Time-of-flight Aerosol Chemical Speciation Monitor Research Articles

Oxidative potential apportionment of atmospheric PM1: a new approach combining high-sensitive online analysers for chemical composition and offline OP measurement technique

Abstract. Source apportionment models were widely used to successfully assign highly time-resolved aerosol data to specific emissions and/or atmospheric chemical processes. These techniques are necessary for targeting the sources affecting air quality and for designing effective mitigation strategies. Moreover, evaluation of the toxicity of airborne particulate matter is important since the classically measured particulate matter (PM) concentrations appear insufficient for characterizing the impact on human health. Oxidative potential (OP) measurement has recently been developed to quantify the capability of PM to induce an oxidative imbalance in the lungs. As a result, this measurement unit could be a better proxy than PM mass concentration to represent PM toxicity. In the present study, two source apportionment analyses were performed using positive matrix factorization (PMF) from organic aerosol (OA) mass spectra measured at a 15 min time resolution using a time-of-flight aerosol chemical speciation monitor (ToF-ACSM) and from 19 trace elements measured on an hourly basis using an online metal analyser (Xact 625i). The field measurements were carried out in summer 2018. While it is common to perform PMF studies individually on ACSMs and more recently on Xact datasets, here we used a two-step methodology leading to a complete PM1 source apportionment. The outputs from both OA PMF and Xact PMF, the inorganic species concentrations from the ACSM, and the black carbon (BC) fractions (fossil fuel and wood burning) measured using an Aethalometer (AE33) were gathered into a single dataset and subjected to a combined PMF analysis. Overall, eight factors were identified, each of them corresponding to a more precise source than performing single PMF analyses. The results show that besides the high contribution of secondary ammonium sulfate (28 %) and organic nitrate (19 %), about 50 % of PM1 originated from distinct combustion sources, including emissions from traffic, shipping, industrial activities, cooking, and biomass burning. Simultaneously, PM1 filters were collected during the experimental period on a 4 h sampling basis. On these filters, two acellular OP assays were performed (dithiothreitol; OPDTT and ascorbic acid; OPAA) and an inversion method was applied on factors issued from all PMFs to assess the contribution of the PM sources to the OP. This work highlights the sensitivity of OPAA to industrial and dust resuspension sources and those of OPDTT to secondary ammonium sulfate, shipping, and biomass burning.

What chemical species are responsible for new particle formation and growth in the Netherlands? A hybrid positive matrix factorization (PMF) analysis using aerosol composition (ACSM) and size (SMPS)

Abstract. Aerosol formation acts as a sink for gas-phase atmospheric species that controls their atmospheric lifetime and environmental effects. To investigate aerosol formation and evolution in the Netherlands, a hybrid positive matrix factorization (PMF) analysis was conducted using observations from May, June, and September 2021 collected in the rural site of Cabauw in the central part of the Netherlands. The hybrid input matrix consists of the full organic mass spectrum acquired from a time-of-flight aerosol chemical speciation monitor (ToF-ACSM), ACSM inorganic species concentrations, and binned particle size distribution concentrations from a scanning mobility particle sizer (SMPS). These hybrid PMF analyses discerned four factors that describe aerosol composition variations: two size-driven factors that are related to new particle formation (NPF) and growth (F4 and F3), as well as two bulk factors driven by composition, not size (F2 and F1). The distribution of chemical species across these factors shows that different compounds are responsible for nucleation and growth of new particles. The smallest-diameter size factor (F4) contains ammonium sulfate and organics and typically peaks during the daytime. Newly formed particles, represented by F4, are mainly correlated with wind from the southwesterly–westerly and easterly sectors that transport sulfur oxides (SOx), ammonia (NH3), and organic precursors to Cabauw. As the particles grow from F4 to F3 and to bulk factors, nitrate and organics play an increasing role, and the particle loading diurnal cycle shifts from daytime to a nighttime maximum. Greater organics availability makes secondary organic aerosol (SOA) more influential in summertime aerosol growth, principally due to volatility differences produced by seasonal variation in photooxidation and temperature.

Biomass burning and aqueous reactions drive the elevation of wintertime PM2.5 in the rural area of the Sichuan basin, China

This study conducted a field campaign using a time-of-flight aerosol chemical speciation monitor (ToF-ACSM) for PM2.5 measurement at a rural site in Sichuan Basin (SCB) during winter. The composition, diurnal variation, and source apportionment of non-refractory PM2.5 were analyzed. During the whole sampling process, the average concentration of PM2.5 was 52.9 μg m−3, in which the organic aerosol (OA) concentration was the highest (25.5 μg m−3), followed by nitrate (11.1 μg m−3), sulfate (8.2 μg m−3), ammonium (6.9 μg m−3) and chloride (1.3 μg m−3). The positive matrix factorization (PMF) model was used to analyze the sources of OA. Five factors, including a hydrocarbon-like organic aerosol (HOA), a coal combustion organic aerosol (CCOA), a biomass burning organic aerosol (BBOA), a less oxidized oxygenated organic aerosol (LO-OOA), and a more oxidized oxygenated organic aerosols (MO-OOA), were resolved. A haze episode was identified whose evolution was found to be mainly driven by BBOA. The backward trajectory and potential source contribution function (PSCF) analysis showed that the regions over northern Chongqing and eastern Sichuan province were potential source regions of BBOA and CCOA. This study can increase our knowledge of PM2.5 characteristics and sources, providing an understanding of the interaction between anthropogenic and natural emissions and atmospheric aging during transport in SCB.

