Aerosol Mass Spectrometer Research Articles

Effects of isoprene on the ozonolysis of Δ3-carene and β-caryophyllene: Mechanisms of secondary organic aerosol formation and cross-dimerization

Elucidating the mutual effects between the different volatile organic compounds (VOCs) is crucial for comprehending the formation mechanism of atmospheric secondary organic aerosols (SOA). Here, the mixed VOCs experiments of isoprene and Δ3-carene/β-caryophyllene were carried out in the presence of O3 using an indoor smog chamber. The suppression effect of isoprene was recognized by the scanning mobility particle sizer spectrometer, online vacuum ultraviolet free electron laser (VUV-FEL) photoionization aerosol mass spectrometry, and quantum chemical calculations. The results indicate that the suppression effect of isoprene on the ozonolysis of Δ3-carene and β-caryophyllene shows fluctuating and monotonous trends, respectively. The carbon content of the precursor could be the main factor for regulating the strength of the suppression effect. Plausible structures and formation mechanisms of several new products generated from the single VOC precursor and VOC-cross-reaction are proposed, which enrich the category of VOC oxidation products. Meanwhile, a new dimerization mechanism of the RO2 + R'O2 reaction is suggested, which offers an intriguing perspective on the gas phase formation process of particle phase accretion products. The present findings provide valuable insights into clarifying the pivotal roles played by isoprene in the interplay between different VOCs and understanding of SOA formation mechanisms of VOC mixtures, especially nearby the emission origins.

Bulk and molecular-level composition of primary organic aerosol from wood, straw, cow dung, and plastic burning

Abstract. During the past decades, the source apportionment of organic aerosol (OA) in ambient air has been improving substantially. The database of source retrieval model-resolved mass spectral profiles for different sources has been built with the aerosol mass spectrometer (AMS). However, distinguishing similar sources (such as wildfires and residential wood burning) remains challenging, as the hard ionization of the AMS mostly fragments compounds and therefore cannot capture detailed molecular information. Recent mass spectrometer technologies of soft ionization and high mass resolution have allowed for aerosol characterization at the molecular formula level. In this study, we systematically estimated the emission factors and characterized the primary OA (POA) chemical composition with the AMS and the extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) for the first time from a variety of solid fuels, including beech logs, spruce and pine logs, spruce and pine branches and needles, straw, cow dung, and plastic bags. The emission factors of organic matter estimated by the AMS and hydrocarbon gases estimated by the total hydrocarbon analyzer are 16.2 ± 10.8 g kg−1 and 30.3 ± 8.5 g kg−1 for cow dung burning, which is generally higher than that of wood (beech, spruce, and pine), straw, and plastic bag burning (in the range from 1.1 to 6.2 g kg−1 and 14.1 to 19.3 g kg−1). The POA measured by the AMS shows that the f60 (mass fraction of m/z 60) varies from 0.003 to 0.04 based on fuel types and combustion efficiency for wood (beech, spruce, and pine) and cow dung burning. On a molecular level, the dominant compound of POA from wood, straw, and cow dung is C6H10O5 (mainly levoglucosan), contributing ∼ 7 % to ∼ 30 % of the total intensity, followed by C8H12O6 with fractions of ∼ 2 % to ∼ 9 %. However, as they are prevalent in all burning of biomass material, they cannot act as tracers for the specific sources. By using the Mann–Whitney U test among the studied fuels, we find specific potential new markers for these fuels from the measurement of the AMS and EESI-TOF. Markers from spruce and pine burning are likely related to resin acids (e.g., compounds with 20–21 carbon atoms). The product from the pyrolysis of hardwood lignins is found especially in beech log burning. Nitrogen-containing species are selected markers primarily for cow dung open burning. These markers in the future will provide support for the source apportionment.

