Aerodyne Aerosol Chemical Speciation Monitor Research Articles

Measurement report: Hygroscopicity of size-selected aerosol particles in the heavily polluted urban atmosphere of Delhi: impacts of chloride aerosol

Abstract. Recent research has revealed the crucial role of wintertime, episodic high chloride (H-Cl) emissions in the Delhi region, which significantly impact aerosol hygroscopicity and aerosol-bound liquid water, thus contributing to the initiation of Delhi fog episodes. However, these findings have primarily relied on modeled aerosol hygroscopicity, necessitating validation through direct hygroscopicity measurements. This study presents the measurements of non-refractory bulk aerosol composition of PM1 from an Aerodyne aerosol chemical speciation monitor and for first-time size-resolved hygroscopic growth factors (nucleation, Aitken, and accumulated mode particles) along with their associated hygroscopicity parameters at 90 % relative humidity using a hygroscopic tandem differential mobility analyzer at the Delhi Aerosol Supersite. Our observations demonstrate that the hygroscopicity parameter for aerosol particles varies from 0.00 to 0.11 (with an average of 0.03 ± 0.02) for 20 nm particles, 0.05 to 0.22 (0.11 ± 0.03) for 50 nm particles, 0.05 to 0.30 (0.14 ± 0.04) for 100 nm particles, 0.05 to 0.41 (0.18 ± 0.06) for 150 nm particles, and 0.05 to 0.56 (0.22 ± 0.07) for 200 nm particles. Surprisingly, our findings demonstrate that the period with H-Cl emissions displays notably greater hygroscopicity (0.35 ± 0.06) in comparison to spans marked by high biomass burning (0.18 ± 0.04) and high hydrocarbon-like organic aerosol (0.17 ± 0.05) and relatively cleaner periods (0.27 ± 0.07). This research presents initial observational proof that ammonium chloride is the main factor behind aerosol hygroscopic growth and aerosol-bound liquid water content in Delhi. The finding emphasizes ammonium chloride's role in aerosol–water interaction and related haze/fog development. Moreover, the high chloride levels in aerosols seem to prevent the adverse impact of high organic aerosol concentrations on cloud condensation nuclei activity.

Analysis of aerosol liquid water content and its role in visibility reduction in Delhi

Aerosols undergo significant changes due to water uptake under high RH conditions, leading to changes in physical, optical, and chemical properties. Detailed assessment and investigation are needed to understand better aerosol liquid water content (ALWC) characteristics in highly polluted regions like Delhi. Therefore, in this study, we examined the mass concentration and the factors governing the ALWC associated with PM2.5 in Delhi for two winters (Dec 2019 to Jan 2020 and Dec 2020 to Feb 2021) using the real-time measurements of NR-PM2.5 from Aerodyne aerosol chemical speciation monitor (ACSM) and the application of thermodynamic modeling (ISORROPIA II). The average NR-PM2.5 mass concentration in the 2020–2021 winter was 152 μg/m3, about 50 % higher than the average mass concentration of 102 μg/m3 in 2019–2020. Consequently, the ALWC was also 60 % higher during 2020–2021, with an average mass concentration of 150 μg/m3. ALWC increased exponentially with RH and is significant when RH > 80 %. Further, all the inorganic components of NR-PM2.5 were found to contribute significantly to ALWC uptake; however, the relative contribution varied in different RH conditions. Ammonium sulphate dominated the ALWC uptake among the inorganic components at low RH, but ammonium nitrate was the dominant contributor at high RH. The decreased chloride mass fraction in inorganics in the recent winters reduced its relative contribution to ALWC. High ALWC mass concentration during high PM2.5 and high RH leads to a significant reduction in visibility. We further validated this visibility reduction by estimating the enhanced light scattering coefficient (f(RH)) and found that the hygroscopic growth is responsible for the enhanced visibility reduction during high RH conditions (> 85 %) when light scattering efficiency increased by a factor of >3.5. Sensitivity tests of f(RH) on mass concentration of inorganic salts showed that all the salts contributed almost equally. As revealed in our study, variations in PM2.5 mass concentration and composition despite similar meteorological conditions between different winters indicate changing regional aerosol emissions. Therefore, long-term observations of ALWC and PM2.5 chemical composition are required to arrive at actionable measures and mitigation strategies. Further, the focus should be on reducing the overall inorganic mass concentrations of PM2.5 in general, decreasing the absolute ALWC, and improving visibility.