Insights into the compositional differences of PM1 and PM2.5 from aerosol mass spectrometer measurements in Beijing, China

Aerosol mass spectrometers (AMS) have been widely used for characterization of submicron aerosol (PM1) species in the world. However, the chemical differences between PM1 and fine particles (PM2.5) in megacities are poorly understood. Here a PM1 high-resolution AMS with standard vaporizer (SV) and a PM2.5 time-of-flight aerosol chemical speciation monitor (ToF-ACSM) with capture vaporizer (CV) were deployed simultaneously in summer and winter in Beijing, China, and the chemical differences of non-refractory aerosol species between PM1 and PM2.5 were characterized. Our results showed that aerosol species in PM2.5 were overall highly correlated with those in PM1 (r2 > 0.8), yet the PM1/PM2.5 ratios varied largely for different aerosol species. Nitrate existed dominantly in PM1 (80–90%), while a considerable fraction of sulfate (30–45%) was observed in the range of 1–2.5 μm (PM1–2.5). Comparatively, PM1 organics showed higher fractions in PM2.5 in summer than winter (∼70%). The changes in PM1/PM2.5 ratios of secondary inorganic aerosol (SIA) depended strongly on relative humidity (RH) in summer with considerable decreases as the increase of RH, while such a RH dependence of PM1/PM2.5 ratios was not significant in winter due to the absence of high RH data. We further compared the source apportionment results of organic aerosol (OA) between PM1 and PM2.5. Similar to previous studies, the SV AMS reported ubiquitously higher primary OA than the CV ToF-ACSM, nearly by a factor of 2 for cooking OA, and the difference in secondary OA composition can be substantial, particularly in winter. With the simultaneous measurements of AMS and ACSM, a parameterized relationship between oxygen-to-carbon (O/C) ratio and CV f44 (fraction of m/z 44 in OA) in summer and winter was developed, which has a potential implication for studying the oxidation and hygroscopicity properties of OA considering the rapid increases in CV ToF-ACSM measurements worldwide.

In-situ measurement of secondary aerosol formation potential using a flow reactor: Livestock agricultural area

Atmospheric ammonia (NH3) is an important particulate matter (PM) precursor. The primary sources of ammonia in agriculture are livestock farming and synthetic fertilizers. Here, an oxidation flow reactor (OFR) was deployed in the vicinity of livestock farming during the summer of 2020 and winter of 2021 to determine the extent of secondary aerosol formation. The OFR was run in a 1-h cycle of different aging times for the daytime and nighttime oxidants of OH and NO3 radicals, respectively. The daytime reaction periods were 05:00–20:00 and 08:00–18:00, respectively, for summer and winter. Ambient and aged PM2.5 were characterized for secondary aerosol formation potential (AFP) using a time-of-flight aerosol chemical speciation monitor (ToF-ACSM). Ambient PM2.5 mean composition during summer was dominated in the order of nitrate (41%), organic matter (33%), ammonium (15%), and sulfate (11%). Secondary AFP was in the higher order, nitrate (71%), ammonium (20%), organic matter (8%), and sulfate (1%). A prominent effect of NH3 was observed when the primary aerosol was aged at high NOx and relative humidity (RH). Source apportionment revealed secondary organic aerosol (SOA)-dominant organic aerosols.

Measurement report: Intensive biomass burning emissions and rapid nitrate formation drive severe haze formation in the Sichuan Basin, China – insights from aerosol mass spectrometry