Mixing state and effective density of aerosol particles during the Beijing 2022 Olympic Winter Games

Abstract. Mixing state and density are two key parameters of aerosol particles affecting their impacts on radiative forcing and human health. Here a single-particle aerosol mass spectrometer in tandem with a differential mobility analyzer and an aerodynamic aerosol classifier was deployed during the Beijing 2022 Olympic Winter Games (OWG) to investigate the impacts of emission controls on particle mixing state and density. Our results show the dominance of carbonaceous particles comprising mainly total elemental carbon (Total-EC, 13.4 %), total organic carbon (Total-OC, 10.5 %) and Total-ECOC (47.1 %). Particularly, the particles containing organic carbon and sulfate were enhanced significantly during OWG, although those from primary emissions decreased. The composition of carbonaceous particles also changed significantly which was characterized by the decreases in EC mixed with nitrate and sulfate (EC-NS), EC mixed with potassium nitrate (KEC-N), and amine-containing particles and increase in ECOC mixed with nitrate and sulfate (ECOC-NS). This result indicates that emission controls during OWG reduced the mixing of EC with inorganic aerosol species and amines yet increased the mixing of EC with organic aerosol. The average effective density (ρeff) of aerosol particles (150–300 nm) was 1.15 g cm−3 during the non-Olympic Winter Games (nOWG), with higher values during OWG (1.26 g cm−3) due to the increase in secondary particle contribution. In addition, the ρeff of most particles increased with the increases in pollution levels and relative humidity, yet they varied differently for different types of particles, highlighting the impacts of aging and formation processes on the changes of particle density and mixing state.

Response of organic aerosol to Delhi's pollution control measures over the period 2011–2018

Some of the world's highest air pollution episodes occur in Delhi, India and studies have shown particulate matter (PM) is the leading air pollutant to cause adverse health effects on Delhi's population. It is therefore vital to chart sources of PM over long time periods to effectively identify trends, particularly as multiple air quality mitigation measures have been implemented in Delhi over the past 10 years but remain unevaluated. An automated offline aerosol mass spectrometry (AMS) method has been developed which has enabled high-throughput analysis of PM filters. This novel offline-AMS method uses an organic solvent mix of acetone and water to deliver high extraction recoveries of organic aerosol (OA) (95.4 ± 8.3%). Positive matrix factorisation (PMF) source apportionment was performed on the OA fraction extracted from PM10 filter samples collected in Delhi in 2011, 2015 and 2018 to provide snapshots of the responses of OA to changes in sources in Delhi. The nine factors of OA resolved by PMF group into four primary source categories: traffic, cooking, coal-combustion and burning-related (solid fuel or open burning). Burning-related OA made the largest contribution during the winter and post-monsoon, when total OA concentrations were at their highest. Annual mean burning-related OA concentrations declined by 47% between 2015 and 2018, likely associated with the 2015 ban on open waste burning and controls and incentives to reduce crop-residue burning. Compositional analysis of OA factors shows municipal waste burning tracers still present in 2018, indicating further scope to reduce burning-related OA. The closure of the two coal power stations, along with initiatives to decrease coal use in industry, businesses, and residential homes, resulted in a significant decrease (87%) in coal-combustion OA. This corresponds to a 17% reduction in total OA, which shows the effectiveness of these measures in reducing PM10. Increases in traffic OA appear to have been offset by the introduction of the Bharat stage emissions standards for vehicles as the increases do not reflect the rapid increase in registered vehicles. However, daytime restrictions on heavy goods vehicles (HGVs) entering the city is linked to large increases in PM10 during the winter and post-monsoon, likely because the large influx of diesel-engine HGVs during the early mornings and evenings is timed with a particularly low planetary boundary layer height that enhances surface concentrations.

Characteristics of Seasonal PM1 Chemical Components in the urban area of Ansan

In this study, chemical properties of particulate matter (PM<sub>1</sub>) present in the urban area of Ansan in 2021 were analyzed using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Intensive observation was conducted during the measurement periods of spring (22 days), summer (29 days), autumn (60 days), and winter (29 days). High concentrations of PM<sub>1</sub> were observed when a wind speed was low (< 0.81 m/s) and a direction of air flow was the east. PM<sub>1</sub> concentration was the highest in spring (March), followed by summer (June and August), winter (December), and autumn (September and October). The main components of PM<sub>1</sub> were organic, followed by nitrate, ammonium, and sulfate. The ratio of organic oxygen to organic carbon (O/C) was high in summer (0.64) and low in winter (0.51); conversely, the ratio of organic hydrogen to organic carbon (H/C) was higher in winter (1.66) than in summer (1.58). As for the oxidation rates of inorganic components, the nitrogen oxidation rate and sulfur oxidation rate were the highest in spring (NOR, 0.12; SOR, 0.64), which directly affected the rise in PM<sub>1</sub> mass concentration in spring. Highly soluble nitrate was the largest component among the inorganic components of PM<sub>1</sub>, and the PM<sub>1</sub> was found to be rich in ammonium in all seasons. PM<sub>1</sub> mass concentration and chemical composition increased with an increase of relative humidity (RH): the concentration of PM<sub>1</sub> in wet conditions (RH > 60%) was found to be more than twice of that in dry conditions (RH < 40%). The largest component of PM<sub>1</sub> in Ansan consisted of organic compounds; however, a high proportion of inorganic components, including nitrate, was also recorded.

