High-resolution Time-of-flight Aerosol Mass Spectrometer Research Articles

Atmospheric aerosol compositions and sources at two national background sites in northern and southern China

Abstract. Although China's severe air pollution has become a focus in the field of atmospheric chemistry and the mechanisms of urban air pollution there have been researched extensively, few field sampling campaigns have been conducted at remote background sites in China, where air pollution characteristics on a larger scale are highlighted. In this study, an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), together with an Aethalometer, was deployed at two of China's national background sites in northern (Lake Hongze site; 33.23° N, 118.33° E; altitude 21 m) and southern (Mount Wuzhi site; 18.84° N, 109.49° E; altitude 958 m) China in the spring seasons in 2011 and 2015, respectively, in order to characterize submicron aerosol composition and sources. The campaign-average PM1 concentration was 36.8 ± 19.8 µg m−3 at the northern China background (NCB) site, which was far higher than that at the southern China background (SCB) site (10.9 ± 7.8 µg m−3). Organic aerosol (OA) (27.2 %), nitrate (26.7 %), and sulfate (22.0 %) contributed the most to the PM1 mass at NCB, while OA (43.5 %) and sulfate (30.5 %) were the most abundant components of the PM1 mass at SCB, where nitrate only constituted a small fraction (4.7 %) and might have contained a significant amount of organic nitrates (5–11 %). The aerosol size distributions and organic aerosol elemental compositions all indicated very aged aerosol particles at both sites. The OA at SCB was more oxidized with a higher average oxygen to carbon (O ∕ C) ratio (0.98) than that at NCB (0.67). Positive matrix factorization (PMF) analysis was used to classify OA into three components, including a hydrocarbon-like component (HOA, attributed to fossil fuel combustion) and two oxygenated components (OOA1 and OOA2, attributed to secondary organic aerosols from different source areas) at NCB. PMF analysis at SCB identified a semi-volatile oxygenated component (SV-OOA) and a low-volatility oxygenated component (LV-OOA), both of which were found to be secondary species and could be formed from precursors co-emitted with BC. Using the total potential source contribution function model, the likely source areas of the major PM1 components at both sites were a on large regional scale in East Asia. The possible sources may include not only emissions from the Chinese mainland but also emissions from ocean-going cargo ships and biomass burning in neighboring countries.

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.

Influences of emission sources and meteorology on aerosol chemistry in a polluted urban environment: results from DISCOVER-AQ California

Abstract. The San Joaquin Valley (SJV) in California experiences persistent air-quality problems associated with elevated particulate matter (PM) concentrations due to anthropogenic emissions, topography, and meteorological conditions. Thus it is important to unravel the various sources and processes that affect the physicochemical properties of PM in order to better inform pollution abatement strategies and improve parameterizations in air-quality models. During January and February 2013, a ground supersite was installed at the Fresno–Garland California Air Resources Board (CARB) monitoring station, where comprehensive, real-time measurements of PM and trace gases were performed using instruments including an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and an Ionicon proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) as part of the NASA Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) campaign. The average submicron aerosol (PM1) concentration was 31.0 µg m−3 and the total mass was dominated by organic aerosols (OA, 55 %), followed by ammonium nitrate (35 %). High PM pollution events were commonly associated with elevated OA concentrations, mostly from primary sources. Organic aerosols had average atomic oxygen-to-carbon (O / C), hydrogen-to-carbon (H / C), and nitrogen-to-carbon (N / C) ratios of 0.42, 1.70, and 0.017, respectively. Six distinct sources of organic aerosol were identified from positive matrix factorization (PMF) analysis of the AMS data: hydrocarbon-like OA (HOA; 9 % of total OA, O / C = 0.09) associated with local traffic, cooking OA (COA; 18 % of total OA, O / C = 0.19) associated with food cooking activities, two biomass burning OA (BBOA1: 13 % of total OA, O / C = 0.33; BBOA2: 20 % of total OA, O / C = 0.60) most likely associated with residential space heating from wood combustion, and semivolatile oxygenated OA (SV-OOA; 16 % of total OA, O / C = 0.63) and low-volatility oxygenated OA (LV-OOA; 24 % of total OA, O / C = 0.90) formed via chemical reactions in the atmosphere. Large differences in aerosol chemistry at Fresno were observed between the current campaign (winter 2013) and a previous campaign in winter 2010, most notably that PM1 concentrations were nearly 3 times higher in 2013 than in 2010. These variations were attributed to differences in the meteorological conditions, which influenced primary emissions and secondary aerosol formation. In particular, COA and BBOA concentrations were greater in 2013 than 2010, where colder temperatures in 2013 likely resulted in increased biomass burning activities. The influence from a nighttime formed residual layer that mixed down in the morning was found to be much more intense in 2013 than 2010, leading to sharp increases in ground-level concentrations of secondary aerosol species including nitrate, sulfate, and OOA, in the morning between 08:00 and 12:00 PST. This is an indication that nighttime chemical reactions may have played a more important role in 2013. As solar radiation was stronger in 2013 the higher nitrate and OOA concentrations in 2013 could also be partly due to greater photochemical production of secondary aerosol species. The greater solar radiation and larger range in temperature in 2013 also likely led to both SV-OOA and LV-OOA being observed in 2013 whereas only a single OOA factor was identified in 2010.

