Aerosol Mass Research Articles

Fine Particle pH and Sensitivity to NH<sub>3</sub> and HNO<sub>3</sub> over South Korea During KORUS-AQ

Using a new approach that constrains thermodynamic modeling of aerosol composition with measured gas-to-particle partitioning of inorganic nitrate, we estimate the acidity levels for aerosol sampled in the South Korean planetary boundary layer during the NASA/NIER KORUS-AQ field campaign. The pH (mean ± 1σ = 2.43±0.68) and aerosol liquid water content determined were then used to determine the ‘chemical regime’ of the inorganic fraction of particulate matter (PM) sensitivity to ammonia and nitrate availability. We found that the aerosol formation is always sensitive to HNO3 levels, especially in highly polluted regions, while it is only exclusively sensitive to NH3 in some rural/remote regions. Nitrate levels are further promoted because dry deposition velocity is low and allows its accumulation in the boundary layer. Because of this, HNO3 reductions achieved by NOX controls prove to be the most effective approach for all conditions examined, and that NH3 emissions can only partially affect PM reduction for the specific season and region. Despite the benefits of controlling PM formation to reduce ammonium-nitrate aerosol and PM mass, changes in the acidity domain can significantly affect other processes and sources of aerosol toxicity (e.g. solubilization of Fe, Cu and other metals) as well as the deposition patterns of these trace species and reactive nitrogen.

In Situ Aerosol Size Spectra Measurements in the Austral Polar Vortex Before and After the Hunga Tonga‐Hunga Ha'apai Volcanic Eruption

AbstractAerosol from the Hunga Tonga‐Hunga Ha'apai (HT‐HH) volcanic eruption (20.6°S) in January 2022 were not incorporated into the austral polar vortex until the following year, March 2023. Within the polar vortex in situ profiles of aerosol size spectra were completed in the austral autumns of 2019 and 2023, from McMurdo Station, Antarctica (78˚S), 30 months prior to and 15 months after the HT‐HH eruption. The measurements indicate that the HT‐HH impact on aerosol size was primarily confined to particles with diameters >0.5 μm leading to differences in aerosol mass, surface area, and extinction from factors of 2–4 at the volcanic layer's peak below 20 km, increasing to ratios of 5–10 above 20 km. Effective radius, with radiative and microphysical implications, increased from ∼0.2 to ∼0.3 μm. An Earth system model with a modal aerosol package compares favorably with the in situ measurements of the HT‐HH aerosol impact.

Chemical Composition of Aerosols from the E-Cigarette Vaping of Natural and Synthetic Cannabinoids.

Vaping cannabinoids in electronic (e)-cigarette devices is rapidly increasing in popularity, particularly among adolescents, although the chemistry affecting the composition of the vape aerosol is not well understood. This work investigates the formation of aerosol mass, bioactive hydroxyquinones, and harmful or potentially harmful carbonyls from the e-cigarette vaping of natural and synthetic cannabinoids e-liquids in propylene glycol and vegetable glycerin (PG/VG) solvent at a 50 mg/mL concentration in a commercial fourth-generation vaping device. The following cannabinoids were studied: cannabidiol (CBD), 8,9-dihydrocannabidiol (H2CBD), 1,2,8,9-tetrahydrocannabidiol (H4CBD), cannabigerol (CBG), and cannabidiolic acid (CBDA). Quantification of analytes was performed using liquid chromatography coupled to accurate mass spectrometry. The addition of cannabinoids significantly increased aerosol and carbonyl formation compared with the PG/VG solvent alone. All cannabinoids in the study formed hydroxyquinones during vaping (up to ∼1% mass conversion) except for CBDA, which primarily decarboxylated to CBD. Hydroxyquinone formation increased and carbonyl formation decreased, with a decreasing number of double bonds among CBD and its synthetic analogues (H2CBD and H4CBD). During the vaping process, ∼3-6% of the cannabinoid mass can be observed as carbonyls under the study conditions. Oxidation of the terpene moiety on the cannabinoids is proposed as a major contributor to carbonyl formation. CBD produced significantly higher concentrations of formaldehyde, acetaldehyde, acrolein, diacetyl, and methylglyoxal compared with the other cannabinoid samples. CBG produced significantly higher levels of acetone, methacrolein, and methylglyoxal. Conversion of CBD to tetrahydrocannabinol (THC) was not observed under the study conditions. The chemical mechanism basis for these observations is discussed. Compared with other modalities of use for CBD and other cannabinoids, vaping has the potential to adversely impact human health by producing harmful products during the heated aerosolization process.

