Aerosol Mass Spectrometer Research Articles

Dense Fog in the Netherlands: Composition of the Nuclei that Contribute Most to the Droplet Number Concentration

Dense fogs, with a visibility of less than 200 m, form a traffic hazard. Usually, models describing their formation use observations at the Cabauw super-site in the Netherlands for evaluation. A key parameter is the number of fog droplets and thus the number of aerosol particles on which the fog droplets form, the so-called fog nuclei (FN). No observational data are available for this key microphysical feature. An assumption is that this number scales with the concentration of the hygroscopic aerosol component sulfate. However, in the Netherlands nitrate and organics are the more important components of the total aerosol and thus possibly also of the FN. This short communication provides the first actual data via measurements with an aerosol mass spectrometer—AMS—for a period with dense fog events observed in November 2011. The aerosol in the relevant size range was composed of about half of the hygroscopic ammonium nitrate/sulfate. The other half consisted of organics; the low O/C ratio indicated that these compounds are rather hydrophobic; the hygroscopicity factor kappa of this mix was estimated at 0.3. This value implies that the activation diameter (the lowest diameter of the FN) was at least 150 nm. The mass distribution was converted into a number distribution which showed a sharp decrease as a function of size for diameters above this threshold. This result implies that the vast majority of the FN have diameters to the activation diameter. These smallest FN contained ammonium nitrate as the major hygroscopic compound. Currently, data for other dense fogs are evaluated to search for a possible generality of this finding.

Sources of organic gases and aerosol particles and their roles in nighttime particle growth at a rural forested site in southwest Germany

Abstract. The composition, sources and chemical transformation of volatile organic compounds (VOCs) and organic aerosol (OA) particles were investigated during July–August 2021 at a rural forested site in southwest Germany, 10 km north of the city of Karlsruhe. VOCs and semi-volatile OA particles were measured with a proton-transfer-reaction mass spectrometer coupled to the CHemical Analysis of aeRosols ONline particle inlet (CHARON–PTR-MS). The CHARON-measured OA mass accounted for 62 ± 18 % on average of the total OA mass (4.2 ± 2.8 µg m−3) measured concurrently with an aerosol mass spectrometer (AMS). The total concentrations of measured VOCs ranged from 7.6 to 88.9 ppb with an average of 31.2 ± 13.4 ppb. Positive matrix factorization (PMF) was used to identify major source factors of VOCs and OA particles. Three types of oxygenated VOC (OVOC), namely aromatic OVOCs, biogenic OVOCs and aged OVOCs, contributed on average 11 % ± 9 %, 37 % ± 29 % and 29 % ± 21 % of total VOC concentrations, respectively. The results of AMS–PMF indicated substantial contributions of oxygenated organic compounds to OA particle mass. Three secondary OA (SOA) factors determined by CHARON–PMF analysis, namely aromatic SOA (5 % ± 7 %), daytime biogenic SOA (17 % ± 17 %) and nighttime biogenic SOA (28 % ± 21 %), consistently showed high contributions to the total CHARON-measured OA mass. Nighttime particle growth was observed regularly in this area, which was mainly attributed to the semi-volatile organic compounds and organic nitrates formed from the oxidation of monoterpenes and sesquiterpenes. This study presents the major sources, real-time transformations of VOCs and OA particles, and nighttime particle formation characteristics for central European forested areas.

Identification and Characterization of Rotigotine Degradation Products by HPLC Coupled DAD and CAD Detectors and HRMS Through Q-Orbitrap and Electrospray Ionization