Dynamic Changes of Composition of Particulate Matter Emissions during Residential Biomass Combustion.

Residential biomass combustion in developing countries produces significant primary particulate matter (PM) emissions. Highly time-resolved aerosol mass spectrometry and aethalometer measurements were used to investigate the dynamic changes of emitted PM chemical composition from a typical improved stove burning with wood and crop straw in China. Combustion temperature and organic aerosol (OA) concentration increased quickly during the ignition stage. The flaming stage was characterized by high combustion temperature and high pollutant [including OA, black carbon (BC), inorganic salts, and polycyclic aromatic hydrocarbons (PAHs)] emissions, while the burnout stage is characterized by low combustion temperature and lower pollutant emissions. OA was the primary emitted species; emission factors of OA in the flaming stage were generally higher (24.5-792%) than those in the burnout stage. Mass spectral signatures of OA were obtained. The ratio of Cl-/OA for wood combustion (0.05 ± 0.01) is much lower than that from burning crop straw (0.32 ± 0.19). Hydrocarbon OA emissions dominated during the ignition and flaming stages. A high percentage of oxidized OA was emitted during the burnout stage. The relationship between PAHs and BC/OA emissions under different burning conditions was investigated, and PAHs may act as intermediate products in the conversion of OA to BC.

Deposition of secondary organic aerosol in human lung model: Effect of photochemically aged aerosol on human respiratory system

Ultrafine particles (UFP) of Secondary Organic Aerosol (SOA) penetrate deep into the human respiratory system and exert fatal effects on human health. However, there is little data on the potential deposited doses of UFP-generated SOA in the human respiratory tract. This study is to estimate the fraction of aerosol deposition using a multiple-path-particle-dosimetry (MPPD) model. For relevancy of real life, the model employed measured concentrations of toluene-derived fresh and aged SOA produced within serially connected smog chamber and PAM-OFR (Potential Aerosol Mass-Oxidation Flow Reactor) under atmospheric environmental conditions (NOx and relative humidity). The number concentrations and chemical composition of fresh and aged aerosols produced within the chambers were measured using Scanning Mobility Particle Sizer (SMPS) and High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS), while the morphology of individual particles was analyzed using Scanning Electron Microscopy (SEM). The number concentration of aged SOA-w/s was more than double compared to that of fresh SOA-w/s (maximum reached after 10 h) with its size less than 100 nm. The O:C ratio for aged SOA-w/s were 0.96 and 1.15 depending on RH (0.96 at 3% RH and 1.15 at 50% RH), and individual spherical particles containing water were present in agglomerates with its size of less than 1 µm. In all inhalable fresh and aged SOA produced in the two chambers, 5–22% of aerosol is deposited in the Head airways, 4–8% in the tracheobronchial, and 8–34% in the alveolar regions. The predominant deposition of the aged aerosol occurred in the alveoli (in the generation 20th lobe), and the deposition faction in the alveoli was 2–3 times higher in the children group than the adults group. This study presented a quantitative exposure assessment of SOA generated under a realistic simulation and suggested the possibility of evaluating long-term exposure to SOA and potential health effects by determining the potential inhalable aerosol doses and the fraction of deposition in the human respiratory system.