A Closure Study of Secondary Organic Aerosol Estimation at an Urban Site of Yangtze River Delta, China

Secondary organic aerosols (SOA) are crucial components of ambient particulate matters. However, their composition and formation mechanisms remain uncertain. To investigate the SOA formation and evaluate various SOA estimation approaches, a comprehensive measurement was conducted at an urban site, Changzhou, in Yangtze River Delta (YRD) region. 98 kinds of volatile organic compounds (VOCs) were measured by an online gas chromatography-mass spectrometer/flame ionization detector (GC-MS/FID). Non-refractory submicron particulate matters (NR-PM1) were measured by an Aerodyne Aerosol Chemical Speciation Monitor (ACSM). Both bottom-up approaches, i.e., VOCs oxidation yield method, and top-down approaches, i.e., elemental carbon (EC) tracer method and ACSM, combined with positive matrix factorization (PMF) method, were utilized to estimate SOA. ACSM-PMF method estimated the highest SOA concentration, followed by EC tracer method. SOA from VOCs oxidation yield method accounted for 43.2 ± 41.9% of that from EC tracer method, suggesting the existence of missing SOA precursors, e.g., semivolatile organic compounds. The influencing factors of SOA formation were investigated and a good correlation of SOA with odd oxygen rather than aerosol liquid water content was found, suggesting the importance of photochemical formation of SOA.

Physical and chemical properties of urban aerosols in São Paulo, Brazil: links between composition and size distribution of submicron particles

Abstract. In this work, the relationships between size and composition of submicron particles (PM1) were analyzed at an urban site in the Metropolitan Area of São Paulo (MASP), a megacity with about 21 million inhabitants. The measurements were carried out from 20 December 2016 to 15 March 2017. The chemical composition was measured with an Aerodyne Aerosol Chemical Speciation Monitor and size distribution with a TSI Scanning Mobility Particle Sizer 3082. PM1 mass concentrations in the MASP had an average mass concentration of 11.4 µg m−3. Organic aerosol (OA) dominated the PM1 composition (56 %), followed by sulfate (15 %) and equivalent black carbon (eBC, 13 %). Four OA classes were identified using positive matrix factorization: oxygenated organic aerosol (OOA, 40 % of OA), biomass burning organic aerosol (BBOA, 13 %), and two hydrocarbon-like OA components (a typical HOA related to vehicular emissions (16 %) and a second HOA (21 %) representing a mix of anthropogenic sources). Particle number concentrations averaged 12 100±6900 cm−3, dominated by the Aitken mode. The accumulation mode increased under relatively high-PM1 conditions, suggesting an enhancement of secondary organic aerosol (SOA) production. Conversely, the contribution of nucleation-mode particles was less dependent on PM1 levels, consistent with vehicular emissions. The relationship between aerosol size modes and PM1 composition was assessed by multilinear regression (MLR) models. Secondary inorganic aerosols were partitioned between Aitken and accumulation modes, related to condensation particle growth processes. Submicron mass loading in the accumulation mode was mostly associated with highly oxidized OOA and also traffic-related emissions. To the authors' knowledge, this is the first work that uses the MLR methodology to estimate the chemical composition of the different aerosol size modes. The chemical composition with size-dependent PM provides innovative information on the properties of both primary and secondary organic aerosols, as well as inorganic aerosols in a complex urban environment. The results emphasize the relevance of vehicular emissions to the air quality at MASP and highlight the key role of secondary processes on the PM1 ambient concentrations in the region since 56 % of PM1 mass loading was attributed to SOA and secondary inorganic aerosol.