Rotigotine (RTG) is a dopamine agonist used in the treatment of Parkinson's disease. As it is susceptible to oxidation, stability studies must be carefully designed for the identification and characterization of all possible degradation products. Here, RTG degradation was evaluated according to the International Conference on Harmonization guidelines under various stress conditions, including acidic and basic hydrolysis, oxidative, metallic, photolytic, and thermal conditions. Additionally, more severe stress conditions were applied to induce RTG degradation. Significant degradation was only observed under oxidative and photolytic conditions. The samples were analyzed by high performance liquid chromatography coupled to photodiode array detectors, charged aerosol, and high-resolution mass spectrometry. Chromatographic analyses revealed the presence of eight substances related to RTG, four of which were already described and were qualified impurities (impurities B, C, K and E) and four new degradation products (DP-1 – DP-4), whose structures were characterized by high-resolution mass spectrometry through Q-Orbitrap and electrospray ionization. In the stress testing of the active pharmaceutical ingredient in solid form, significant RTG degradation was observed in the presence of the oxidative matrix. The results corroborate the literature that confirm the high susceptibility of RTG to oxidation and the importance of using different detectors to detect degradation products in forced degradation studies.

Observation-constrained kinetic modeling of isoprene SOA formation in the atmosphere

Abstract. Isoprene has the largest global non-methane hydrocarbon emission, and the oxidation of isoprene plays a crucial role in the formation of secondary organic aerosol (SOA). Two primary processes are known to contribute to SOA formation from isoprene oxidation: (1) the reactive uptake of isoprene-derived epoxides on acidic or aqueous particle surfaces and (2) the absorptive gas–particle partitioning of low-volatility oxidation products. In this study, we developed a new multiphase condensed isoprene oxidation mechanism that includes these processes with key molecular intermediates and products. The new mechanism was applied to simulate isoprene gas-phase oxidation products and SOA formation from previously published chamber experiments under a variety of conditions and atmospheric observations during the Southern Oxidant and Aerosol Studies (SOAS) field campaign. Our results show that SOA formation from most of the chamber experiments is reasonably reproduced using our mechanism, except when the concentration ratios of initial nitric oxide to isoprene exceed ∼ 2, the formed SOA is significantly underpredicted. The SOAS simulations also reasonably agree with the measurements regarding the diurnal pattern and concentrations of different product categories, while the total isoprene SOA remains underestimated. The molecular compositions of the modeled SOA indicate that multifunctional low-volatility products contribute to isoprene SOA more significantly than previously thought, with a median mass contribution of ∼ 57 % to the total modeled isoprene SOA. However, this contribution is intricately intertwined with IEPOX-derived SOA (IEPOX: isoprene-derived epoxydiols), posing challenges for their differentiation using bulk aerosol composition analysis (e.g., the aerosol mass spectrometer with positive matrix factorization). Furthermore, the SOA from these pathways may vary greatly, mainly dependent on the volatility estimation and treatment of particle-phase processes (i.e., photolysis and hydrolysis). Our findings emphasize that the various pathways to produce these low-volatility species should be considered in models to more accurately predict isoprene SOA formation. The new condensed isoprene chemical mechanism can be further incorporated into regional-scale air quality models, such as the Community Multiscale Air Quality Modelling System (CMAQ), to assess isoprene SOA formation on a larger scale.

Evaluation of a new real-time source apportionment system of PM2.5 and its implication on rapid aging of vehicle exhaust

Accurate identification and rapid analysis of PM2.5 sources and formation mechanisms are essential to mitigate PM2.5 pollution. However, studies were limited in developing a method to apportion sources to the total PM2.5 mass in real-time. In this study, we developed a real-time source apportionment method based on chemical mass balance (CMB) modeling and a mass-closure PM2.5 composition online monitoring system in Shenzhen, China. Results showed that secondary sulfate, secondary organic aerosol (SOA), vehicle emissions and secondary nitrate were the four major PM2.5 sources during autumn 2019 in Shenzhen, together contributed 76 % of PM2.5 mass. The novel method was verified by comparing with other source apportionment methods, including offline filter analysis, aerosol mass spectrometry, and carbon isotopic analysis. The comparison of these methods showed that the new real-time method obtained results generally consistent with the others, and the differences were interpretable and implicative. SOA and vehicle emissions were the major PM2.5 and OA contributors by all methods. Further investigation on the OA sources indicated that vehicle emissions were not only the main source of primary organic aerosol (POA), but also the main contributor to SOA by rapid aging of the exhaust in the atmosphere. Our results demonstrated the great potential of the new real-time source apportionment method for aerosol pollution control and deep understandings on emission sources.