Abstract. Haze pollution is a severe environmental problem, caused by elevation of fine particles (aerodynamic diameter <2.5 µm, PM2.5), which is related to secondary aerosol formation, unfavourable synoptic conditions and regional transport, etc. The regional haze formation in basin areas, along with intensive emission of precursors, high relative humidity and poor dispersion conditions, is still limitedly understood. In this study, a field campaign was conducted to investigate the factors resulting in haze formation in the Sichuan Basin (SCB) during winter in 2021. The fine aerosol chemical composition was characterised using a time-of-flight aerosol chemical speciation monitor (ToF-ACSM), which also provided detailed information on the sources for organic aerosols (OAs). The average concentration of non-refractory fine particles (NR-PM2.5) was 98.5±38.7 µg m−3, and organics aerosols, nitrate, sulfate, ammonium and chloride took up 40.3 %, 28.8 %, 10.6 %, 15.3 % and 5.1 % of PM2.5. Three factors, including a hydrocarbon-like OA (HOA), a biomass burning OA (BBOA) and an oxygenated OA (OOA), were identified by applying the positive matrix factorisation (PMF) analysis, and they constituted 24.2 %, 24.2 % and 51.6 % of OA on average, respectively. Nitrate formation was promoted by gas-phase and aqueous-phase oxidation, while sulfate was mainly formed through aqueous-phase process. OOA showed strong dependence on Ox, demonstrating the contribution of photooxidation to OOA formation. OOA concentration increased as aerosol liquid water content (ALWC) increased within 200 µg m−3 and kept relatively constant when ALWC >200 µg m−3, suggesting the insignificant effect of aqueous-phase reactions on OOA formation. Among the three haze episodes identified during the whole campaign, the driving factors were different: the first haze episode (H1) was driven by nitrate formation through photochemical and aqueous-phase reactions, and the second haze episode (H2) was mainly driven by the intense emission of primary organic aerosols from biomass burning and vehicle exhaust, while the third haze episode (H3) was mainly driven by reactions involving nitrate formation and biomass burning emission. HOA and BBOA were scavenged, while OOA, nitrate and sulfate formation was enhanced by aqueous-phase reactions during fog periods, which resulted in the increase of O:C from pre-fog to post-fog periods. This study revealed the factors driving severe haze formation in the SCB and implied the benefit of controlling nitrate as well as intense biomass burning and vehicle exhaust emission for the mitigation of heavy aerosol pollution in this region.

Roles of Relative Humidity and Particle Size on Chemical Aging of Tropical Peatland Burning Particles: Potential Influence of Phase State and Implications for Hygroscopic Property

AbstractPeatland fires in Southeast Asia are an important source of primary organic aerosol (POA). Chemical aging of POA in the atmosphere produces oxygenated POA (OPOA). The OPOA production influences optical and hygroscopic properties, modulating the regional climate. However, the roles of environmental parameters such as relative humidity (RH) on chemical aging of peatland burning particles have rarely been investigated. Utilizing the potential aerosol mass (PAM) reactor, we conducted laboratory experiments for POA aging of particles generated from smoldering combustions of surface peat, fern, and Acacia leaves. The corresponding experiments for secondary organic aerosol formation were also separately conducted. Properties and chemical compositions of the resulting particle were quantified by both the hygroscopic tandem differential mobility analyzer and time‐of‐flight aerosol chemical speciation monitor (ToF‐ACSM). Conversion of peat combustion from POA to OPOA was pronounced when RH in the PAM reactor was higher. Considering that previous electromicroscopic observations demonstrated that peat combustion POA is likely (semi)solid, we postulate that oxidation of fresh peatland burning particles is faster at an elevated RH due to reduced viscosity following hygroscopic growth. Hygroscopicity parameter (κ) of aged POA particles linearly correlated with the mass fraction of OPOA that was quantified by the ToF‐ACSM. The above results highlight the importance of simultaneously measuring the chemical aging and particle phase state of peatland burning POA for quantifying their climatic impacts.

A local marine source of atmospheric particles in the High Arctic

The chemical composition of non-refractory submicron aerosol (NR-PM1) was characterized at the Villum Research Station (Villum) at Station Nord in North Greenland during spring-summer 2016 using a Time of Flight Aerosol Chemical Speciation Monitor (ToF-ACSM). The composition is dominated by sulfate (48%) and organic species (40%). Positive Matrix Factorization (PMF) identified three key factors corresponding to a primary hydrocarbon-like organic aerosol (HOA), and two types of secondary organic aerosol: oxygenated organic aerosol (OOA) and a marine organic aerosol (MOA). The HOA factor accounts for 5% of the organic aerosol mass, which is consistent with previous findings at Villum. The OOA factor accounts for 77% of the organic aerosol mass and correlates with accumulation mode particles, which supports previous findings indicating that oxidized organic aerosols are predominantly from long-range transport during winter and spring at Villum. The MOA factor was characterized by mass spectral fragments of methane sulfonic acid (MSA) from atmospheric oxidation of dimethyl sulfide, for which reason the MOA factor is considered to be of biogenic origin. MOA accounts for 18% of the organic aerosol mass and correlates with locally produced Aitken mode particles. This indicates that biogenic processes are not only a significant source of aerosols at Villum, but MOA also appears to be formed in the vicinity of the measurement site. This local geographical origin was confirmed through air mass back trajectory modelling and source-receptor analysis. During May, air masses frequently arrived from the east, with source regions for the MOA factor and therewith MSA located in the Barents Sea and Lincoln Sea with lesser contributions from the Greenland Sea. During June, air mass origin shifted to the west, with source regions for the MOA factor and MSA shifting correspondingly to Baffin Bay and the Canadian Arctic Archipelago. While shifting transport patterns between May and June lead to shifting source regions, sea ice likely played a role as well. During May, marginal ice zones were present in the Barents Sea between Svalbard and Franz Josef Land, while during June, sea ice in the northern part of Baffin Bay retreated and sea ice in the Canadian Arctic Archipelago decreased. Although May and June experienced different transport patterns and sea ice conditions, levels of the MOA factor and MSA were similar between the months. This is likely due to similarities between marine biological activities in the Barents Sea and Baffin Bay. This research highlights the complex relationship between transport patterns, sea ice conditions, and atmospheric particle concentrations. Multiyear aerosol chemical composition from several High Arctic sites is encouraged to determine the full effects of ocean-atmosphere interactions and transport patterns on atmospheric aerosol concentrations.