Influence of biomass burning vapor wall loss correction on modeling organic aerosols in Europe by CAMx v6.50

Abstract. Increasing evidence from experimental studies suggests that the losses of semi-volatile vapors to chamber walls could be responsible for the underestimation of organic aerosol (OA) in air quality models that use parameters obtained from chamber experiments. In this study, a box model with a volatility basis set (VBS) scheme was developed, and the secondary organic aerosol (SOA) yields with vapor wall loss correction were optimized by a genetic algorithm based on advanced chamber experimental data for biomass burning. The vapor wall loss correction increases the SOA yields by a factor of 1.9–4.9 and leads to better agreement with measured OA for 14 chamber experiments under different temperatures and emission loads. To investigate the influence of vapor wall loss correction on regional OA simulations, the optimized parameterizations (SOA yields, emissions of intermediate-volatility organic compounds from biomass burning, and enthalpy of vaporization) were implemented in the regional air quality model CAMx (Comprehensive Air Quality Model with extensions). The model results from the VBS schemes with standard (VBS_BASE) and vapor-wall-loss-corrected parameters (VBS_WLS), as well as the traditional two-product approach, were compared and evaluated by OA measurements from five Aerodyne aerosol chemical speciation monitor (ACSM) or aerosol mass spectrometer (AMS) stations in the winter of 2011. An additional reference scenario, VBS_noWLS, was also developed using the same parameterization as VBS_WLS except for the SOA yields, which were optimized by assuming there is no vapor wall loss. The VBS_WLS generally shows the best performance for predicting OA among all OA schemes and reduces the mean fractional bias from −72.9 % (VBS_BASE) to −1.6 % for the winter OA. In Europe, the VBS_WLS produces the highest domain average OA in winter (2.3 µg m−3), which is 106.6 % and 26.2 % higher than VBS_BASE and VBS_noWLS, respectively. Compared to VBS_noWLS, VBS_WLS leads to an increase in SOA by up to ∼80 % (in the Balkans). VBS_WLS also leads to better agreement between the modeled SOA fraction in OA (fSOA) and the estimated values in the literature. The substantial influence of vapor wall loss correction on modeled OA in Europe highlights the importance of further improvements in parameterizations based on laboratory studies for a wider range of chamber conditions and field observations with higher spatial and temporal coverage.

Characteristics, evolution, and potential source regions of submicron aerosol in Beijing, China

Atmospheric fine particulate pollution has been a dramatically environmental concern in all seasons in the megacity Beijing in recent years. A long-term real-time monitoring campaign of non-refractory submicron aerosol (NR-PM1) at a southeastern urban site in Beijing from July 13, 2017 to May 26, 2018 using an Aerodyne Aerosol Chemical Speciation Monitor (ACSM) was carried out to investigate the characteristics and evolution processes of NR-PM1 and its potential source effects. The annual average concentration of NR-PM1 during the entire study period was 40.8 μg/m3, lower than that of NR-PM1 from July 2011 to June 2012, and its seasonal variation presented the order of autumn and spring > winter > summer. The average concentration of organic species Org in the entire study was 15.1 μg/m3 and accounted for 37% of NR-PM1, being consistently a significant component of NR-PM1 in the four seasons. The average concentrations of SO42− and NO3− were 8.6 and 11.1 μg/m3, respectively, accounting for 21% and 27% of NR-PM1, and NO3− and its contribution to NR-PM1 exceeded those of SO42−, suggesting that secondary nitrate became a more dramatic pollutant. Note that SO42− in summer accounted for 27% of NR-PM1, higher than those in the other seasons, indicating that secondary sulfate formation was greatly important in summer, however, NO3− in summer accounted for 22% of NR-PM1, lower than those in the other seasons, more likely due to relatively high temperature in summer being favorable for dissociation of nitrate. NH4+ and Cl− species presented lower mass concentrations and mass fractions, and the seasonal variation of NH4+ was similar to NO3−, yet Cl− presented a typical seasonal change related to intense fossil fuel combustion during the heating period in winter and biomass burning in autumn with an order of winter > autumn > spring > summer. All aerosol species exhibited different diurnal cycles, of which Org presented a bimodal mode, SO42− and Cl− showed a flatter diurnal pattern, however, NO3− and NH4+ displayed more similar single-peak patterns. The conversion of SO2 to SO42− presented an obvious seasonal variation with summer > autumn > spring > winter driven by different factors. The conversion of NO2 to NO3− also showed a significant seasonal change characterized by autumn > summer and spring > winter controlled by different factors. Relative humidity, temperature and wind speed during the study period were significant meteorological elements influencing NR-PM1 and its species, and heavy haze pollution episodes largely occurred under high relative humidity and low wind speed. High potential source regions influencing NR-PM1 pollution in Beijing in all seasons presented dramatically distributions related to wind directions.