Characterizing leaf-deposited particles: Single-particle mass spectral analysis and comparison with naturally fallen particles

The size and composition of particulate matter (PM) are pivotal in determining its adverse health effects. It is important to understand PM's retention by plants to facilitate its atmospheric removal. However, the distinctions between the size and composition of naturally fallen PM (NFPM) and leaf-deposited PM (LDPM) are not well-documented. Here we utilize a single-particle aerosol mass spectrometer, coupled with a PM resuspension chamber, to analyze these differences. We find that LDPM particles are 6.8–97.3% larger than NFPM. Employing a neural network algorithm based on adaptive resonance theory, we have identified distinct compositional profiles: NFPM predominantly consists of organic carbon (OC; 31.2%) and potassium-rich components (19.1%), whereas LDPM are largely composed of crustal species (53.9–60.6%). Interestingly, coniferous species retain higher OC content (11.5–13.7%) compared to broad-leaved species (0.5–1.2%), while the levoglucosan content exhibit an opposite trend. Our study highlights the active role of tree leaves in modifying PM composition beyond mere passive capture, advocating for a strategic approach to species selection in urban greening initiatives to enhance PM mitigation. These insights provide guidance for urban planners and environmentalists in implementing nature-based solutions to improve urban air quality.

Aerosol Mass Spectrometry

Mass spectrometry is widely used in various scientific fields. In atmospheric chemistry, there has been a long call for a detailed on-line analysis of the chemical composition of aerosol particles (i.e., particles in the solid or liquid state) in the atmosphere resulting in the development of the so-called aerosol mass spectrometers in the past 20 years. These instruments allow the measurement of the chemical composition of particles with sizes of ca. 50–800 nm, typically at minute resolution. Their development and possible applications are discussed in this review.

A multi-instrumental approach for calibrating real-time mass spectrometers using high-performance liquid chromatography and positive matrix factorization

Abstract. Obtaining quantitative information for molecular species present in aerosols from real-time mass spectrometers such as an extractive electrospray time-of-flight mass spectrometer (EESI) and an aerosol mass spectrometer (AMS) can be challenging. Typically, molecular species are calibrated directly through the use of pure standards. However, in some cases (e.g., secondary organic aerosol (SOA) formed from volatile organic compounds (VOCs)), direct calibrations are impossible, as many SOA species can either not be purchased as pure standards or have ambiguous molecular identities. In some cases, bulk OA sensitivities are used to estimate molecular sensitivities. This approach is not sufficient for EESI, which measures molecular components of OA, because different species can have sensitivities that vary by a factor of more than 30. Here, we introduce a method to obtain EESI calibration factors when standards are not available, and we provide a thorough analysis of the feasibility, performance, and limitations of this new technique. In this method, complex aerosol mixtures were separated with high-performance liquid chromatography (HPLC) followed by aerosol formation via atomization. The separated aerosols were then measured by an EESI and an AMS, which allowed us to obtain sensitivities for some species present in standard and SOA mixtures. Pure compounds were used to test the method and characterize its uncertainties, and obtained sensitivities were consistent within ±20 % when comparing direct calibrations vs. HPLC calibrations for a pure standard and within a factor of 2 for a standard mixture. In some cases, species were not completely resolved by chromatography, and positive matrix factorization (PMF) of AMS data enabled further separation. This method should be applicable to other real-time MS techniques. Improvements in chromatography are possible that would allow better separation in complex mixtures.

Exploring secondary aerosol formation associated with elemental carbon in the lower free troposphere