Characterization of submicron particles during biomass burning and coal combustion periods in Beijing, China

An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed along with other observation instruments to measure the characteristics of PM1 (particulate matter with a vacuum aerodynamic diameter of ≤1μm) during the biomass burning period (October 1 to 27; BBP) and the coal combustion period (December 10 to 31; CCP) in Beijing in 2014. The average PM1 mass concentrations during the BBP and CCP were 82.3 and 37.5μgm−3, respectively. Nitrate, ammonium and other pollutants emitted by the burning processes, especially coal combustion, increased significantly in association with increased pollution levels. Positive matrix factorization (PMF) was applied to a unified high-resolution mass spectra database of organic species with NO+ and NO2+ ions to discover the relationships between organic and inorganic species. One inorganic factor was identified in both periods, and another five and four distinct organic factors were identified in the BBP and CCP, respectively. Secondary organic aerosols (SOAs) accounted for 55% of the total organic aerosols (OAs) during the BBP, which is higher than the proportion during the CCP (oxygenated OA, 40%). The organic nitrate and inorganic nitrate were first successfully separated through the PMF analysis based on the HR-ToF-AMS observations in Beijing, and organic nitrate components accounted for 21% and 18% of the total nitrate mass during the BBP and CCP, respectively. Although the PM1 mass concentration during the CCP was much lower than in the BBP, the average concentration of polycyclic aromatic hydrocarbons (PAHs) during the CCP (107.3±171.6ngm−3) was ~5 times higher than that in the BBP (21.9±21.7ngm−3).

Comparison of Chemical Composition of Particulate Matter Emitted from a Gasoline Direct Injected (GDI) Vehicle and a Port Fuel Injected (PFI) Vehicle using High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS)

Particulate matter (PM) in the atmosphere has wideranging health, environmental, and climate effects, many of which are attributed to fine-mode secondary organic aerosols. PM concentrations are significantly enhanced by primary particle emissions from traffic sources. Recently, in order to reduce CO₂ and increase fuel economy, gasoline direct injected (GDI) engine technology is increasingly used in vehicle manufactures. The popularization of GDI technique has resulted in increasing of concerns on environmental protection. In order to better understand variations in chemical composition of particulate matter from emissions of GDI vehicle versus a port fuel injected (PFI) vehicle, a high time resolution chemical composition of PM emissions from GDI and PFI vehicles was measured at facility of Transport Pollution Research Center (TPRC), National Institute of Environmental Research (NIER), Korea. Continuous measurements of inorganic and organic species in PM were conducted using an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToFAMS). The HR-ToF-AMS provides insight into nonrefractory PM composition, including concentrations of nitrate, sulfate, hydrocarbon-like and oxygenated organic aerosol, and organic mass with 20 sec time resolution. Many cases of PM emissions during the study were dominated by organic and nitrate aerosol. An overview of observed PM characteristics will be provided along with an analysis of comparison of GDI vehicle versus PFI vehicle in PM emission rates and oxidation states.