Real-time non-refractory PM1 chemical composition, size distribution and source apportionment at a coastal industrial park in the Yangtze River Delta region, China

This study present real-time measurements of the chemical composition and particle number size distributions (PNSD) of submicron particulate matter (PM1) in winter at a coastal industrial park in the Yangtze River Delta region of China. Positive matrix factorization (PMF) analysis identified three PNSD factors and three organic aerosol (OA) factors. Contributions and potential source regions of these factors were investigated for four typical periods during the PM1 formation and dissipation process. Results show that the relative contributions from aged 250 nm- factor, fresh 35 nm- and 80 nm- factors were strongly affected by local fresh emissions and regional new particle formation. The non-refractory PM1 measured by Aerodyne aerosol chemical speciation monitor is indicative of the chemical composition of aged 250 nm-factor, but not fresh 35 nm- and 80 nm-factors. The contributions of NO3− and SO42− to NR-PM1 were largely dictated by whether the air mass trajectory went over the sea or the continent. NO3− was abundant (up to 44% of NR-PM1) in cold and dry continental air masses, while SO42− formation (up to 39% of NR-PM1) was preferred in humid and warm marine air masses. Among the three OA source factors, more-oxidized oxygenated OA (MO-OOA) was the most abundant OA factor (44–66% of total OA) throughout the entire field campaign, while an enhanced contribution of 39% from hydrocarbon-like OA (HOA) was observed prior to heavy pollution period. On average, secondary components SO42−, NO3−, NH4+, MO-OOA and less-oxidized oxygenated OA (LO-OOA) contributed 90 ± 7% of NR-PM1, while primary components HOA and Cl− accounted for the remaining 10 ± 7%.

Chemical composition and sources of submicron aerosol in a coastal city of China: Results from the 2017 BRICS summit study

Chemical compositions of non-refractory submicron aerosol (NR-PM1) were measured via an Aerodyne Aerosol Chemical Speciation Monitor at the coastal city Xiamen during the 2017 BRICS summit from August 10 to September 10. Mean hourly concentration of NR-PM1 was 13.55 ± 8.83 μg m−3 during the study period, decreasing from 18.83 μg m−3 before-BRICS to 13.02 μg m−3 in BRCIS I and 8.42 μg m−3 in BRICS II. Positive matrix factor analyses resolved four organic aerosols (OA): a hydrocarbon-like OA (HOA, 14.78%), a cooking-related OA (COA, 28.21%), a biomass burning OA (BBOA, 18.00%), and an oxygenated OA (OOA, 39.22%). The contributions of local pollutants like nitrate and HOA reduced, while the proportions of sulfate and OOA increased during the control episodes. The diurnal patterns of NR-PM1 species and OA components in each episode were characterized. The results showed that BC, nitrate, COA, and HOA had peaks in the morning and evening, which became less obvious under the emission control. Moreover, the diurnal variations of all species in Ep 3 with emission control were much flatter due to the effect of transport. Backward trajectories analysis confirmed the long-range transport of air masses from the continent, which resulted in the high proportions of sulfate (43.69%) and OOA (50.28%) in Ep 3. Our study implies the significant effect of emission control on reducing primary pollutants, but the formation of particles during the long-range transport need to be paid more attention when set the air quality control strategies in coastal cities.

Characteristics and Sources of Black Carbon Aerosol in a Mega-City in the Western Yangtze River Delta, China