The variability of element carbon (EC) mixed with secondary species significantly complicates the assessment of its environmental impact, reflecting the complexity and diversity of EC-containing particles' composition and morphology during their ascent and regional transport. While the catalytic role of EC in secondary aerosol formation is recognized, the effects of heterogeneous chemistry on secondary species formation within diverse EC particle types are not thoroughly understood, particularly in the troposphere. Alpine sites offer a prime environment to explore EC properties post-transport from the ground to the free troposphere. Consequently, we conducted a comprehensive study on the genesis of secondary aerosols in EC-containing particles at Mt. Hua (altitude: 2069 m) from 1 May to 10 July, using a single particle aerosol mass spectrometer (SPAMS). Our analysis identified six major EC particle types, with EC-K, EC-SN, and EC-NaK particles accounting for 27.6 %, 27.0 %, and 19.6 % of the EC particle population, respectively. The concentration-weighted trajectory (CWT) indicated that the lower free troposphere over Mt. Hua is significantly affected by anthropogenic emissions at ground-level, predominantly from northwestern and eastern China. Atmospheric interactions are crucial in generating high sulfate levels in EC-SN and EC-OC particles (> 70 %) and notable nitrate levels in EC-K, EC-BB, and EC-Fe particles (> 80 %). The observed high chloride content in EC-OC particles (56 ± 32 %) might enhance chlorine's reactivity with organic compounds via heterogeneous reactions within the troposphere. Distinct diurnal cycles for sulfate and nitrate are mainly driven by varying transport dynamics and formation processes, showing minimal dependency on EC particle types. Enhanced nocturnal oxalate conversion in EC-Fe particles is likely due to the aqueous oxidation of precursors, with Fe-catalyzed Fenton reactions enhancing OH radical production. This investigation provides critical insights into EC's role in secondary aerosol development during its transport in the lower free troposphere.

Measurements of particulate methanesulfonic acid above the remote Arctic Ocean using a high resolution aerosol mass spectrometer

Methanesulfonic acid (MSA) is an important product from the oxidation of dimethyl sulfide (DMS), and thus is often used as a tracer for marine biogenic sources and secondary organic aerosol. MSA also contributes to aerosol mass and potentially to the formation of cloud condensation nuclei and new particles. However, measurements of MSA at high temporal resolution in the remote Arctic are scarce, which limits our understanding of its formation, climate change impact and regional transport. Here, we applied a validated quantification method to determine the mass concentration of MSA and non-sea salt sulfate (nss-SO4) in PM2.5 in the marine boundary layer, using a high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) during a research cruise to the Arctic and North Atlantic Ocean, between 55 °N and 68 °N (26th May to June 23, 2022). With this method, the concentrations of MSA in the remote Arctic marine boundary layer were determined for the first time. Results show that the average MSA concentration was 0.025 ± 0.03 μg m−3, ranging from <0.01 to 0.32 μg m−3. The lowest MSA level was found towards the northern leg of the cruise (near Sisimut (67 °N)) with air masses from sea ice over the northern polar region, and the highest MSA concentrations were observed over the Atlantic open ocean. The diurnal cycles of gas MSA, particulate MSA and nss-SO4 peaked in the afternoon, about one hour later than that of peak of solar radiation, which suggests that photochemical process is an important mechanism for the conversion of DMS into MSA above the remote ocean. The mass ratio of MSA to nss-SO4 (MSA/nss-SO4) presents a temperature dependence, which indicates that the addition branching pathway favors MSA formation, while thermal decay of intermediate radicals could be a possible pathway for sulfate formation. Finally, we found that the MSA/nss-SO4 ratio is around 0.22-0.25 in the remote northern marine atmosphere.

Single particle mass spectral signatures from on-road and non-road vehicle exhaust particles and their application in refined source apportionment using deep learning

With advances in vehicle emission control technology, updating source profiles to meet the current requirements of source apportionment has become increasingly crucial. In this study, on-road and non-road vehicle particles were collected, and then the chemical compositions of individual particles were analyzed using single particle aerosol mass spectrometry. The data were grouped using an adaptive resonance theory neural network to identify signatures and establish a mass spectral database of mobile sources. In addition, a deep learning-based model (DeepAerosolClassifier) for classifying aerosol particles was established. The objective of this model was to accomplish source apportionment. During the training process, the model achieved an accuracy of 98.49 % for the validation set and an accuracy of 93.36 % for the testing set. Regarding the model interpretation, ideal spectra were generated using the model, verifying its accurate recognition of the characteristic patterns in the mass spectra. In a practical application, the model performed hourly source apportionment at three specific field monitoring sites. The effectiveness of the model in field measurement was validated by combining traffic flow and spatial information with the model results. Compared with other machine learning methods, our model achieved highly automated source apportionment while eliminating the need for feature selection, and it enables end-to-end operation. Thus, in the future, it can be applied in refined and online source apportionment of particulate matter.