Chemical composition, sources, and aging process of submicron aerosols in Beijing: Contrast between summer and winter

AbstractTo investigate the seasonal characteristics of submicron aerosol (PM1) in Beijing urban areas, a high‐resolution time‐of‐flight aerosol‐mass‐spectrometer (HR‐ToF‐AMS) was utilized at an urban site in summer (August to September 2011) and winter (November to December 2010), coupled with multiple state of the art online instruments. The average mass concentrations of PM1 (60–84 µg m−3) and its chemical compositions in different campaigns of Beijing were relatively consistent in recent years. In summer, the daily variations of PM1 mass concentrations were stable and repeatable. Eighty‐two percent of the PM1 mass concentration on average was composed of secondary species, where 62% is secondary inorganic aerosol and 20% secondary organic aerosol (SOA). In winter, PM1 mass concentrations changed dramatically because of the different meteorological conditions. The high average fraction (58%) of primary species in PM1 including primary organic aerosol (POA), black carbon, and chloride indicates primary emissions usually played a more important role in the winter. However, aqueous chemistry resulting in efficient secondary formation during occasional periods with high relative humidity may also contribute substantially to haze in winter. Results of past OA source apportionment studies in Beijing show 45–67% of OA in summer and 22–50% of OA in winter can be composed of SOA. Based on the source apportionment results, we found 45% POA in winter and 61% POA in summer are from nonfossil sources, contributed by cooking OA in both seasons and biomass burning OA (BBOA) in winter. Cooking OA, accounting for 13–24% of OA, is an important nonfossil carbon source in all years of Beijing and should not be neglected. The fossil sources of POA include hydrocarbon‐like OA from vehicle emissions in both seasons and coal combustion OA (CCOA) in winter. The CCOA and BBOA were the two main contributors (57% of OA) for the highest OA concentrations (>100 µg m−3) in winter. The POA/ΔCO ratios in winter and summer are 11 and 16 µg m−3 ppm−1, respectively, similar to ratios from western cities. Higher OOA/Ox (= NO2 + O3) ratio (0.49 µg m−3 ppb−1) in winter study than these ratios from western cities (0.03–0.16 µg m−3 ppb−1) was observed, which may be due to the aqueous reaction or extra SOA formation contributed by semivolatile organic compounds from various primary sources (e.g., BBOA or CCOA) in Beijing. The evolution of oxygen to carbon ratio (O/C) with photochemical age allows to estimate an equivalent rate constant for chemical aging of OA in summer as kOH ~ 4.1 × 10−12 cm3 molecule−1 s−1, which is of the same order as obtained in other anthropogenic influenced areas and may be useful for OA modeling.

Formation of secondary aerosols from gasoline vehicle exhaust when mixing with SO<sub>2</sub>

Abstract. Sulfur dioxide (SO2) can enhance the formation of secondary aerosols from biogenic volatile organic compounds (VOCs), but its influence on secondary aerosol formation from anthropogenic VOCs, particularly complex mixtures like vehicle exhaust, remains uncertain. Gasoline vehicle exhaust (GVE) and SO2, a typical pollutant from coal burning, are directly co-introduced into a smog chamber, in this study, to investigate the formation of secondary organic aerosols (SOA) and sulfate aerosols through photooxidation. New particle formation was enhanced, while substantial sulfate was formed through the oxidation of SO2 in the presence of high concentration of SO2. Homogenous oxidation by OH radicals contributed a negligible fraction to the conversion of SO2 to sulfate, and instead the oxidation by stabilized Criegee intermediates (sCIs), formed from alkenes in the exhaust reacting with ozone, dominated the conversion of SO2. After 5 h of photochemical aging, GVE's SOA production factor revealed an increase by 60–200 % in the presence of high concentration of SO2. The increase could principally be attributed to acid-catalyzed SOA formation as evidenced by the strong positive linear correlation (R2 = 0.97) between the SOA production factor and in situ particle acidity calculated by the AIM-II model. A high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) resolved OA's relatively lower oxygen-to-carbon (O : C) (0.44 ± 0.02) and higher hydrogen-to-carbon (H : C) (1.40 ± 0.03) molar ratios for the GVE / SO2 mixture, with a significantly lower estimated average carbon oxidation state (OSc) of −0.51 ± 0.06 than −0.19 ± 0.08 for GVE alone. The relative higher mass loading of OA in the experiments with SO2 might be a significant explanation for the lower SOA oxidation degree.

Modeling of the chemical composition of fine particulate matter: Development and performance assessment of EASYWRF-Chem