Organic aerosol source apportionment by using rolling positive matrix factorization: Application to a Mediterranean coastal city

We investigated the contributions and the evolution of organic aerosol (OA) sources at the Marseille-Longchamp supersite (MRS-LCP, France) based on Time-of-flight Aerosol Chemical Speciation Monitor (ToF-ACSM) measurements of non-refractory PM 1 over a fourteen-month period (1 February – 3 April 2018). The OA source apportionment was performed by positive matrix factorization (PMF) using the novel “rolling window” approach implemented in the Source Finder Professional (SoFi Pro). Here, PMF is performed over a 14-days window moving over the entire OA dataset, in order to account for the temporal variability of the source profiles. Six factors were resolved, including hydrocarbon-like organic aerosol (HOA) which is related to traffic exhausts, cooking-like organic aerosol (COA), biomass burning aerosol (BBOA), less oxidized organic aerosol (LOOA), more oxidized organic aerosol (MOOA) and a new defined source related to the mix between shipping and industrial plumes (Sh-IndOA). While HOA and COA consistently contribute to the total OA with on average 11.2% (ranging between 9.2 and 12.1% over the seasons) and 11.5% (11–12.1%), respectively, BBOA (11.7% on average) shows a larger seasonal variability with 18% in winter and no contribution in summer. BBOA profiles during winter were attributed to fresh biomass burning emissions from domestic heating, and more oxygenated profiles were assigned to regional land and agricultural waste burning for spring and early autumn. Sh-IndOA fraction is estimated to 4.5% (3.7–6.1%) and contributes to the total OA mass concentrations to a minor extent. The secondary organic aerosol (SOA) fraction includes both LOOA with 21.5% (18.8–27.2%) and MOOA with 39.6% (36.8–42.6%). Based on the f44/f43 analysis these sources appeared to be more linked to biogenic influences in summer, whereas the concentrations were associated with oxidized anthropogenic sources (biomass burning and road traffic) for the rest of the year. The investigation of MOOA geographical origins suggests some influence of air masses transported from the Rhône Valley and the west basin of the Mediterranean Sea. • OA source apportionment over 14 months at an urban background site. • Positive matrix factorization using the novel rolling window approach. • A new defined source of OA related to shipping and industrial plumes. • Highest contribution of SOA during every season.

Nontarget Screening Exhibits a Seasonal Cycle of PM2.5 Organic Aerosol Composition in Beijing.

The molecular composition of atmospheric particulate matter (PM) in the urban environment is complex, and it remains a challenge to identify its sources and formation pathways. Here, we report the seasonal variation of the molecular composition of organic aerosols (OA), based on 172 PM2.5 filter samples collected in Beijing, China, from February 2018 to March 2019. We applied a hierarchical cluster analysis (HCA) on a large nontarget-screening data set and found a strong seasonal difference in the OA chemical composition. Molecular fingerprints of the major compound clusters exhibit a unique molecular pattern in the Van Krevelen-space. We found that summer OA in Beijing features a higher degree of oxidation and a higher proportion of organosulfates (OSs) in comparison to OA during wintertime, which exhibits a high contribution from (nitro-)aromatic compounds. OSs appeared with a high intensity in summer-haze conditions, indicating the importance of anthropogenic enhancement of secondary OA in summer Beijing. Furthermore, we quantified the contribution of the four main compound clusters to total OA using surrogate standards. With this approach, we are able to explain a small fraction of the OA (∼11-14%) monitored by the Time-of-Flight Aerosol Chemical Speciation Monitor (ToF-ACSM). However, we observe a strong correlation between the sum of the quantified clusters and OA measured by the ToF-ACSM, indicating that the identified clusters represent the major variability of OA seasonal cycles. This study highlights the potential of using nontarget screening in combination with HCA for gaining a better understanding of the molecular composition and the origin of OA in the urban environment.