Enhancing Fine Aerosol Simulations in the Remote Atmosphere with Machine Learning

Global aerosol models often underestimate the mass concentration of aerosols in the remote troposphere, as evidenced by aircraft measurements. This study leveraged data from the NASA Atmospheric Tomography Mission (ATom), which provides remote aerosol concentrations, to refine algorithms for simulating these concentrations. Using the GEOS-Chem model, we simulate five fine aerosol types and enhance the simulation results using five machine-learning algorithms: Random Forest, XGBoost, SVM, KNN, and LightGBM, and compare the performance of these algorithms. Additionally, we evaluate the refinement effect of algorithms based on decision trees on a validation dataset. The results demonstrate that GEOS-Chem generally underestimated aerosol mass concentration. Among the tested algorithms, algorithms based on decision trees, particularly the Random Forest algorithm and the LightGBM algorithm, exhibited a superior performance, significantly improving prediction accuracy and computational efficiency in both the training and testing phases, as well as on the validation dataset.

Particulate emissions from cooking: emission factors, emission dynamics, and mass spectrometric analysis for different cooking methods

Abstract. Since most people, especially in developed countries, spend most of their time indoors, they are heavily exposed to indoor aerosols, which can potentially lead to adverse health effects. A major source of indoor aerosols are cooking activities, which release large quantities of particulate emissions (in terms of both number and mass), often with complex compositions. To investigate the characteristics of cooking emissions and what influences these emissions, we conducted a comprehensive study by cooking 19 dishes with different ingredients and cooking methods. The emissions were monitored in real time with several online instruments that measured both physical and chemical particle properties as well as trace gas concentrations. The same instrumentation was used to study the influence of cooking emissions on the ambient aerosol load at two German Christmas markets. In contrast to previous studies, which often focus on individual aspects or emission variables, this broad and coherent approach allows a comparison of the influence of different parameters (e.g., ingredients, cooking method, cooking temperature, cooking activities) on the emissions. We found an influence of cooking emissions on six variables: number concentration of smaller (particle diameter dp > 5 nm) and larger (dp > 250 nm) particles, particulate matter (PM: PM1, PM2.5, PM10), black carbon (BC), PAHs (polycyclic aromatic hydrocarbons), and organic aerosol mass concentration. In general, similar emission characteristics were observed for dishes with the same cooking method, mainly due to similar cooking temperature and use of oil. The temporal dynamics in the emissions of the aforementioned variables, as well as the sizes of the emitted particles, were mainly influenced by the cooking temperature and the activities during cooking. Emissions were quantified using emission factors, with the highest values for grilled dishes, 1 to 2 orders of magnitude lower for oil-based cooking (baking, stir-frying, deep-frying), and the lowest for boiled dishes. For the identification of cooking emissions with the Aerodyne aerosol mass spectrometer (AMS), and more generally for the identification of new AMS markers for individual organic aerosol types, we propose a new plot type that takes into account the mass spectral variability for individual aerosol types. Combining our results and those of previous studies for the quantification of cooking-related organic aerosols with the AMS, we recommend the use of relative ionization efficiency values higher than the default value for organics (RIEOrg = 1.4): 2.17 ± 0.48 for rapeseed-oil-based cooking and 5.16 ± 0.77 for soybean-oil-based cooking.

A fully coupled solid-particle microphysics scheme for stratospheric aerosol injections within the aerosol–chemistry–climate model SOCOL-AERv2

Abstract. Recent studies have suggested that injection of solid particles such as alumina and calcite particles for stratospheric aerosol injection (SAI) instead of sulfur-based injections could reduce some of the adverse side effects of SAI such as ozone depletion and stratospheric heating. Here, we present a version of the global aerosol–chemistry–climate model SOCOL-AERv2 and the Earth system model (ESM) SOCOLv4 which incorporate a solid-particle microphysics scheme for assessment of SAI of solid particles. Microphysical interactions of the solid particle with the stratospheric sulfur cycle were interactively coupled to the heterogeneous chemistry scheme and the radiative transfer code (RTC) for the first time within an ESM. Therefore, the model allows simulation of heterogeneous chemistry at the particle surface as well as feedbacks between microphysics, chemistry, radiation and climate. We show that sulfur-based SAI results in a doubling of the stratospheric aerosol burden compared to the same mass injection rate of calcite and alumina particles with a radius of 240 nm. Most of the sulfuric acid aerosol mass resulting from SO2 injection does not need to be lifted to the stratosphere but is formed after in situ oxidation and subsequent water uptake in the stratosphere. Therefore, to achieve the same radiative forcing, larger injection rates are needed for calcite and alumina particle injection than for sulfur-based SAI. The stratospheric sulfur cycle would be significantly perturbed, with a reduction in stratospheric sulfuric acid burden by 53 %, when injecting 5 Mt yr−1 (megatons per year) of alumina or calcite particles of 240 nm radius. We show that alumina particles will acquire a sulfuric acid coating equivalent to about 10 nm thickness if the sulfuric acid is equally distributed over the whole available particle surface area in the lower stratosphere. However, due to the steep contact angle of sulfuric acid on alumina particles, the sulfuric acid coating would likely not cover the entire alumina surface, which would result in available surface for heterogeneous reactions other than the ones on sulfuric acid. When applying realistic uptake coefficients of 1.0, 10−5 and 10−4 for H2SO4, HCl and HNO3, respectively, the same scenario with injections of calcite particles results in 94 % of the particle mass remaining in the form of CaCO3. This likely keeps the optical properties of the calcite particles intact but could significantly alter the heterogeneous reactions occurring on the particle surfaces. The major process uncertainties of solid-particle SAI are (1) the solid-particle microphysics in the injection plume and degree of agglomeration of solid particles on the sub-ESM grid scale, (2) the scattering properties of the resulting agglomerates, (3) heterogeneous chemistry on the particle surface, and (4) aerosol–cloud interactions. These uncertainties can only be addressed with extensive, coordinated experimental and modelling research efforts. The model presented in this work offers a useful tool for sensitivity studies and incorporating new experimental results on SAI of solid particles.