The European emission Adaptation SYstem for the WRF-Chem model (EASYWRF-Chem) has been developed to generate chemical information supporting the WRF-Chem requirements from any emission inventory based on the CORINAIR methodology. Using RADM2 and RACM2 mechanisms, “emission species” are converted into “model species” thanks to the SAPRC methodology for gas phase pollutant and the PM10 and PM2.5 fractions. Furthermore, by adapting US EPA PM2.5 profiles, the processing of aerosol chemical speciation profiles separates the unspeciated PM2.5 emission into five chemical families: sulfates, nitrates, elemental carbon, organic aerosol and unspeciated aerosol. The evaluation of the model has been performed by separately comparing model outcomes with (i) meteorological measurements; (ii) NO2, O3, PM10 and PM2.5 mass concentrations from the regional air quality monitoring network; (iii) hourly-resolved data from four field campaign measurements, in winter and in summer, on two sites in the French northern region. In the latter, a High Resolution — Time of Flight — Aerosol Mass Spectrometer (HR-ToF-AMS) provided non-refractory PM1 concentrations of sulfate, nitrate and ammonium ions as well as organic matter (OM), while an aethalometer provided black carbon (BC) concentrations in the PM2.5 fraction.Meteorological data (temperature, wind, relative humidity) are well simulated for all the time series data except for specific events as wind direction changes or rainfall. For particulate matter, results are presented by considering firstly the total mass concentration of PM2.5 and PM10. EASYWRF-Chem simulations overestimated the PM10 mass concentrations by +22% and +4% for summer and winter periods respectively, whereas for the finer PM2.5 fraction, mass concentrations were overestimated by +20% in summer and underestimated by −13% in winter.Simulated sulfate concentrations were underestimated and nitrate concentrations were overestimated but hourly variations were well represented. Ammonium particulate matter was well simulated for all seasons. Although simulated particulate OM concentrations in PM2.5 were underestimated, their hourly variations were well reproduced by the model. At least BC measurements revealed that EASYWRF-Chem forecast performance was higher in winter than during summer when BC concentrations were very low.

Airmass aging metrics derived from particle and other measurements near Fort Worth

Abstract The composition, concentration, and size of submicron particulate matter (PM1) were measured at five-minute resolution by an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) at a semi-rural location northwest of the Dallas-Fort Worth, TX, area during June 2011. Because of increased organic aerosol (OA) levels, focus here is placed on the period from June 17–30. The total measured PM1 mass concentration ranged between 1.1 and 16.5 μg m−3, with a mean of 4.4 ± 2.6 (one s.d.) μg m−3. Significant variability is observed in the time series of total PM1 and of four individual HR-ToF-AMS species, particularly between June 21 and 25. The average PM1 mass composition was dominated by OA (55.0 ± 14.8%) and sulfate (30.7 ± 12.3%). Organic aerosol concentrations were correlated positively with carbon monoxide (CO) (R = 0.81). This study uses a variety of aging metrics and their relations to OA/ΔCO to characterize secondary organic aerosol. Photochemical age is estimated by using the toluene to benzene ratio. The average photochemical age was 26.7 ± 5.3 h. Other metrics of age used in this work include the ratio of sulfate to total sulfur and the ratio of nitrogen oxides to total reactive nitrogen. The correlations between the OA/ΔCO and nitrogen aging metrics indicate consistent aging, and a weak relationship is observed between OA/ΔCO and sulfur aging. However, the relationship between photochemical age and OA/ΔCO does not show a statistically significant correlation.

New Methodology for Quantifying Polycyclic Aromatic Hydrocarbons (PAHs) Using High-Resolution Aerosol Mass Spectrometry

This article presents a new methodology to potentially quantify polycyclic aromatic hydrocarbon (PAH) isomers using high-resolution time of flight aerosol mass spectrometer (HR-AMS). The fragmentation of PAHs within the HR-AMS is such that significant signal remains at the molecular ion. After quantifying the molecular ion signal and taking into account potential interferences, the amount of the parent PAH in the aerosol may be inferred once its fragmentation pattern is also known. The potential of this approach was evaluated using mixed gasoline and diesel engine exhaust sampled under varying conditions. This dataset led to the identification and quantification within the aerosol mass spectra of the molecular ions associated with 53 PAH isomers, including both unsubstituted and functionalized species. An evaluation of anticipated interferences shows that interferences from larger molecular weight PAHs (i.e., PAH/PAH interferences) could be constrained based on the fragmentation behavior of PAHs from exis...