Size‐Dependent Nighttime Formation of Particulate Secondary Organic Nitrates in Urban Air

AbstractParticulate secondary organic nitrates play a key role in understanding secondary organic aerosol production, ozone formation, and the atmospheric nitrogen cycle. However, the formation of particulate secondary organic nitrates in ambient air remains poorly understood. In this study, the nighttime formation processes of particulate secondary organic nitrates were investigated based on size‐resolved aerosols measured in urban air of China with a soot particle long‐time‐of‐flight aerosol mass spectrometer. The results show a bimodal size distribution of particulate secondary organic nitrates, peaking at ∼350 nm in condensation mode (100–400 nm) and ∼750 nm in droplet mode (400–2,500 nm), respectively. The nighttime formation processes of particulate secondary organic nitrates in the two size modes were respectively governed by temperature‐dependent condensation and aqueous‐phase processing. In particular, the mass concentration of particulate secondary organic nitrates in condensation mode was positively correlated with nitrate radical production and negatively correlated with temperature, suggesting that the formation processes were associated with the gas‐particle conversion of nitrate radical oxidation products. In contrast, the enhanced particulate secondary organic nitrates in droplet mode were predominantly contributed by aqueous‐phase processing, as indicated by the strong positive correlation with aerosol liquid water content and typical fragment ions from aqueous processing products (r = 0.52–0.59, P < 0.01). Our results highlight the potential of a size‐dependent mechanism to elucidate the formation processes of particulate secondary organic nitrates.

In-depth study of the formation processes of single atmospheric particles in the south-eastern margin of the Tibetan Plateau

Abstract. The unique geographical location of the Tibetan Plateau (TP) plays an important role in regulating global climate change, but the impacts of the chemical components and atmospheric processing on the size distribution and mixing state of individual particles are rarely explored in the south-eastern margin of the TP, which is a transport channel for pollutants from Southeast Asia to the TP during the pre-monsoon season. Thus a single-particle aerosol mass spectrometer (SPAMS) was deployed to investigate how the local emissions of chemical composition interact with the transporting particles and assess the mixing state of different particle types and secondary formation in this study. The TP particles were classified into six distinct types, mainly including the largest fraction of the potassium-rich (K-rich) type in the total particles (30.9 %), followed by the biomass burning (BB) type (18.7 %). Most particle types were mainly transported from the sampling site's surroundings and along the Sino-Myanmar border, but the air mass trajectories from north-eastern India and Myanmar show a greater impact on the number fraction of the BB (31.7 %) and dust (18.2 %) types, respectively. Then, the two episodes with high particle concentrations showed that the differences in the meteorological conditions in the same trajectory clusters could cause significant changes in chemical components, especially the dust and aged elemental carbon (aged EC) types, which changed by a total of 93.6 % and 72.0 %, respectively. Ammonium and dust particles distribute at a relatively larger size (∼600 nm), but the size peak of other types is present at ∼440 nm. Compared with the abundant sulfate (97HSO4-), the low nitrate (62NO3-) internally mixed in TP particles is mainly due to the fact that nitrate is more volatilized during the transport process. The formation mechanism of secondary speciation demonstrates that the formation capacity of atmospheric oxidation is presumably affected by the convective transmission and the regional transport in the TP. However, the relative humidity (RH) could significantly promote the formation of secondary species, especially 97HSO4- and 18NH4+. This study provides new insights into the particle composition and size, mixing state, and ageing mechanism in high time resolution over the TP region.

Chemically distinct particle-phase emissions from highly controlled pyrolysis of three wood types