PM2.5 composition and sources in the San Joaquin Valley of California: A long-term study using ToF-ACSM with the capture vaporizer

The San Joaquin Valley (SJV) of California has suffered persistent particulate matter (PM) pollution despite many years of control efforts. To further understand the chemical drivers of this problem and to support the development of State Implementation Plan for PM, a time-of-flight aerosol chemical speciation monitor (ToF-ACSM) outfitted with a PM2.5 lens and a capture vaporizer has been deployed at the Fresno-Garland air monitoring site of the California Air Resource Board (CARB) since Oct. 2018. The instrument measured non-refractory species in PM2.5 continuously at 10-min resolution. In this study, the data acquired from Oct. 2018 to May 2019 were analyzed to investigate the chemical characteristics, sources and atmospheric processes of PM2.5 in the SJV. Comparisons of the ToF-ACSM measurement with various co-located aerosol instruments show good agreements. The inter-comparisons indicated that PM2.5 in Fresno was dominated by submicron particles during the winter whereas refractory species accounted for a major fraction of PM2.5 mass during the autumn associated with elevated PM10 loadings. A rolling window positive matrix factorization analysis was applied to the organic aerosol (OA) mass spectra using the Multilinear Engine (ME-2) algorithm. Three distinct OA sources were identified, including vehicle emissions, local and regional biomass burning, and formation of oxygenated species. There were significant seasonal variations in PM2.5 composition and sources. During the winter, residential wood burning and oxidation of nitrogen oxides were major contributors to the occurrence of haze episodes with PM2.5 dominated by biomass burning OA and nitrate. In autumn, agricultural activities and wildfires were found to be the main cause of PM pollution. PM2.5 concentrations decreased significantly after spring and were dominated by oxygenated OA during March to May. Our results highlight the importance of using seasonally dependent control strategies to mitigate PM pollution in the SJV.

Mediterranean nascent sea spray organic aerosol and relationships with seawater biogeochemistry

Abstract. The organic mass fraction from sea spray aerosol (SSA) is currently a subject of intense research. The majority of this research is dedicated to measurements in ambient air. However a number of studies have recently started to focus on nascent sea spray aerosol. This work presents measurements collected during a 5-week cruise in May and June 2017 in the central and western Mediterranean Sea, an oligotrophic marine region with low phytoplankton biomass. Surface seawater was continuously pumped into a bubble-bursting apparatus to generate nascent sea spray aerosol. Size distributions were measured with a differential mobility particle sizer (DMPS). Chemical characterization of the submicron aerosol was performed with a time-of-flight aerosol chemical speciation monitor (ToF-ACSM) operating with 10 min time resolution and with filter-based chemical analysis on a daily basis. Using positive matrix factorization analysis, the ToF-ACSM non-refractory organic matter (OMNR) was separated into four different organic aerosol types, identified as primary OA (POANR), oxidized OA (OOANR), methanesulfonic acid type OA (MSA-OANR), and mixed OA (MOANR). In parallel, surface seawater biogeochemical properties were monitored providing information on phytoplankton cell abundance and seawater particulate organic carbon (1 h time resolution) and seawater surface microlayer (SML) dissolved organic carbon (DOC) (on a daily basis). Statistically robust correlations (for n>500) were found between MOANR and nanophytoplankton cell abundance, as well as between POANR, OOANR, and particulate organic carbon (POC). Parameterizations of the contributions of different types of organics to the submicron nascent sea spray aerosol are proposed as a function of the seawater biogeochemical properties for use in models.

Measurement report: Fourteen months of real-time characterisation of the submicronic aerosol and its atmospheric dynamics at the Marseille–Longchamp supersite

Abstract. This study reports results of PM1 chemical composition determined using a Time-of-Flight Aerosol Chemical Speciation Monitor (ToF-ACSM) over a 14-month period (1 February 2017–13 April 2018) at the Marseille–Longchamp supersite (MRS-LCP) in France. Parallel measurements were performed with an aethalometer, an ultrafine particle monitor and a suite of instruments to monitor regulated pollutants (PM2.5, PM10, NOx, O3 and SO2). The average PM1 chemical composition over the period was dominated by organic aerosol (OA; 49.7 %) and black carbon (BC; 17.1 %), while sulfate accounted for 14.6 %, nitrate for 10.2 %, ammonium for 7.9 % and chloride for 0.5 % only. Wintertime was found to be the season contributing the most to the annual PM1 mass concentration (30 %), followed by autumn (26 %), summer (24 %) and spring (20 %). During this season, OA and BC concentrations were found to contribute 32 % and 31 % of their annual concentrations, respectively, as a combined result of heavy urban traffic, high emissions from residential heating and low planetary boundary layer (PBL) height. Most (75 %) of the 15 days exceeding the target daily PM2.5 concentration value recommended by the World Health Organization (WHO) occurred during this season. Local and long-range pollution episodes with contrasting chemical composition could be distinguished, accounting for 40 % and 60 % of the exceedance days, respectively. Enhanced OA and BC concentrations, mostly originating from domestic wood burning under nocturnal land breeze conditions, were observed during local pollution episodes, while high levels of oxygenated OA and inorganic nitrate were associated with medium-/long-range transported particles. In summertime, substantially higher concentrations of sulfate were found, with an average and a maximum contribution to the PM1 mass of 24 % and 66 %, respectively. Results from k-means clustering analysis of daily profiles of sulfate concentrations clearly reveal the significant influence of local harbour/industrial activities on air quality in addition to the more regional contribution of shipping traffic that originates from the Mediterranean basin.