Identifying the seeding signature in cloud particles from hydrometeor residuals

Abstract. Cloud seeding experiments for modifying clouds and precipitation have been underway for nearly a century; yet practically all the attempts to link precipitation enhancement or suppression to the presence of seeding materials within clouds remain elusive. In 2019, the Cloud–Aerosol Interaction and Precipitation Enhancement Experiment (CAIPEEX) investigated residuals of cloud hydrometeors in seeded and non-seeded clouds with an airborne mini aerosol mass spectrometer (mAMS). The mAMS was utilized in conjunction with a counterflow virtual impactor (CVI) inlet with a cutoff diameter size of approximately 7 µm. The evaporated cloud droplets from the CVI inlet as cloud residuals were evaluated through the mAMS. The chlorine (Cl) associated with hygroscopic materials, i.e. calcium chloride (CaCl2) and potassium (K), which serve as the oxidizing agents in the flares, is found in relatively higher concentrations in the seeded clouds compared to the non-seeded clouds. In convective clouds, Cl and K as cloud residuals were found even at a vertical distance of 2.25 km from the cloud base. Major findings from the seeding impact are an increase in the number concentration of small (&lt; 20 µm) droplets and an indication of raindrop formation at 2.25 km above the cloud base. It is demonstrated that the seed particle signature can be traced inside clouds along with the microphysical impacts.

Seasonal characterization of chemical and optical properties of water-soluble organic aerosol in Beijing

Water-soluble organic aerosol (WSOA) plays a crucial role in altering radiative forcing and impacting human health. However, our understanding of the seasonal variations of WSOA in Chinese megacities after the three-year clean air action plan is limited. In this study, we analyzed PM2.5 filter samples collected over one year (2020−2021) in Beijing to characterize the seasonal changes in the chemical and optical properties of WSOA using an offline aerosol mass spectrometer along with spectroscopy techniques. The mean mass concentration of WSOA during the observation period was 8.84 ± 7.12 μg m−3, constituting approximately 64–67 % of OA. Our results indicate the contribution of secondary OA (SOA) increased by 13–28 % due to a substantial reduction in primary emissions after the clean air action plan. The composition of WSOA exhibited pronounced seasonal variations, with a predominant contribution from less oxidized SOA in summer (61 %) and primary OA originating from coal combustion and biomass burning during the heating season (34 %). The mass absorption efficiency of WSOA at 365 nm in winter was nearly twice that in summer, suggesting that WSOA from primary emissions possesses a stronger light-absorbing capability than SOA. On average, water-soluble brown carbon accounted for 33–48 % of total brown carbon absorption. Fluorescence analysis revealed humic-like substances as the most significant fluorescence component of WSOA, constituting 82 %. Furthermore, both absorption and fluorescence chromophores were associated with nitrogen-containing compounds, highlighting the role of nitrogen-containing species in influencing the optical properties of WSOA. The results are important for chemical transport models to accurately simulate the WSOA and its climate effects.

Chemical properties and single-particle mixing state of soot aerosol in Houston during the TRACER campaign