Sources and chemical characterization of organic aerosol during the summer in the eastern Mediterranean

Abstract. The concentration and chemical composition of non-refractory fine particulate matter (NR-PM1) and black carbon (BC) levels were measured during the summer of 2012 in the suburbs of two Greek cities, Patras and Athens, in an effort to better understand the chemical processing of particles in the high photochemical activity environment of the eastern Mediterranean. The composition of PM1 was surprisingly similar in both areas, demonstrating the importance of regional sources for the corresponding pollution levels. The PM1 average mass concentration was 9–14 μg m−3. The contribution of sulfate was around 38 %, while organic aerosol (OA) contributed approximately 45 % in both cases. PM1 nitrate levels were low (2 %). The oxygen to carbon (O : C) atomic ratio was 0.50 ± 0.08 in Patras and 0.47 ± 0.11 in Athens. In both cases PM1 was acidic. Positive matrix factorization (PMF) was applied to the high-resolution organic aerosol mass spectra obtained by an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). For Patras, five OA sources could be identified: 19 % very oxygenated OA (V-OOA), 38 % moderately oxygenated OA (M-OOA), 21 % biogenic oxygenated OA (b-OOA), 7 % hydrocarbon-like OA (HOA-1) associated with traffic sources and 15 % hydrocarbon-like OA (HOA-2) related to other primary emissions (including cooking OA). For Athens, the corresponding source contributions were: V-OOA (35 %), M-OOA (30 %), HOA-1 (18 %) and HOA-2 (17 %). In both cities the major component was OOA, suggesting that under high photochemical conditions most of the OA in the eastern Mediterranean is quite aged. The contribution of the primary sources (HOA-1 and HOA-2) was important (22 % in Patras and 35 % in Athens) but not dominant.

Characterization of Single Particles in Urban Atmospheric Aerosols Over Nagoya Based on Mass Spectral Analysis

Mass spectral analysis of single aerosol particles was performed using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) in the urban area of Nagoya, Japan, for five days in the autumn of 2010. An ion-series analysis was applied to the single-particle mass spectra; the sum of the masses at Δ of 1, 3, 4, and 5 divided by the total mass of organics (fΔ1,3-5) was used as an indicator of the degree of oxygenation of the organics. The organic mass fraction (Forg) and fΔ1,3-5 of single particles varied substantially, and the results for the entire period indicate that two groups of particles with high and low fΔ1,3-5 were present. The organics in particles with high Forg were less oxygenated, whereas those with low Forg were more oxygenated; these different particles were associated with hydrocarbon-like organic aerosols (HOA) and low-volatility oxygenated organic aerosols (LV-OOA), respectively, based on the PMF analysis of the MS mode data. The size distributions of the two types of part...

Marine and urban influences on summertime PM2.5 aerosol in the Po basin using mobile measurements

We report ambient measurements using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) on a mobile platform in the southeast Po Valley (Italy) in summer 2012. During the PEGASOS southbound campaign measurements of non-refractory aerosol were performed in urban and rural environments as well as near the coast of the Adriatic Sea. Organic source apportionment analysis of the aerosol mass spectrometer data was carried out using positive matrix factorization and multilinear engine (ME-2) receptor modelling. Five major organic aerosol components were identified: hydrocarbon-like organic aerosol (HOA), semi-volatile oxygenated organic aerosol (SVOOA), low volatility oxygenated organic aerosol (LVOOA), cooking organic aerosol (COA) and a regionally influenced highly oxygenated organic aerosol (HOOA). Essential changes in both aerosol composition and concentration were induced by the ventilation and recirculation of air masses in the East-West direction of the valley (land/sea breeze system) and via the Apennine mountain range (mountain/valley wind system). An urban increment of the non-refractory aerosol mass concentration in Bologna of about 1.6–2.3 μg/m3 compared to the surrounding regions was quantified which can be explained by the sum of local contributions from cooking activities and from hydrocarbon-like aerosol related to traffic emissions.

Characterization of aerosol composition, concentrations, and sources at Baengnyeong Island, Korea using an aerosol mass spectrometer

To improve understanding of the sources and chemical properties of particulate pollutants on the western side of the Korean Peninsula, an Aerodyne High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) measured non-refractory fine (PM1) particles from May to November, 2011 at Baengnyeong Island, South Korea. Organic matter and sulfate were generally the most abundant species and exhibited maximum concentrations of 36 μg/m3 and 39 μg/m3, respectively. Nitrate concentrations peaked at 32 μg/m3 but were typically much lower than sulfate and organic matter concentrations. May, September, October, and November featured the highest monthly average concentrations, with lower concentrations typically observed from June through August. Potential source contribution function (PSCF) analysis and individual case studies revealed that transport from eastern China, an area with high SO2 emissions, was associated with high particulate sulfate concentrations at the measurement site. Observed sulfate aerosol sometimes was fully neutralized by ammonium but often was acidic; the average ammonium to sulfate molar ratio was 1.49. Measured species size distributions revealed a range of sulfate particle size distributions with modes between 100 and 600 nm. Organic aerosol source regions were widespread, including contributions from eastern China and South Korea. Positive matrix factorization (PMF) analysis indicated three “factors,” or types of organic aerosol, comprising one primary, hydrocarbon-like organic aerosol (HOA) and two oxidized organic aerosol (OOA) components, including a more oxidized (MO-OOA) and a less oxidized (LO-OOA) oxidized organic aerosol. On average, HOA and OOA contributed 21% and 79% of the organic mass (OM), respectively, with the MO-OOA fraction nearly three times as abundant as the LO-OOA fraction. Biomass burning contributions to observed OM were low during the late spring/early summer agricultural burning season in eastern China, since airflow into eastern China during the Asian Monsoon generally prevents transport of emissions eastward to the Korean Peninsula. Concentrations of the m/z 60 AMS biomass burning marker were more abundant in autumn, when transport patterns appeared to bring some smoke from fires in northern Asia to the island.