Altitude Aerosol Measurements in Central France: Seasonality, Sources and Free‐Troposphere/Boundary Layer Segregation

AbstractThe chemical composition of nonrefractory submicron aerosol particles was measured at the Puy‐de‐Dôme (PUY) station (1,465 m a.s.l) during 2015 using a Time‐of‐Flight Aerosol Chemical Speciation Monitor (ToF‐ACSM). These aerosol chemistry measurements are combined with online black carbon (BC) measurements to provide an overview of the submicron aerosol composition. Averaged over the entire year, and normalized to standard temperature and pressure, organic aerosol (OA) dominates the PM1 concentration during all seasons and within all air mass types (2.12 ± 1.73 µgm−3), and is responsible for summertime increases in aerosol concentration. Highest mass concentrations were measured during the summer, when air masses were arriving over mainland Europe and lowest in the winter months (when most air masses were of Atlantic origin). OA source apportionment was performed separately during each season, using the Source Finder (SoFi) interface for the multilinear engine. The PUY site, situated at 1,465 m a.s.l, although mainly sampling in the atmospheric boundary layer, it is sometimes sampling in the lower free troposphere (FT), providing the opportunity to identify the characteristics of FT aerosol. In order to accurately identify these sampling periods, the methodology described in Farah et al. (2018), during the same time period (2015/2016), was applied to the data. During this period, FT air masses are sampled approximately 20% of the time. This work provides, on one hand, a description of long‐term aerosol chemical properties at a remote regional site in central Europe and, on the other hand a characteristic chemical signature of FT aerosols over this region. This data can be used to improve our understanding of the transport and aging properties of aerosols at regional observation sites.

Effects of continental emissions on cloud condensation nuclei (CCN) activity in the northern South China Sea during summertime 2018

Abstract. Aerosol particles in marine atmosphere have been shown to significantly affect cloud formation, atmospheric optical properties, and climate change. However, high temporally and spatially resolved atmospheric measurements over the sea are currently sparse, limiting our understanding of aerosol properties in marine atmosphere. In this study, a ship-based cruise campaign was conducted over the northern South China Sea (SCS) region during summertime 2018. The chemical composition of non-refractory PM1 (NR-PM1), the particle number size distribution (PNSD), and size-resolved cloud condensation nuclei (CCN) activity were measured by a time-of-flight aerosol chemical speciation monitor (ToF-ACSM) and the combination of a cloud condensation nuclei counter (CCNc) and a scanning mobility particle sizer (SMPS). Overall, aerosol particles exhibited a unimodal distribution centering at 60–80 nm and the chemical composition of the NR-PM1 was dominated by sulfate (∼ 46 %), which likely originated from anthropogenic emissions rather than dimethyl sulfide (DMS) oxidation. Two polluted episodes (P1 and P2) were observed, and both were characterized by high particle number concentrations (NCN) which originated from local emissions and from emissions in inland China via long-range transport. The concentrations of trace gases (i.e., O3, CO, NOx) and particles (NCN and NCCN at ss = 0.34 %) were elevated during P2 at the end of the campaign and decreased with offshore distance, further suggesting important impacts of anthropogenic emissions from the inland Pearl River Delta (PRD) region. Two relatively clean periods (C1 and C2) prior to and after tropical storm Bebinca were classified and the air was affected by air masses from the southwest and from the Indo-Chinese Peninsula, respectively. Chemical composition measurements showed an increase in organic mass fraction during P2 compared to C2; however, no obviously different κ values were obtained from the CCNc measurements, implying that the air masses carried pollutants from local sources during long-range transport. We report an average value of about 0.4 for the aerosol hygroscopicity parameter κ, which falls within the literature values (i.e., 0.2–1.0) for urban and remote marine atmosphere. In addition, our results showed that the CCN fraction (NCCN∕NCN, tot) and the κ values had no clear correlation either with the offshore distance or with concentrations of the particles. Our study highlights dynamical variations in particle properties and the impact of long-range transport from continental China and the Indo-Chinese Peninsula on the northern SCS region during summertime.