Abstract. Wood pyrolysis is a distinct process that precedes combustion and contributes to biomass and biofuel burning gas-phase and particle-phase emissions. Pyrolysis is defined as the thermochemical degradation of wood, the products of which can be released directly or undergo further reaction during gas-phase combustion. To isolate and study the processes and emissions of pyrolysis, a custom-made reactor was used to uniformly heat small blocks of wood in a nitrogen atmosphere. Pieces of maple, Douglas fir, and oak wood (maximum of 155 cm3) were pyrolyzed in a temperature-controlled chamber set to 400, 500, or 600 ∘C. Real-time particle-phase emissions were measured with a soot particle aerosol mass spectrometer (SP-AMS) and correlated with simultaneous gas-phase emission measurements of CO. Particle and gas emissions increased rapidly after inserting a wood sample, remained high for tens of minutes, and then dropped rapidly leaving behind char. The particulate mass-loading profiles varied with elapsed experiment time, wood type and size, and pyrolysis chamber temperature. The chemical composition of the emitted particles was organic (C, H, O), with negligible black carbon or nitrogen. The emitted particles displayed chemical signatures unique to pyrolysis and were notably different from flaming or smoldering wood combustion. The most abundant fragment ions in the mass spectrum were CO+ and CHO+, which together made up 23 % of the total aerosol mass on average, whereas CO2+ accounted for less than 4 %, in sharp contrast with ambient aerosol where CO2+ is often a dominant contributor. The mass spectra also showed signatures of levoglucosan and other anhydrous sugars. The fractional contribution of m/z 60, traditionally a tracer for anhydrous sugars including levoglucosan, to total loading (f60) was observed to be between 0.002 and 0.039, similar to previous observations from wildfires and controlled wood fires. Atomic ratios of oxygen and hydrogen to carbon, O:C and H:C as calculated from AMS mass spectra, varied between 0.41–0.81 and 1.06–1.57, respectively, with individual conditions lying within a continuum of O:C and H:C for wood's primary constituents: cellulose, hemicellulose, and lignin. This work identifies the mass spectral signatures of particle emissions directly from pyrolysis, including f60 and the CO+/CO2+ ratio, through controlled laboratory experiments in order to help in understanding the importance of pyrolysis emissions in the broader context of wildfires and controlled wood fires.

Evolution of organic carbon in the laboratory oxidation of biomass-burning emissions

Abstract. Biomass burning (BB) is a major source of reactive organic carbon into the atmosphere. Once in the atmosphere, these organic BB emissions, in both the gas and particle phases, are subject to atmospheric oxidation, though the nature and impact of the chemical transformations are not currently well constrained. Here we describe experiments carried out as part of the FIREX FireLab campaign, in which smoke from the combustion of fuels typical of the western United States was sampled into an environmental chamber and exposed to high concentrations of OH, to simulate the equivalent of up to 2 d of atmospheric oxidation. The evolution of the organic mixture was monitored using three real-time time-of-flight mass spectrometric instruments (a proton transfer reaction mass spectrometer, an iodide chemical ionization mass spectrometer, and an aerosol mass spectrometer), providing measurements of both individual species and ensemble properties of the mixture. The combined measurements from these instruments achieve a reasonable degree of carbon closure (within 15 %–35 %), indicating that most of the reactive organic carbon is measured by these instruments. Consistent with our previous studies of the oxidation of individual organic species, atmospheric oxidation of the complex organic mixture leads to the formation of species that on average are smaller and more oxidized than those in the unoxidized emissions. In addition, the comparison of mass spectra from the different fuels indicates that the oxidative evolution of BB emissions proceeds largely independent of fuel type, with different fresh smoke mixtures ultimately converging into a common, aged distribution of gas-phase compounds. This distribution is characterized by high concentrations of several small, volatile oxygenates, formed from fragmentation reactions, as well as a complex pool of many minor oxidized species and secondary organic aerosol, likely formed via functionalization processes.

Chemical evolution of primary and secondary biomass burning aerosols during daytime and nighttime

Abstract. Primary emissions from wood and pellet stoves were aged in an atmospheric simulation chamber under daytime and nighttime conditions. The aerosol was analyzed with online aerosol mass spectrometry and offline Fourier transform infrared spectroscopy (FTIR). Measurements using the two techniques agreed reasonably well in terms of the organic aerosol (OA) mass concentration, OA:OC trends, and concentrations of biomass burning markers – lignin-like compounds and anhydrosugars. Based on aerosol mass spectrometry, around 15 % of the primary organic aerosol (POA) mass underwent some form of transformation during daytime oxidation conditions after 6–10 h of atmospheric exposure. A lesser extent of transformation was observed during the nighttime oxidation. The decay of certain semi-volatile (e.g., levoglucosan) and less volatile (e.g., lignin-like) POA components was substantial during aging, highlighting the role of heterogeneous reactions and gas–particle partitioning. Lignin-like compounds were observed to degrade under both daytime and nighttime conditions, whereas anhydrosugars degraded only under daytime conditions. Among the marker mass fragments of primary biomass burning OA (bbPOA), heavy ones (higher m/z) were relatively more stable during aging. The biomass burning secondary OA (bbSOA) became more oxidized with continued aging and resembled that of aged atmospheric organic aerosols. The bbSOA formed during daytime oxidation was dominated by acids. Organonitrates were an important product of nighttime reactions in both humid and dry conditions. Our results underline the importance of changes to both the primary and secondary biomass burning aerosols during their atmospheric aging. Heavier fragments from aerosol mass spectrometry seldom used in atmospheric chemistry can be used as more stable tracers of bbPOA and, in combination with the established levoglucosan marker, can provide an indication of the extent of bbPOA aging.