Abstract. A high-resolution soot particle aerosol mass spectrometer (SP-AMS) was used to selectively measure refractory black carbon (rBC) and its associated coating material using both the ensemble size-resolved mass spectral mode and the event trigger single particle (ETSP) mode in Houston, Texas, in summer 2022. This study was conducted as part of the Department of Energy Atmospheric Radiation Measurement (ARM) program's TRacking Aerosol Convection interactions ExpeRiment (TRACER) field campaign. The study revealed an average (±1σ) rBC concentration of 103 ± 176 ng m−3. Additionally, the coatings on the BC particles were primarily composed of organics (59 %; 219 ± 260 ng m−3) and sulfate (26 %; 94 ± 55 ng m−3). Positive matrix factorization (PMF) analysis of the ensemble mass spectra of BC-containing particles resolved four distinct types of soot aerosol, including an oxidized organic aerosol (OOABC,PMF) factor associated with processed primary organic aerosol, an inorganic sulfate factor (SO4,BC,PMF), an oxidized rBC factor (O-BCPMF), and a mixed mineral dust–biomass burning aerosol factor with significant contribution from potassium (K-BBBC,PMF). Additionally, K-means clustering analysis of the single-particle mass spectra identified eight different clusters, including soot particles enriched in hydrocarbon-like organic aerosol (HOABC,ETSP), sulfate (SO4,BC,ETSP), two types of rBC, OOA (OOABC,ETSP), chloride (ClBC,ETSP), and nitrate (NO3,BC,ETSP). The single-particle measurements demonstrate substantial variation in BC coating thickness with coating-to-rBC mass ratios ranging from 0.1 to 100. The mixing state index (χ), which denotes the degree of homogeneity of the soot aerosol, varied from 4 % to 94 % with a median of 40 %, indicating that the aerosol population lies in between internal and external mixing but has large temporal and source type variability. In addition, a significant fraction of BC-containing particles, a majority enriched with oxidized organics and sulfate, exhibit sufficiently high κ values and diameters conducive to activation as cloud nuclei under atmospherically relevant supersaturation conditions. This finding bears significance in comprehending the aging processes of rBC-containing particles and their activation into cloud droplets. Our analysis highlights the complex nature of soot aerosol and underscores the need to comprehend its variability across different environments for accurate assessment of climate change.

Comprehensive the seasonal characterization of atmospheric submicron particles at urban sites in the North China Plain

To comprehensively investigate the seasonal variations in submicron particles (PM1 = NR-PM1 + BC) composition, sources and chemical processes, an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), along with a multiangle absorption photometer (MAAP), was deployed to observe at urban sites in the North China Plain from October 1, 2015, to July 31, 2016. The PM1 average mass were 36.4 ± 39.0, 32.9 ± 20.7, 40.4 ± 52.4 and 99.0 ± 88.7 μg m−3 in spring, summer, autumn and winter, respectively. On the whole, the OA accounted for the largest component of PM1 during the four seasons, with the highest contribution in winter, accounting for 49% on average, followed by autumn (47%), spring (40%) and summer (31%). The secondary inorganic aerosol (SIA) mass concentration in summer was the lowest but contributed the most to PM1 in summer (62%), and it was higher than that in spring (46%), autumn (43%) and winter (41%). Positive matrix factorization (PMF) was used to differentiate the high-resolution mass spectra (HRMS) of organic aerosol (OA) into six factors, including two secondary OA (highly oxidized, low-volatility oxygenated organic aerosols (LV-OOA) and less oxidized, semi-volatile oxygenated OA (SV-OOA)) and four primary OA (including cooking-related OA (COA), hydrocarbon-like OA (HOA), biomass burning OA (BBOA) and coal combustion OA (CCOA)). OOA (LV-OOA + SV-OOA) exhibited the highest OA loading in summer (59%), while POA (CCOA + COA + HOA) exhibited the highest OA loading in winter (62%). The OA exhibited similar bimodal diurnal patterns during the four seasons, the nitrate and sulfate seasonal diurnal variations slightly differed, and the peak value occurred at night in winter and in the morning during the other seasons. The trend of the LV-OOA and SV-OOA diurnal variation in spring, autumn and winter appeared small difference, and the summer vary differently compared to other seasons. However, the diurnal mass concentration in winter was much higher than other seasons. The COA diurnal pattern peaked at noon and at night during the four seasons, corresponding to the peak hours of dining activities. The HOA, BBOA and CCOA seasonal diurnal patterns showed low concentrations during the daytime and high concentrations at night. OA on HPD was 6, 7 and 7 times higher than that on CD in spring, autumn and winter. The SIA concentration significantly increased on HPD in spring (69.3 μg m−3, 52%), autumn (80.6 μg m−3, 50%) and winter (82.4 μg m−3, 43%). The organic nitrate average mass concentrations were 0.6 ± 0.5, 0.7 ± 0.2, 0.8 ± 1.2 and 2.5 ± 2.3 μg m−3 in spring, summer, autumn and winter, respectively. The organic nitrate diurnal pattern appeared at night was higher than that during the daytime in spring, autumn and winter. The opposite diurnal pattern emerged in summer. The average mass concentration of polycyclic aromatic hydrocarbons (PAHs) during the entire observation period reached 73.2 ± 154.2 ng m−3, and the seasonal average mass were 30.4 ± 30.6, 10.7 ± 4.0, 40.5 ± 10.3 and 220.3 ± 246.7 ng m−3 in spring, summer, autumn and winter, respectively. The highest diurnal values in spring, summer, autumn and winter were 44.2, 11.7, 71.6 and 366.8 ng m−3, respectively.