Electronic cigarettes Alter cardiac rhythm and heart rate variability hyperacutely in mice

AimsThere has been an unprecedented rise in electronic cigarette (EC) usage likely because of its perception of being safer than smoking. Recent studies show that EC exposures impact heart rate (HR) and heart rate variability (HRV), but how they are affected by the timing and frequency of exposures remain unclear. We examine the electrocardiographic (EKG) effects induced by brief EC exposures over time, their relation to EC aerosol particle and mass concentrations, and potential to promote prooxidative effects in the lungs. Methods & resultsSix 10-week-old C57BL/6 mice, implanted with telemetry devices to monitor EKG activity continuously, were exposed once per week for three weeks to two EC exposures, each lasting 15-min followed by 45-min post-exposure periods. Filtered air (primary) and PBS (secondary) were used as controls. EC aerosol induced bradycardia and increased time domain parameters during EC exposures with significant reductions in the post-exposure periods. Log-transformed frequency domain parameters were significantly elevated during and after exposures (p < 0.001). HRV changes occurred within minutes with similar trends observed in particle number and mass concentrations of EC aerosol. HR and HRV varied by week and parameter, with Week 2 and 3 effects overshadowing those in Week 1. ECs induced prooxidative effects in the lungs as evidenced by elevated potential for hydroxyl radical generation in bronchoalveolar lavage fluid of exposed mice (p = 0.003). ConclusionShort-term EC exposures altered murine HR and HRV within minutes during and after exposures, effects that were modulated by the timing and frequency of EC exposures.

Size-speciated chemistry of aerosols during the continental to marine air-mass transition phase from tropical Western Ghats environment in peninsular India

Atmospheric aerosol characteristics from the Western Ghats (WG), a region that plays a prominent role in modulating the Indian monsoon, was evaluated to study the impacts of long-range transport, local sources, and cloud processing on their chemical properties. Size-segregated aerosols collected from Ponmudi (8.8°N, 77.1°E), a tropical high altitude location (960 m a.s.l.) in the southern part of the WG, during the continental to marine air-mass transition phase (January–April 2020–2021) were analysed for major chemical components, including carbonaceous species, water-soluble ionic species, metallic elements and aerosol liquid water (ALW). The major aerosol components during the north-east monsoon period were identified as (NH4)2SO4, organic matter, and ALW derived from long-range transported biomass emission plumes undergoing cloud processing and aqueous-phase reactions with SO2. Positive Matrix Factorization (PMF) analysis revealed the presence of aged and mixed aerosol types, with influence from local anthropogenic emissions and secondary formation processes. The source profiles for different air-masses indicate that the IGP air-mass is dominated by anthropogenic continental sources rich in sulphates, while the East Asian air-mass comprises highly aged continental emissions rich in organics and mixed with marine emissions from the Bay of Bengal. Fine mode aerosol mass was reconstructed, and organic matter to organic carbon conversion factor was estimated after mass closure, which revealed relatively high values for East-Asian air-mass, providing evidence for their oxidation during long-range transport. The hill station was also influenced by local urban valley emissions transported to the site via daytime convection and sea-breeze circulation. Consequently, the aerosol system over this region exhibited a complex mixture, with elemental carbon particles coexisting with sea-salt, sulphate, and secondary water-soluble organics. The findings highlight the need for further studies to understand the role of chemically processed and mixed aerosol system in modifying regional climate dynamics and air quality over such sensitive ecosystems.