Aerosol characterization over the southeastern United States using high-resolution aerosol mass spectrometry: spatial and seasonal variation of aerosol composition and sources with a focus on organic nitrates

Abstract. We deployed a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and an Aerosol Chemical Speciation Monitor (ACSM) to characterize the chemical composition of submicron non-refractory particulate matter (NR-PM$_{1}$) in the southeastern USA. Measurements were performed in both rural and urban sites in the greater Atlanta area, Georgia (GA), and Centreville, Alabama (AL), for approximately 1 year as part of Southeastern Center for Air Pollution and Epidemiology study (SCAPE) and Southern Oxidant and Aerosol Study (SOAS). Organic aerosol (OA) accounts for more than half of NR-PM1 mass concentration regardless of sampling sites and seasons. Positive matrix factorization (PMF) analysis of HR-ToF-AMS measurements identified various OA sources, depending on location and season. Hydrocarbon-like OA (HOA) and cooking OA (COA) have important, but not dominant, contributions to total OA in urban sites (i.e., 21–38 % of total OA depending on site and season). Biomass burning OA (BBOA) concentration shows a distinct seasonal variation with a larger enhancement in winter than summer. We find a good correlation between BBOA and brown carbon, indicating biomass burning is an important source for brown carbon, although an additional, unidentified brown carbon source is likely present at the rural Yorkville site. Isoprene-derived OA factor (isoprene-OA) is only deconvolved in warmer months and contributes 18–36 % of total OA. The presence of isoprene-OA factor in urban sites is more likely from local production in the presence of NOx than transport from rural sites. More-oxidized and less-oxidized oxygenated organic aerosol (MO-OOA and LO-OOA, respectively) are dominant fractions (47–79 %) of OA in all sites. MO-OOA correlates well with ozone in summer but not in winter, indicating MO-OOA sources may vary with seasons. LO-OOA, which reaches a daily maximum at night, correlates better with estimated nitrate functionality from organic nitrates than total nitrates. Based on the HR-ToF-AMS measurements, we estimate that the nitrate functionality from organic nitrates contributes 63–100 % to the total measured nitrates in summer. Furthermore, the contribution of organic nitrates to total OA is estimated to be 5–12 % in summer, suggesting that organic nitrates are important components in the ambient aerosol in the southeastern USA. The spatial distribution of OA is investigated by comparing simultaneous HR-ToF-AMS measurements with ACSM measurements at two different sampling sites. OA is found to be spatially homogeneous in summer due possibly to stagnant air mass and a dominant amount of regional secondary organic aerosol (SOA) in the southeastern USA. The homogeneity is less in winter, which is likely due to spatial variation of primary emissions. We observe that the seasonality of OA concentration shows a clear urban/rural contrast. While OA exhibits weak seasonal variation in the urban sites, its concentration is higher in summer than winter for rural sites. This observation from our year-long measurements is consistent with 14 years of organic carbon (OC) data from the SouthEastern Aerosol Research and Characterization (SEARCH) network. The comparison between short-term measurements with advanced instruments and long-term measurements of basic air quality indicators not only tests the robustness of the short-term measurements but also provides insights in interpreting long-term measurements. We find that OA factors resolved from PMF analysis on HR-ToF-AMS measurements have distinctly different diurnal variations. The compensation of OA factors with different diurnal trends is one possible reason for the repeatedly observed, relatively flat OA diurnal profile in the southeastern USA. In addition, analysis of long-term measurements shows that the correlation between OC and sulfate is substantially stronger in summer than winter. This seasonality could be partly due to the effects of sulfate on isoprene SOA formation as revealed by the short-term intensive measurements.

