roads during the morning and evening traffic rush hours; BBOA had its maximum enhancement in the residential areas during the evening hours and RIOA was enhanced in both the city center (emissions from restaurants) and in the residential areas (emissions from residential cooking). In contrast, secondary components (OOA, sulfate (SO4), nitrate (NO3), ammonium (NH4), and chloride (Cl)) had very homogeneous distributions in time and space. We were able to determine a total PM2.5 urban increment in Tartu of 6.0 µg m−3 over a regional background concentration of 4.0 µg m−3 (i.e., a factor of 2.5 increase). Traffic exhaust emissions were identified as the most important source of this increase, with eBC and HOA explaining on average 53.3 and 20.5 % of the total increment, respectively.