A single particle soot photometer (SP2) was deployed in urban Nanjing, located in the Yangtze River Delta (China), to investigate the mixing state and sources of ambient refractory black carbon (rBC) from 26 January to 25 February 2014, along with an in-situ measurement of submicron aerosol chemical species by an aerodyne aerosol chemical speciation monitor (ACSM). The results showed that anthropogenic activities associated with firework emissions can be a significant source for rBC-containing particles during the period of the Chinese New Year, resulting from the evident peaks of rBC at midnight. During the residual periods, namely regular day (RD), the diurnal cycles of rBC presented two typical peaks that can be attributed to a synergistic influence of local traffic emissions and boundary layer changes throughout a day. Three coating factors, including organics, sulfate, and nitrate (-rich), were resolved using a positive matrix factorization (PMF) approach to explain the potential contribution of non-rBC coatings (i.e., organics, sulfate, and nitrate) to the coating thickness of rBC-containing particles. As the results show, organic aerosols (OAs) might be a major contributor to the coating thickness of rBC-coating particles during the whole period. The relative coating thickness (a ratio between coated particle size to BC core) exhibited a positive relationship with sulfate, indicative of the favorable coating factor during the episode caused by firework emissions. Source apportionment of rBC was performed via a multiple linear regression between the total rBC mass and each ACSM-PMF factor (rBC-ACSM-PMF). On average, biomass burning emissions accounted for 43%, being the largest contributor during the RD period, whereas local traffic emissions played a major role during the new year time.

Composition analysis and formation pathway comparison of PM1 between two pollution episodes during February 2017 in Beijing, China

SO42−, NO3− and NH4+ (SNA) are the major components of particulate matter in Beijing. In this study, hourly concentrations of SNA in PM1 were measured through an Aerodyne Aerosol Chemical Speciation Monitor (ACSM) at an urban site of Beijing, from February 3rd to 20th of 2017. The analysis of the differences between two pollution cases during the sampling period was further conducted. The results showed that the concentrations of NO3−, SO42− and NH4+ were 38.9 ± 10.5 μg/m3, 41.9 ± 22.2 μg/m3 and 31.3 ± 10.6 μg/m3 respectively in the first case. A negative correlation was reflected between the PM2.5 concentrations and the following two ratios: 1) NO3−/SO42−; 2) [NH4+] to ([NO3−]+2[SO42−]), with a correlation coefficient of −0.92 and −0.76 respectively. In the second case, the PM2.5 concentrations (proportions) were much higher, with values of 49.9 ± 17.0 μg/m3 (22.9 ± 7.7%), 42.3 ± 15.8 μg/m3 (20.3 ± 7.2%) and 33.1 ± 10.1 μg/m3 (15.3 ± 4.3%). In contrast. The two ratios were positively correlated with the PM2.5 concentrations, along with the correlation coefficient of 0.77 and 0.62. Hence, it is palpable that two pollution cases were sulfate and nitrate dominant in respective. The emission characteristics due to the Chinese Spring Festival before P1 might be a major cause. A modeling-monitoring coupled approach was established for the recognition of the secondary conversion of SO42− and NO3−. Results showed that sulfate/nitrate aged ratio (SAR and NAR) and sulphur oxidation ratio (SOR) in the second case were 0.48 ± 0.23, 0.22 ± 0.07 and 0.38 ± 0.23. They were all higher than those of the first case whose values were 0.32 ± 0.15, 0.18 ± 0.05 and 0.22 ± 0.12, which indicated that secondary conversion of precursors was enhanced in the second case. Although the OH concentrations were of no obvious difference in both cases, the average concentrations of H2O2, NO2 and the relative humidity were much higher in the second case, which provided sufficient conditions and time for the formation of SO42− and NO3−.

Insights into submicron particulate evolution, sources and influences on haze pollution in Beijing, China

The real-time continuous measurements of non-refractory submicron aerosol (NR-PM1) species including organics (Org), sulfate (SO42−), nitrate (NO3−), ammonium (NH4+) and chloride (Cl−) in winter from 10 December 2015 to 30 January 2016 in Beijing were performed with an Aerodyne Aerosol Chemical Speciation Monitor (ACSM). The average concentration of NR-PM1 was 81.24 μg m−3, with the mean concentration in heavy haze days being 220.00 μg m−3, ∼3 times higher than that in light haze days and ∼15 times higher than that in clean days. Org was the most significant component of NR-PM1 species, accounting for 53% of the total NR-PM1 for the entire study. SO42− was also a significant component, accounting for 23% of the total NR-PM1. However, NO3−, NH4+ and Cl− composition together accounted for 25% of the total NR-PM1. All NR-PM1 species presented remarkably diurnal cycles in haze days, characterized by the highest concentrations occurring at midnight, and the lowest concentrations occurring at daytime. Note that the sulfur oxidation ratios were higher than the nitrogen oxidation ratios for the entire study, especially during the haze periods. The formation of sulfate was mainly affected by relative humidity (RH), while that of nitrate was more associated with NH3. Heterogeneous oxidation of NO2 on the surfaces of aerosol particles might be a significant pathway of nitrate formations during haze periods. NR-PM1 was mainly from secondary chemical reactions contributing 46.1%, vehicle emissions contributing 22.3%, coal combustion contributing 16.1%, and biomass burning contributing 15.6% in clean days. However, compared to the clean-day source contributions, the haze-day secondary source contribution to NR-PM1 increased to 66.8%, indicating that NR-PM1 in haze days was dramatically dominated by the secondary pollutants.