Improved Time-Resolved Measurements of Inorganic Ions in Particulate Matter by PILS-IC Integrated with a Sample Pre-Concentration System

A particle-into-liquid sampler coupled with ion chromatograph (PILS-IC) for the on-line measurement of inorganic ions has been modified by the insertion of two ion-exchange pre-concentration cartridges that enrich the sample during the period of the IC analysis. The limits of detection of the modified instrument were 10-15 times lower and the time coverage 24 times higher (from 2 to 48 min per hour) than those of the original PILS-IC setup. The instrumental performance in terms of recovery and break-through volume from the cartridges was satisfactory. The modified PILS-IC was operated in comparison with a diffusion denuder line and with a high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) during a short intensive measurement period organized in the framework of the European Monitoring and Evaluation Programme (EMEP), a co-operative program for monitoring and evaluation of the long-range transmission of the air pollutants in Europe. The instrument showed a quantitative response in agreem...

Chemical composition and size distribution of summertime PM<sub>2.5</sub> at a high altitude remote location in the northeast of the Qinghai–Xizang (Tibet) Plateau: insights into aerosol sources and processing in free troposphere

Abstract. Aerosol filter samples were collected at a high-elevation mountain observatory (4180 m a.s.l.) in the northeastern part of the Qinghai–Xizang (Tibet) Plateau (QXP) during summer 2012 using a low-volume sampler and a micro-orifice uniform deposit impactor (MOUDI). These samples were analyzed for water-soluble inorganic ions (WSIs), organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC), and total organic nitrogen (TON) to elucidate the size-resolved chemical composition of free tropospheric aerosols in the QXP region. The average mass concentration of the sum of the analyzed species in PM2.5 (particle matter) (WSIs + OC + EC + TON) was 3.74 μg sm−3, 36% of which was sulfate, 18% OC, 17 % nitrate, 10% ammonium, 6.6% calcium, 6.4% TON, 2.6% EC, 1.5 % sodium, 0.9% chloride, 0.5% magnesium, and 0.3% potassium. The size distributions of sulfate and ammonium peaked in the accumulation mode (0.32–0.56 μm), whereas the size distributions of both nitrate and calcium peaked in the range of 1.8–3.2 μm, suggesting the formation of nitrate on mineral dust. OC, EC and TON were also predominantly found in the accumulation mode. The bulk chemical composition and the average oxidation degree of water-soluble organic matter (WSOM) were assessed using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). WSOM was found to be highly oxidized in all PM2.5 samples with an average oxygen-to-carbon atomic ratio (O / C) of 1.16 and an organic mass-to-organic carbon ratio (OM / OC) of 2.75. The highly oxidized WSOM was likely related to active cloud processing during upslope air mass transport coupled with strongly oxidizing environments caused by snow/ice photochemistry. High average ratios of OC / EC (7.6) and WSOC / OC (0.79) suggested that organic aerosols were primarily made of secondary species. Secondary organic aerosol (SOA) was estimated on average accounting for 80% (62–96%) of the PM2.5, indicating that SOA is an important component of free tropospheric aerosols over the northern QXP.

Chemical characterization of biogenic secondary organic aerosol generated from plant emissions under baseline and stressed conditions: inter- and intra-species variability for six coniferous species

Abstract. The largest global source of secondary organic aerosol (SOA) in the atmosphere is derived from the oxidation of biogenic emissions. Plant stressors associated with a changing environment can alter both the quantity and composition of the compounds that are emitted. Alterations to the biogenic volatile organic compound (BVOC) profile could impact the characteristics of the SOA formed from those emissions. This study investigated the impacts of one global change stressor, increased herbivory, on the composition of SOA derived from real plant emissions. Herbivory was simulated via application of methyl jasmonate (MeJA), a proxy compound. Experiments were repeated under pre- and post-treatment conditions for six different coniferous plant types. Volatile organic compounds (VOCs) emitted from the plants were oxidized to form SOA via dark ozone-initiated chemistry. The SOA chemical composition was measured using a Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-AMS). The aerosol mass spectra of pre-treatment biogenic SOA from all plant types tended to be similar with correlations usually greater than or equal to 0.90. The presence of a stressor produced characteristic differences in the SOA mass spectra. Specifically, the following m/z were identified as a possible biogenic stress AMS marker with the corresponding HR ion(s) shown in parentheses: m/z 31 (CH3O+), m/z 58 (C2H2O2+, C3H6O+), m/z 29 (C2H5+), m/z 57 (C3H5O+), m/z 59 (C2H3O2+, C3H7O+), m/z 71 (C3H3O2+, C4H7O+), and m/z 83 (C5H7O+). The first aerosol mass spectrum of SOA generated from the oxidation of the plant stress hormone, MeJA, is also presented. Elemental analysis results demonstrated an O : C range of baseline biogenic SOA between 0.3 and 0.47. The O : C of standard MeJA SOA was 0.52. Results presented here could be used to help identify a biogenic plant stress marker in ambient data sets collected in forest environments.