Characterization of submicron particles by time-of-flight aerosol chemical speciation monitor (ToF-ACSM) during wintertime: aerosol composition, sources, and chemical processes in Guangzhou, China

Abstract. Particulate matter (PM) pollution in China is an emerging environmental issue which policy makers and the public have increasingly paid attention to. In order to investigate the characteristics, sources, and chemical processes of PM pollution in Guangzhou, field measurements were conducted from 20 November 2017 to 5 January 2018, with a time-of-flight aerosol chemical speciation monitor (ToF-ACSM) and other collocated instruments. Mass concentrations of non-refractory submicron particulate matter (NR-PM1) measured by the ToF-ACSM correlated well with those of PM2.5 or PM1.1 measured by filter-based methods. The organic mass fraction increased from 45 % to 53 % when the air switched from non-pollution periods to pollution episodes (EPs), indicating significant roles of organic aerosols (OAs) during the whole study. Based on the mass spectra measured by the ToF-ACSM, positive matrix factorization (PMF) with the multilinear engine (ME-2) algorithm was performed to deconvolve OA into four factors, including hydrocarbon-like OA (HOA, 12 %), cooking OA (COA, 18 %), semi-volatile oxygenated OA (SVOOA, 30 %), and low-volatility oxygenated OA (LVOOA, 40 %). Furthermore, we found that SVOOA and nitrate were significantly contributed from local traffic emissions while sulfate and LVOOA were mostly attributed to regional pollutants. Comparisons between this work and other previous studies in China show that secondary organic aerosol (SOA) fraction in total OA increases spatially across China from the north to the south. Two distinctly opposite trends for NR-PM1 formation were observed during non-pollution periods and pollution EPs. The ratio of secondary PM (SPM = SVOOA + LVOOA + sulfate + nitrate + ammonium) to primary PM (PPM = HOA + COA + chloride), together with peroxy radicals RO2∗ and ozone, increased with increasing NR-PM1 concentration during non-pollution periods, while an opposite trend of these three quantities was observed during pollution EPs. Furthermore, oxidation degrees of both OA and SOA were investigated using the f44∕f43 space and the results show that at least two OOA factors are needed to cover a large range of f44 and f43 in Guangzhou. Comparisons between our results and other laboratory studies imply that volatile organic compounds (VOCs) from traffic emissions, in particular from diesel combustion and aromatic compounds, are the most likely SOA precursors in Guangzhou. Peroxy radical RO2∗ was used as a tracer for SOA formed through gas-phase oxidation. For non-pollution periods, SOA concentration was reasonably correlated with RO2∗ concentration during both daytime and nighttime, suggesting that gas-phase oxidation was primarily responsible for SOA formation. However, there was no correlation between SOA and RO2∗ in pollution EPs, suggesting a dramatically changed mechanism for SOA formation. This conclusion can also be supported by different features of SOA in a van Krevelen diagram between non-pollution periods and pollution EPs. Furthermore, for pollution EPs, when NR-PM1 mass concentration was divided into six segments, in each segment except for the lowest one SOA concentration was correlated moderately with RO2∗ concentration, suggesting that gas-phase oxidation still plays important roles in SOA formation. The intercepts of the above linear regressions, which likely correspond to the extent of other mechanisms (i.e., heterogeneous and multiphase reactions), increase with increasing NR-PM1 mass concentration. Our results suggest that while gas-phase oxidation contributes predominantly to SOA formation during non-pollution periods, other mechanisms such as heterogeneous and multiphase reactions play more important roles in SOA formation during pollution EPs than gas-phase oxidation.

Sub micron aerosol variability and its ageing process at a high altitude site in India: Impact of meteorological conditions

The effect of relative humidity and temperature on the submicron aerosol variability and its ageing process was studied over a high altitude site, Mahabaleshwar in south-west India. The mass composition of non-refractory particulate matter of 1 μm (NR-PM1) size was obtained using Time of Flight Aerosol Chemical Speciation Monitor (ToF-ACSM) along with the measurements on a few trace gases during winter (December 2017–February 2018) and summer season (20th March - 5th May 2018). Sulfate exhibited strong dependence on the relative humidity (RH) as its mass fraction increased with the increase in RH. The Sulfate oxidation ratio (SOR) calculated during summer season also showed an increasing trend with RH indicating the influence of aqueous phase oxidation on sulfate fraction. On the other hand, OOA showed remarkable enhancement in its mass fraction with the increase in temperature along with the corresponding increase in f44 and tropospheric ozone. OOA, ozone and f44 ratio increased 14–34%, 8–26% and 25–43% respectively with the increase in temperature from 18 to 30 °C. This is indicative of the dominance of photochemical ageing processes during high temperature conditions. The extent of photochemical ageing was found to be higher during summer season (mean temperature ∼25.4 ± 2.6 °C) as compared to winter season (mean temperature ∼20.5 ± 2.6 °C). The nitrate diurnal was majorly governed by gas to particle partitioning process during winter season, whereas the summertime nitrate diurnal was influenced primarily by its formation rate. The non parametric wind regression analysis revealed that the mass concentration during winter was majorly contributed by distant sources from north east direction while during summer the local sources were more dominant.