PM1 Chemical Characterization during the ACU15 Campaign, South of Mexico City

The “Aerosoles en Ciudad Universitaria 2015” (ACU15) campaign was an intensive experiment measuring chemical and optical properties of aerosols in the winter of 2015, from 19 January to 19 March on a site in the south of Mexico City. The mass concentration and chemical composition of the non-refractory submicron particulate matter (NR-PM1) was determined using an Aerodyne Aerosol Chemical Speciation Monitor (ACSM). The total NR-PM1 mass concentration measured was lower than reported in previous campaigns that took place north and east of the city. This difference might be explained by the natural variability of the atmospheric conditions, as well as the different sources impacting each site. However, the composition of the aerosol indicates that the aerosol is more aged (a larger fraction of the mass corresponds to sulfate and to low-volatility organic aerosol (LV-OOA)) in the south than the north and east areas; this is consistent with the location of the sources of PM and their precursors in the city, as well as the meteorological patterns usually observed in the metropolitan area.

Distribution Characteristics of Air Pollutants and Aerosol Chemical Components Under Different Weather Conditions in Jiaxing

Distribution characteristics of air pollutants and aerosol chemical components under different weather conditions were investigated in Jiaxing between May 1 and 31, 2015. The particulate matter (PM), gaseous pollutants, chemical components in PM1.0, and aerosol number concentrations ranging from 10 nm to 10 μm were measured using the SHARP-5030 monitoring instrument, Thermo EMS system, Aerodyne Aerosol Chemical Speciation Monitor (ACSM), and Wide-Range Particle Spectrometer (WPS), respectively. The average concentrations of PM2.5, PM1.0, SO2, NO2, O3, and CO were 52.8 μg·m-3, 37.2 μg·m-3, 10.3 μg·m-3, 38.1 μg·m-3, 92.1 μg·m-3, and 1.2 mg·m-3 during the observation period. The chemical components of OA, SO42-, NO3-, NH4+, and Cl-in PM1.0 had average concentrations of 2.18, 1.24, 0.87, 0.63, and 0.08 μg·m-3, respectively. The aerosol number concentrations were mainly centralized in Aitken mode (20-100 nm), with a value of 12411.2 cm-3. The nuclei mode aerosols (10-20 nm) followed the number concentrations with 4946.6 cm-3. The concentration distributions and diurnal variations of PM and gaseous pollutants, and the distributions of chemical components of PM1.0 varied under different weather conditions. The concentrations of chemical components were ranked in the order of OA > SO42- > NO3- > NH4+ > Cl- on rainy days and sunny days, and in the order of OA > NO3- > SO42- > NH4+ > Cl- on new particle formation (NPF) days. The OA and NO3- concentrations on NPF days were 1.61 and 1.42 times larger than those on sunny days, suggesting that the components of OA and NO3- were the main substances influencing the NPF events. Additionally, the diurnal variations of aerosols in different modes varied under different types of weather conditions.