A laboratory study of secondary organic aerosol formation in an oxidation flow reactor

Secondary organic aerosol is formed through the atmospheric oxidation of gas-phase organic compounds and primary aerosols. Despite the potential risks that this class of particles poses to human health and climate, how primary emissions contribute to the formation of secondary organic aerosols remains largely unknown. This study examines the formation of secondary organic aerosols resulting from the oxidation of soot nanoparticles generated by a premixed laminar ethylene–air-rich flame. The exhaust gases and particles from the flame are conveyed into an oxidation flow reactor to simulate the atmospheric conditions in which secondary aerosol formation reactions occur. The pristine and oxidized aerosols are analyzed online using a scanning mobility particle sizer system to assess their size distributions. Moreover, collected aerosols are chemically characterized using a high-resolution time-of-flight aerosol mass spectrometer. The secondary aerosol formed exhibits an increase in mean diameter under different oxidation conditions and reveals an enhanced concentration compared to primary aerosols. These changes are accompanied by significant alterations in the chemical composition of the aerosols.

Bridging New Observational Capabilities and Process-Level Simulation: Insights into Aerosol Roles in the Earth System

Abstract The spatial distribution of ambient aerosol particles significantly impacts aerosol–radiation–cloud interactions, which contribute to the largest uncertainty in global anthropogenic radiative forcing estimations. However, the atmospheric boundary layer and lower free troposphere have not been adequately sampled in terms of spatiotemporal resolution, hindering a comprehensive characterization of various atmospheric processes and impeding our understanding of the Earth system. To address this research data gap, we have leveraged the development of uncrewed aerial systems (UAS) and advanced measurement techniques to obtain mesoscale spatial data on aerosol microphysical and optical properties around the U.S. Southern Great Plains (SGP) atmospheric observatory. Our study also benefits from state-of-the-art laboratory facilities that include three-dimensional molecular imaging techniques enabled by secondary ion mass spectrometry and nanogram-level chemical composition analysis via micronebulization aerosol mass spectrometry. Through our study, we have developed a framework for observation–modeling integration, enabling an examination of how various assumptions about the organic–inorganic components mixing state, inferred from chemical analysis, affect clouds and radiation in observation-constrained model simulations. By integrating observational constraints (derived from offline chemical analysis of the aerosol surface using collected samples) with in situ UAS observations, we have identified a prominent role of organic-enriched nanometer layers located at the surface of aerosol particles in determining profiles of aerosol optical and hygroscopic properties over the SGP observatory. Furthermore, we have improved the agreement between predicted clouds and ground-based cloud lidar measurements. This UAS–model–laboratory integration exemplifies how these new advanced capabilities can significantly enhance our understanding of aerosol–radiation–cloud interactions.