Characterization of Particulate Emissions from Biodiesel using High Resolution Time of Flight Aerosol Mass Spectrometer

In the past several decades, biofuels have emerged as candidates to help mitigate the issues of global warming, fossil fuel depletion and, in some cases, atmospheric pollution. To date, the only biofuels that have achieved any significant penetration in the global transportation sector are ethanol and biodiesel. The global consumption of biodiesel was rapidly increased from 2005. The goal of this study was to examine the chemical composition on particulate pollutant emissions from a diesel engine operating on several different biodiesels. Tests were performed on non-road diesel engine. Experiments were performed on 5 different fuel blends at 2 different engine loading conditions (50% and 75%). 5 different fuel blends were ultra-low sulfur diesel (ULSD, 100%), soy biodiesel (Blend 20% and Blend 100%) and canola biodiesel (Blend 20% and Blend 100%). The chemical properties of particulate pollutants were characterized using an Aerodyne High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS). Organic matter and nitrate were generally the most abundant aerosol components and exhibited maximum concentration of <TEX>$1207{\mu}g/m^3$</TEX> and <TEX>$30{\mu}g/m^3$</TEX>, respectively. On average, the oxidized fragment families (<TEX>$C_xH_yO_1{^+}$</TEX>, and <TEX>$C_xH_yO_z{^+}$</TEX>) account for ~13% of the three family sum, while ~87% comes from the <TEX>$C_xH_y{^+}$</TEX> family. The two peaks of <TEX>$C_2H_3O_2$</TEX> (m/z 59.01) and <TEX>$C_3H_7O$</TEX> (m/z 59.04) located at approximately m/z 59 could be used to identify atmospheric particulate matter directly to biodiesel exhaust, as distinguished from that created by petroleum diesel in the AMS data.

Investigating a two-component model of solid fuel organic aerosol in London: processes, PM&amp;lt;sub&amp;gt;1&amp;lt;/sub&amp;gt; contributions, and seasonality

Abstract. Solid fuel emissions, including those from biomass burning, are increasing in urban areas across the European Union due to rising energy costs and government incentives to use renewable energy sources for heating. In order to help protect human health as well as to improve air quality and pollution abatement strategies, the sources of combustion aerosols, their contributions, and the processes they undergo need to be better understood. A high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was therefore deployed at an urban background site between January and February 2012 to investigate solid fuel organic aerosols (SFOA) in London. The variability of SFOA was examined and the factors governing the split between the two SFOA factors derived from Positive Matrix Factorisation (PMF) were assessed. The concentrations of both factors were found to increase during the night and during cold periods, consistent with domestic space heating activities. The split between the two factors is likely governed predominantly by differences in burn conditions where SFOA1 best represents more efficient burns and SFOA2 best represents less efficient burns. The differences in efficiency may be due to burner types or burn phase, for example. Different fuel types and levels of atmospheric processing also likely contribute to the two factors. As the mass spectral profile of SFOA is highly variable, the findings from this study may have implications for improving future source apportionment and factorisation analyses. During the winter, SFOA was found to contribute 38% to the total non-refractory submicron organic aerosol (OA) mass, with similar contributions from both SFOA factors (20% from SFOA1 and 18% from SFOA2). A similar contribution of SFOA was derived for the same period from a compact time-of-flight AMS (cToF-AMS), which measured for a full calendar year at the same site. The seasonality of SFOA was investigated using the year-long data set where concentrations were greatest in the autumn and winter. During the summer, SFOA contributed 11% to the organic fraction, where emissions resulted from different anthropogenic activities such as barbecues and domestic garden wood burning. The significant contribution of SFOA to total organic mass throughout the year suggests that the negative effects on health and air quality, as well as climate, are not just confined to winter as exposure to these aerosols and the associated black carbon can also occur during the summer, which may have significant implications for air-quality policies and mitigation strategies.