Source apportionment of submicron organic aerosol collected from Atlanta, Georgia, during 2014–2015 using the aerosol chemical speciation monitor (ACSM)

The Aerodyne Aerosol Chemical Speciation Monitor (ACSM) was redeployed at the Jefferson Street (JST) site in downtown Atlanta, Georgia (GA) for 1 year (March 20, 2014–February 08, 2015) to chemically characterize non-refractory submicron particulate matter (NR-PM1) in near real-time and to assess whether organic aerosol (OA) types and amounts change from year-to-year. Submicron organic aerosol (OA) mass spectra were analyzed by season using multilinear engine (ME-2) to apportion OA subtypes to potential sources and chemical processes. A suite of real-time collocated measurements from the Southeastern Aerosol Research and Characterization (SEARCH) network was compared with ME-2 factor solutions to aid in the interpretation of OA subtypes during each season. OA tracers measured from high-volume filter samples using gas chromatography interfaced with electron ionization-mass spectrometry (GC/EI-MS) also aided in identifying OA sources. The initial application of ME-2 to the yearlong ACSM dataset revealed that OA source apportionment by season was required to better resolve sporadic OA types. Spring and fall OA mass spectral datasets were separated into finer periods to capture potential OA sources resulting from non-homogeneous emissions during transitioning periods. NR-PM1 was highest in summer (16.7 ± 8.4 μg m−3) and lowest in winter (8.0 ± 5.7 μg m−3), consistent with prior studies. OA dominated NR-PM1 mass (56–74% on average) in all seasons. Hydrocarbon-like OA (HOA) from primary emissions was observed in all seasons, averaging 5–22% of total OA mass. Strong correlations of HOA with carbon monoxide (CO) (R = 0.71–0.88) and oxides of nitrogen (NOx) (R = 0.55–0.79) indicated that vehicular traffic was the likely source. Biomass burning OA (BBOA) was observed in all seasons, with lower contributions (2%) in summer and higher in colder seasons (averaging 8–20% of total OA mass). BBOA correlated strongly with levoglucosan (R = 0.78–0.95) during colder seasons, which supports that BBOA is likely derived from fresh biomass/residential burning. However, weaker correlation with levoglucosan (R = 0.38) in summer suggested a more aged aerosol. During warmer seasons, OA from the reactive uptake of isoprene epoxydiols (IEPOX) onto acidic sulfate aerosol was resolved by ME-2 (denoted as IEPOX-OA), averaging 25–29% of the total OA mass. Temporal variation of IEPOX-OA was nearly coincident with that of 91Fac OA (a factor dominated by a distinct ion at m/z 91). The largest contribution of IEPOX-OA to total OA (29%) was found in summer, whereas the largest contribution of 91Fac to total OA (24%) occurred in early fall. Moderate negative correlation between IEPOX-OA and aerosol acidity was observed during late spring (−0.67) and summer (−0.42), consistent with laboratory studies showing that IEPOX-OA is enhanced in the presence of acidic aerosols. Finally, the largest OA mass in all seasons (46–70% of total OA) was derived from oxygenated OA denoted as low-volatility oxygenated OA (LV-OOA) and semi-volatile oxygenated OA (SV-OOA).

Seasonal changes in the PM1 chemical composition north of Mexico City

An Aerodyne Aerosol Chemical Speciation Monitor (ACSM; Aerodyne Inc.) was deployed at a site north of Mexico City from November 13, 2013 to April 30, 2014 to investigate the seasonal variability of the chemical composition of submicron particles. The ACSM provides real time information on mass concentration of the non-refractory main species (nitrate, sulfate, ammonium, chloride and organic compounds) in particulate matter less than 1 μm (NR-PM 1 ) with a 30-min time resolution. Meteorological variables (temperature, relative humidity, and wind speed and direction), as well as concentrations of black carbon, PM 1 , PM 2.5 , CO, SO 2 , NO, NO 2 , and O 3 , were also measured. The total NR-PM 1 mass concentrations plus black carbon (which must be close to the PM 1 total mass) showed a good correlation with PM 1 mass concentration measured with a Tapered Element Oscillating Micro-Balance, an indication of the soundness of the ACSM data. In average, the composition of the aerosol as well as its diurnal variability were similar to observations in previous studies using similar instruments (MCMA-2003 and MILAGRO). However, it was observed that the aerosol was persistently acidic during November and December probably due to a higher relative humidity, lower temperature, and more frequent winds from the NW, where the Tula industrial complex is located. A lower concentration of ammonia (NH 3 ) in the gas phase might affect the PM acidity too. These results suggest a seasonal variability in the aerosol chemistry in Mexico City, which should be verified with more long-term studies.

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.