In Situ Characterization of Bioaerosols at the Single-Particle Level Using Single-Particle Mass Spectrometry: A Promising Tool for Defending Human Health against Bioaerosol Transmission.

Bioaerosol transmission is one of the important transmission pathways of COVID-19 and other infectious respiratory diseases caused by viral infection. The ability to detect bioaerosols and characterize encapsulated pathogens both in situ and in real time is crucial for early warning and monitoring of the progress of an epidemic or pandemic. The lack of a powerful analytical tool for distinguishing between bioaerosols and nonbioaerosols as well as for identification of pathogen species contained in the bioaerosols is the bottleneck in related fields. Herein, a promising solution for in situ and real-time accurate and sensitive detection of bioaeorosols is proposed by integrating single-particle aerosol mass spectrometry, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, and fluorescence spectroscopy. The proposed mass spectrometry aims at detecting bioaerosols in a range of 0.5-10 μm with adequate sensitivity and specificity. This single-particle bioaerosol mass spectrometry would not only be a powerful tool that can be useful for the authorities and public health monitoring but also would be an example of advances in mass spectrometry.

Photoaging of phenolic secondary organic aerosol in the aqueous phase: evolution of chemical and optical properties and effects of oxidants

Abstract. While gas-phase reactions are well established to have significant impacts on the mass concentration, chemical composition, and optical properties of secondary organic aerosol (SOA), the aqueous-phase aging of SOA remains poorly understood. In this study, we performed a series of long-duration photochemical aging experiments to investigate the evolution of the composition and light absorption of the aqueous SOA (aqSOA) from guaiacyl acetone (GA), a semivolatile phenolic carbonyl that is common in biomass burning smoke. The aqSOA was produced from reactions of GA with hydroxyl radical (•OH-aqSOA) or a triplet excited state of organic carbon (3C∗-aqSOA) and was then photoaged in water under conditions that simulate sunlight exposure in northern California for up to 48 h. The effects of increasing aqueous-phase •OH or 3C∗ concentration on the photoaging of the aqSOA were also studied. High-resolution aerosol mass spectrometry (HR-AMS) and UV–Vis spectroscopy were utilized to characterize the composition and the light absorptivity of the aqSOA and to track their changes during aging. Compared to •OH-aqSOA, the 3C∗-aqSOA is produced more rapidly and shows less oxidation, a greater abundance of oligomers, and higher light absorption. Prolonged photoaging promotes fragmentation and the formation of more volatile and less light-absorbing products. More than half of the initial aqSOA mass is lost, and substantial photobleaching occurs after 10.5 h of prolonged aging under simulated sunlight illumination for 3C∗-aqSOA and 48 h for •OH-aqSOA. By performing positive matrix factorization (PMF) analysis of the combined HR-AMS and UV–Vis spectral data, we resolved three generations of aqSOA with distinctly different chemical and optical properties. The first-generation aqSOA shows significant oligomer formation and enhanced light absorption at 340–400 nm. The second-generation aqSOA is enriched in functionalized GA species and has the highest mass absorption coefficients in 300–500 nm, while the third-generation aqSOA contains more fragmented products and is the least light absorbing. These results suggest that intermediately aged phenolic aqSOA is more light absorbing than other generations, and that the light absorptivity of phenolic aqSOA results from a competition between brown carbon (BrC) formation and photobleaching, which is dependent on aging time. Although photoaging generally increases the oxidation of aqSOA, a slightly decreased O/C of the •OH-aqSOA is observed after 48 h of prolonged photoaging with additional •OH exposure. This is likely due to greater fragmentation and evaporation of highly oxidized compounds. Increased oxidant concentration accelerates the transformation of aqSOA and promotes the decay of BrC chromophores, leading to faster mass reduction and photobleaching. In addition, compared with •OH, photoaging by 3C∗ produces more low-volatility functionalized products, which counterbalances part of the aqSOA mass loss due to fragmentation and evaporation.