Characterization of anthropogenic organic aerosols by TOF-ACSM with the new capture vaporizer

Abstract. A new capture vaporizer (CV) has been developed and used recently in the Aerodyne aerosol mass spectrometer (AMS) and aerosol chemical speciation monitor (ACSM) instead of the standard vaporizer (SV) to reduce the particle bounce. It is important to characterize the CV performance in different environments. In this study, we characterized specific organic aerosols (OAs) from vehicle, cooking, biomass burning, and coal burning emissions by a time-of-flight ACSM (TOF-ACSM) with the CV. Their corresponding marker ions that have been defined in the previous SV-based analysis are still valid in the CV mass spectra. Spectra of OAs from cooking and vehicle exhaust show similarities in distinct alkyl fragments but different ratios of m∕z 55 and 57. Ions related to polycyclic aromatic hydrocarbons are present in the OA spectra obtained from burning lignite and bituminous coal but not in the spectra obtained from burning anthracite. Although the relative intensities of m∕z 60 and 73 are much lower in the CV spectra than in the SV spectra for biomass burning OA, they are still relatively greater compared with the spectra for other sources. Our data suggest an atmospheric background of f60 of below 0.03 % for CV. Moreover, we deployed the CV TOF-ACSM along with a SV AMS in urban Beijing during the winter of 2017 to characterize ambient OA with strong anthropogenic influences. The CV TOF-ACSM shows a collection efficiency (CE) of about unity. The CV and SV data show consistent mass concentrations of sulfate, nitrate, ammonium, and OA. Six OA factors are identified by the positive matrix factorization (PMF) analysis for both the CV and the SV data. The SV and CV PMF factors show good correlations in mass concentrations. The SV and CV factors related to coal combustion and cooking differ significantly in loadings, explained by the PMF uncertainty and the lack of understanding of the relative ionization efficiency and CE for primary OA. The CV factors related to secondary sources show greater loadings than the SV factors, which may be associated with the changes in signal-to-noise ratios of various ions in the PMF analysis. Our results support improved mass quantification and useful source identification by the CV for ambient particles in the polluted urban environment. The difference in factor loadings between SV and CV should be considered when interpreting or comparing the PMF results among studies.

Diesel Soot and Amine-Containing Organic Sulfate Aerosols in an Arctic Oil Field.

The rapid decrease in Arctic sea ice is motivating development and increasing oil and gas extraction activities. However, few observations of these local Arctic emissions exist, limiting the understanding of impacts on atmospheric composition and climate. To address this knowledge gap, the chemical composition of atmospheric aerosols was measured within the North Slope of Alaska oil fields during August and September 2016 using an aerosol time-of-flight mass spectrometer (ATOFMS) and a time-of-flight aerosol chemical speciation monitor (ToF-ACSM). Plumes from oil and gas extraction activities were characterized by soot internally mixed with sulfate (matching diesel soot) and organic carbon particles containing aminium sulfate salts. Sea spray aerosol at the coastal site was frequently internally mixed with sulfate and nitrate, from multiphase chemical processing from elevated NOx and SO2 within the oil field. Background (nonplume) air masses were characterized by aged combustion aerosol. No periods of "clean" (nonpolluted) Arctic air were observed. The composition of the nonrefractory aerosol measured with the ACSM was similar during plume and background periods and was consistent with the mass concentrations of nonrefractory particles measured by ATOFMS. Two ultrafine aerosol growth events were observed during oil field background periods and were correlated with fine mode amine-containing particles.

A Significant Portion of Water-Soluble Organic Matter in Fresh Biomass Burning Particles Does Not Contribute to Hygroscopic Growth: An Application of Polarity Segregation by 1-Octanol-Water Partitioning Method.

The importance of water-soluble organic matter (WSOM) on the hygroscopic growth of particles is recognized, yet roles of different categories of WSOM are under debate. We segregated WSOM from Indonesian biomass burning particles by the 1-octanol-water partitioning method. The method is based on the 1-octanol-water partition coefficient (KOW), which correlates with water solubility. The segregated WSOM was analyzed using the humidified tandem differential mobility analyzer (HTDMA) and time-of-flight aerosol chemical speciation monitor (ToF-ACSM). Both the hygroscopicity parameter κ and the fractional contribution of m/z 44 (f44), which serves as a metric for degree of oxygenation, increased with polarity. This result experimentally evidenced that highly polar/water-soluble OM is highly hygroscopic/oxygenated. Positive matrix factorization (PMF) identified three factors from the ToF-ACSM data. Deconvolution of κ by PMF factors demonstrated that the less polar fractions, which occupy approximately 20-60% of WSOM dependent on the biomass type, almost do not contribute to water uptake under subsaturated conditions. This result highlights that categorization of WSOM will be needed to understand how hygroscopic growth of aerosol particles is regulated.