Laboratory characterization of an aerosol chemical speciation monitor with PM2.5measurement capability

ABSTRACTThe Aerodyne Aerosol Chemical Speciation Monitor (ACSM) is well suited for measuring non-refractory particulate matter up to approximately 1.0 µm in aerodynamic diameter (NR-sub-PM1). However, for larger particles the detection efficiency is limited by losses in the sampling inlet system and through the standard aerodynamic focusing lens. In addition, larger particles have reduced collection efficiency due to particle bounce at the vaporizer. These factors have limited the NR-sub-PM1 ACSM from meeting PM2.5 (particulate matter with aerodynamic diameter smaller than 2.5 µm) monitoring standards. To overcome these limitations, we have redesigned the sampling inlet, the aerodynamic lens, and particle vaporizer. Both the new lens and vaporizer are tested in the lab using a quadruple aerosol mass spectrometer (QAMS) system equipped with light scattering module. Our results show that the capture vaporizer introduces additional thermal decomposition of both inorganic and organic compounds, requiring modi...

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 (> months), with short time resolution (< 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.

Inorganic Salt Interference on CO2+ in Aerodyne AMS and ACSM Organic Aerosol Composition Studies.

Aerodyne aerosol mass spectrometer (AMS) and Aerodyne aerosol chemical speciation monitor (ACSM) mass spectra are widely used to quantify organic aerosol (OA) elemental composition, oxidation state, and major environmental sources. The OA CO2+ fragment is among the most important measurements for such analyses. Here, we show that a non-OA CO2+ signal can arise from reactions on the particle vaporizer, ion chamber, or both, induced by thermal decomposition products of inorganic salts. In our tests (eight instruments, n = 29), ammonium nitrate (NH4NO3) causes a median CO2+ interference signal of +3.4% relative to nitrate. This interference is highly variable between instruments and with measurement history (percentiles P10-90 = +0.4 to +10.2%). Other semi-refractory nitrate salts showed 2-10 times enhanced interference compared to that of NH4NO3, while the ammonium sulfate ((NH4)2SO4) induced interference was 3-10 times lower. Propagation of the CO2+ interference to other ions during standard AMS and ACSM data analysis affects the calculated OA mass, mass spectra, molecular oxygen-to-carbon ratio (O/C), and f44. The resulting bias may be trivial for most ambient data sets but can be significant for aerosol with higher inorganic fractions (>50%), e.g., for low ambient temperatures, or laboratory experiments. The large variation between instruments makes it imperative to regularly quantify this effect on individual AMS and ACSM systems.

Fossil and non-fossil source contributions to atmospheric carbonaceous aerosols during extreme spring grassland fires in Eastern Europe

Abstract. In early spring the Baltic region is frequently affected by high-pollution events due to biomass burning in that area. Here we present a comprehensive study to investigate the impact of biomass/grass burning (BB) on the evolution and composition of aerosol in Preila, Lithuania, during springtime open fires. Non-refractory submicron particulate matter (NR-PM1) was measured by an Aerodyne aerosol chemical speciation monitor (ACSM) and a source apportionment with the multilinear engine (ME-2) running the positive matrix factorization (PMF) model was applied to the organic aerosol fraction to investigate the impact of biomass/grass burning. Satellite observations over regions of biomass burning activity supported the results and identification of air mass transport to the area of investigation. Sharp increases in biomass burning tracers, such as levoglucosan up to 683 ng m−3 and black carbon (BC) up to 17 µg m−3 were observed during this period. A further separation between fossil and non-fossil primary and secondary contributions was obtained by coupling ACSM PMF results and radiocarbon (14C) measurements of the elemental (EC) and organic (OC) carbon fractions. Non-fossil organic carbon (OCnf) was the dominant fraction of PM1, with the primary (POCnf) and secondary (SOCnf) fractions contributing 26–44 % and 13–23 % to the total carbon (TC), respectively. 5–8 % of the TC had a primary fossil origin (POCf), whereas the contribution of fossil secondary organic carbon (SOCf) was 4–13 %. Non-fossil EC (ECnf) and fossil EC (ECf) ranged from 13–24 and 7–13 %, respectively. Isotope ratios of stable carbon and nitrogen isotopes were used to distinguish aerosol particles associated with solid and liquid fossil fuel burning.