Laboratory evaluation of organic aerosol relative ionization efficiencies in the aerodyne aerosol mass spectrometer and aerosol chemical speciation monitor

Organic aerosol (OA) mass concentrations measured by the Aerodyne Aerosol Mass Spectrometer (AMS) and Aerosol Chemical Species Monitor (ACSM) depend on particle relative ionization efficiency (RIEOA). Here, a series of laboratory experiments were conducted to investigate how RIEOA differs for different classes of OA and between AMS and ACSM instruments. For OA surrogates with high oxidation state ( OSc¯), the measured RIEOA is 1.60 ± 0.56 for all instruments. However, for OA surrogates with lower OSc¯, the absolute magnitude and the variability of the measured RIEOA increases. The increase in RIEOA is different between the AMS and ACSMs due to differences in m/z-dependent ion transmission/detection efficiencies in the mass spectrometers. A new metric is introduced to explore RIEOA—the fractional contribution of ions at less than or equal to m/z 50 (fΣm/z50 ). When fΣm/z50 is high (>64%, similar to ambient OA), the average RIEOA is 1.23 ± 0.62. This supports the use of a default RIEOA of 1.4 for typical ambient conditions, where secondary OA dominates the OA budget. When fΣm/z50 is less than 64%, the RIEOA increases as higher m/z ions contribute more to the total signal. These observations reflect the fact that the observed RIEOA is a combination of multiple processes. The fΣm/z50 may be used as a metric to determine if primary-like OA is contributing significantly to total OA. Overall, the results indicate that changes in RIEOA are most important for studies measuring primary-like OA, and the magnitude of the changes will depend on the instrument being used to measure the OA.

Secondary aerosol formation in incense burning particles by O3 and OH oxidation via single particle mixing state analysis

Incense burning is a common religious activity that emits abundant gaseous and particulate pollutants into the atmosphere. During their atmospheric lifetime, these gases and particles are subjected to oxidation, leading to the formation of secondary pollutants. We examined the oxidation of incense burning plumes under O3 exposure and dark condition using an oxidation flow reactor connected to a single particle aerosol mass spectrometer (SPAMS). Nitrate formation was observed in incense burning particles, mainly attributable to the ozonolysis of nitrogen-containing organic compounds. With UV on, nitrate formation was significantly enhanced, likely due to HNO3/HNO2/NOx uptake triggered by OH chemistry, which is more effective than ozone oxidation. The extent of nitrate formation is insensitive to O3 and OH exposure, possibly due to the diffusion limitation on interfacial uptake. The O3-UV-aged particles are more oxygenated and functionalized than O3-Dark-aged particles. Oxalate and malonate, two typical secondary organic aerosol (SOA) components, were found in O3-UV-aged particles. Our work reveals that nitrate, accompanied by SOA, can rapidly form in incense-burning particles upon photochemical oxidation in the atmosphere, which could deepen our understanding of air pollution caused by religious activities.

Online study of the plasma-accelerated aging process and toxicity of polyethylene terephthalate

Plastic aging occurs in all environmental media and affects their environmental behavior and toxicity. In this study, non-thermal plasma was applied to simulate the aging process of plastics, with polyethylene terephthalate (PET-film) being used as a model. The surface morphology, mass defects, toxicity of aged PET-film and the generation of airborne fine particles were comprehensively characterized. The surface of PET films began to become rough and then gradually became uneven, generating pores, protrusions and cracks. The toxicity of aged PET films was assessed in Caenorhabditis elegans which significantly reduced head thrashing, body bending and brood size. A single particle aerosol mass spectrometry instrument was used to characterize the size distribution and chemical composition of airborne fine particles in real-time. Few particles were observed during the first 90 min, while the generation of particles accelerated significantly after aging time beyond 90 min. For two pieces of PET film with surface area of 5 cm2, during the 180 min, at least 15113 ± 153 fine particles were generated, having a unimodal size distribution with a peak of 0.4 µm. The main components of these particles included metals, inorganic non-metals, and organic components. The results provide useful information on plastic aging and are beneficial in assessing the potential environmental risks.