Examination of the Influence of Alternative Fuels on Particulate Matter Properties Emitted from a Non-Proprietary Combustor

The aviation sector, like most other sectors, is moving towards becoming net zero. In the medium to long term, this will mean an increase in the use of sustainable aviation fuels. Research exists on the impact of fuel composition on non-volatile particulate matter (nvPM) emissions. However, there is more sparsity when considering the impact on volatile particulate matter (vPM) emissions. Here, nine different fuels were tested using an open-source design combustor rig. An aerosol mass spectrometer (AMS) was used to examine the mass-loading and composition of vPM, with a simple linear regression algorithm used to compare relative mass spectrum similarity. The diaromatic, cycloalkane and aromatic contents of the fuels were observed to correlate with the measured total number concentration and nvPM mass concentrations, resulting in an inverse correlation with increasing hydrogen content. The impacts of fuel properties on other physical properties within the combustion process and how they might impact the particulate matter (PM) are considered for future research. Unlike previous studies, fuel had a very limited impact on the organic aerosol’s composition at the combustor exit measurement location. Using a novel combination of Positive Matrix Factorization (PMF) and high-resolution AMS analysis, new insight has been provided into the organic composition. Both the alkane organic aerosol (AlkOA) and quenched organic aerosol (QOA) factors contained CnH2n+1, CnH2n−1 and CnH2n ion series, implying alkanes and alkenes in both, and approximately 12% oxygenated species in the QOA factor. These results highlight the emerging differences in the vPM compositional data observed between combustor rigs and full engines.

Analysis and identification of degradation products in gas, particle, and liquid phases of polypropylene and polyethyleneterephthalate microplastics aging through non-thermal plasma simulation.

Plastic aging can cause alterations in the physical and chemical characteristics of plastics, as well as their behavior in the environment. Due to the extremely slow natural aging process, laboratory simulated aging methods have to be used. In this study, non-thermal plasma (NTP) was adopted to investigate the aging process of polypropylene (PP) and polyethylene terephthalate (PET) microplastics. Various analytical instruments, including proton transfer reaction mass spectrometry and single-particle aerosol mass spectrometry, were employed to examine and identify the organic constituents of the gas, liquid, and particle phase degradation products, as well as to monitor the degradation process. The results showed that after 90min of aging, both PP and PET surfaces showed yellowing, and the carbonyl index of PP increased while that of PET decreased, with an increase in crystallinity. The organic components of reaction products, such as ketones, esters, acids, and alcohols, increased with longer aging times. Gas products mainly contain aromatic hydrocarbons, while particles from aged PET contain compounds with benzene rings and metal elements. Liquid products from aged PP show a significant presence of branched alkanes. Based on this analysis, degradation mechanisms of PP and PET by NTP were proposed. This investigation represents the initial systematically exploration of the release of organic substances during the degradation of microplastics mediated by NTP. It provides significant insights into the detrimental organic compounds emitted during this process, thereby offering valuable information for understanding the environmental and human health implications of natural microplastic degradation. Furthermore, it addressed the requirements for increased attention to the potential environmental risks associated with these harmful components.

An updated modeling framework to simulate Los Angeles air quality - Part 1: Model development, evaluation, and source apportionment.

This study describes a modeling framework, model evaluation, and source apportionment to understand the causes of Los Angeles (LA) air pollution. A few major updates are applied to the Community Multiscale Air Quality (CMAQ) model with a high spatial resolution (1 km × 1 km). The updates include dynamic traffic emissions based on real-time, on-road information and recent emission factors and secondary organic aerosol (SOA) schemes to represent volatile chemical products (VCPs). Meteorology is well predicted compared to ground-based observations, and the emission rates from multiple sources (i.e., on-road, volatile chemical products, area, point, biogenic, and sea spray) are quantified. Evaluation of the CMAQ model shows that ozone is well predicted despite inaccuracies in nitrogen oxide (NO x ) predictions. Particle matter (PM) is underpredicted compared to concurrent measurements made with an aerosol mass spectrometer (AMS) in Pasadena. Inorganic aerosol is well predicted, while SOA is underpredicted. Modeled SOA consists of mostly organic nitrates and products from oxidation of alkane-like intermediate volatility organic compounds (IVOCs) and has missing components that behave like less-oxidized oxygenated organic aerosol (LO-OOA). Source apportionment demonstrates that the urban areas of the LA Basin and vicinity are NO x -saturated (VOC-sensitive), with the largest sensitivity of O3 to changes in VOCs in the urban core. Differing oxidative capacities in different regions impact the nonlinear chemistry leading to PM and SOA formation, which is quantified in this study.