Bioaerosol Identification by Wide Particle Size Range Single Particle Mass Spectrometry

The properties of bioaerosols are complex and diverse, and have a direct impact on the environment, climate, and human health. The effective identification of bioaerosols in the atmosphere is very significant with regard to accurately obtaining the atmospheric chemical characteristics of bioaerosols and making biological early warnings and predictions. To improve the detection of large particle bioaerosol and non-bioaerosol interference in the process of bioaerosol recognition this study detected a variety of bioaerosols and abiotic aerosols based on a single particle aerosol mass spectrometer (SPAMS). Furthermore, the bioaerosol particle identification and classification algorithm based on Zawadowicz the ratio of phosphate to organic nitrogen is optimized to distinguish bioaerosols from abiotic aerosols. The influence of ionized laser energy on classification methods is thoroughly explored here. The results show that 15 kinds of pure fungal aerosols were detected by SPAMS based on a wide size range sampling system, and that fungal aerosols with a particle size of up to 10 μm can be detected. Through the mass spectra peak ratio method of PO3−/PO2− and CNO−/CN−, when discriminating abiotic aerosols such as disruptive biomass combustion particles, automobile exhaust, and dust from pure bacterial aerosols, the discrimination degree is up to 97.7%. The optimized ratio detection method of phosphate to organic nitrogen has strong specificity, which can serve as the discriminant basis for identifying bioaerosols in SPAMS analytical processes.

Development and evaluation of an improved offline aerosol mass spectrometry technique

Abstract. The offline aerosol mass spectrometry technique is a useful tool for the source apportionment of organic aerosol (OA) in areas and periods during which an aerosol mass spectrometer (AMS) is not available. However, the technique is based on the extraction of aerosol samples in water, while several atmospheric OA components are partially or fully insoluble in water. In this work an improved offline technique was developed and evaluated in an effort to capture most of the partially soluble and insoluble organic aerosol material, reducing significantly the uncertainty of the corresponding source apportionment. A major advantage of the proposed approach is that no corrections are needed for the offline analysis to account for the limited water solubility of some OA components. The improved offline AMS analysis was tested in three campaigns: two during winter and one during summer. Collocated online AMS measurements were performed for the evaluation of the offline method. Source apportionment analysis was performed separately for the online and the offline measurements using positive matrix factorization (PMF). The PMF results showed that the fractional contribution of each factor to the total OA differed between the online and the offline PMF results by less than 15 %. The differences in the AMS spectra of the factors of the two approaches could be significant, suggesting that the use of factor profiles from the literature in the offline analysis may lead to complications. Part of the good agreement between the online and the offline PMF results is due to the ability of the improved offline AMS technique to capture a bigger part of the OA, including insoluble organic material. This was evident by the significant fraction of submicrometer suspended insoluble particles present in the water extract and by the reduced insoluble material on the filters after the extraction process. More than half of the elemental carbon (EC) was on average missing from the filters after the water extraction. Significant EC concentrations were measured in the produced aerosol that was used as input to the AMS during the offline analysis.

Emissions from ships’ activities in the anchorage zone: A potential source of sub-micron aerosols in port areas

Busan Port is among the world’s top ten most air-polluted ports, but the role of the anchorage zone as a significant contributor to pollution has not been studied. To assess the emission characteristics of sub-micron aerosols, a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed in Busan, South Korea from September 10 to October 6, 2020. The concentration of all AMS-identified species and black carbon were highest when the winds came from the anchorage zone (11.9 µg·m−3) and lowest with winds from the open ocean (6.64 µg·m−3). The positive matrix factorization model identified one hydrocarbon-like organic aerosol (HOA) and two oxygenated organic aerosol (OOA) sources. HOAs were highest with winds from Busan Port, while oxidized OOAs were predominant with winds from the anchorage zone (less oxidized) and the open ocean (more oxidized). We calculated the emissions from the anchorage zone using ship activity data and compared them to the total emissions from Busan Port. Our results suggest that emissions from ship activities in the anchorage zone should be considered a significant source of pollution in the Busan Port area, especially given the substantial contributions of gaseous emissions (NOx: 8.78%; volatile organic compounds: 7.52%) and their oxidized moieties as secondary aerosols.