Modeling the contribution of leads to sea spray aerosol in the high Arctic

Abstract. Elongated open-water areas in sea ice (leads) release sea spray particles to the atmosphere. However, there is limited knowledge on the amount, properties and drivers of sea spray emitted from leads, and no existing parameterization of this process is available for use in models. In this work, we use measurements of aerosol fluxes from Nilsson et al. (2001) to produce an estimate of the location, timing and amount of sea spray emissions from leads at the scale of the Arctic Ocean for 1 year. Lead fractions are derived using sea ice data sets from numerical models and satellite detection. The proposed parameterization estimates that leads account for 0.3 %–9.8 % of the annual sea salt aerosol number emissions in the Arctic Ocean regions where sea ice concentration is greater than 80 %. Assuming similar size distributions to those from emissions from the open ocean, leads account for 30 %–85 % of mass emissions in sea ice regions. The total annual mass of sea salt emitted from leads, 0.1–2.1 Tg yr−1, is comparable to the mass of sea salt aerosol transported above sea ice from the open ocean, according to the MERRA-2 reanalysis. In addition to providing the first estimates of possible upper and lower bounds of sea spray emissions from leads, the conceptual model developed in this work is implemented and tested in the regional atmospheric chemistry model WRF-Chem. Given the estimates obtained in this work, the impact of sea spray from leads on Arctic clouds and radiative budget needs to be further explored.

Aqueous photochemical aging of water-soluble smoke particles from crop straws burning

Most aqueous oxidation studies focus on single model precursors, while the photochemical aging of actual water soluble organic matter (WSOM) in particles emitted from biomass burning remains poorly understood. In this study, gas chromatography-mass spectrometry (GC/MS) was first used to analyze the WSOM in smoke particles emitted from three crop straws burning. The results show that the dominant WSOM in three crop straws (CS) smoke are phenolic substances with small differences. Aqueous photochemical aging of WSOM in CS smoke was investigated under simulated sunlight exposure. High-resolution aerosol mass spectrometry (HR-AMS) analyzed aqueous secondary organic aerosol (aqSOA) and it was found that the oxidation degree of aqSOA increased with prolonged aging. No obvious increase in the abundance of N-containing organic ions was observed over the course of aqueous aging. As aqueous aging progresses, the pH of the solution gradually decreases, accompanied by the continuous generation of organic acids. Studies on dithiothreitol (DTT) activity indicate that the impact of aqueous photochemical aging on health is not significant.The solution after photoaging shows relatively lower light absorption ability than the initial solution. The aqueous photochemical aging also led to a gradual reduction of fluorescence at excitation/emission = 250–260 nm/350 nm (protein-like substances) for CS smoke WSOM, suggesting the significant degradation of chromophores. However, three-dimensional excitation-emission matrix (EEM) fluorescence combined with parallel factor analysis (PARAFAC) revealed that aqueous aged CS smoke WSOM contains compounds with high humification index, confirming that the fluorophore composition is altered by aqueous aging. The humic-like substance (HULIS) concentration increased for the first 3 h and then decreased, closely matching the pattern of a new fluorescence peak. Finally, GC/MS analysis of the products indicated that there was obvious decline in proportion of methoxyphenol. The results of this study are important for understanding the aqueous-phase oxidation reactions of CS smoke WSOM in the atmosphere and their light-absorption characteristics and health impacts.

Aerosol Vertical Turbulent Mass Flux Retrievals Through Novel Remote Sensing Algorithm

AbstractIntegrated measurements of aerosol, radiation, cloud, and turbulent transport in the planetary boundary layer (PBL) are essential for understanding and modeling climate and air quality. Here, we developed a new technique for the identification of convective turbulent regions and deriving the vertical distribution of aerosol turbulent mass fluxes within PBL. The algorithm uses retrievals from coherent Doppler lidars and a high spectral resolution lidar. The technique was applied to study particle mass fluxes over 2 months (November–December 2020) during the campaign conducted at the DOE Atmospheric Radiation Measurement Southern Great Plains (SGP) site in Lamont, Oklahoma. The algorithm developed here is capable of continuously deriving vertically resolved (curtains) aerosol mass fluxes. Our data analysis shows that at the site, the 30‐min averaged fluxes at 135 m above the surface were mainly positive (upward) at ∼1 μg m−2 s−1, suggesting that the surface is the primary source of the particle mass supplied to the boundary layer at the SGP site. Analyses of the individual case studies have revealed that not all the derived fluxes can be linked to surface emissions. Both positive and negative values in a range of ±5 μg m−2 s−1 can be caused by convective thermals interacting between the residual layer and the mixed layer and by rotation of the horizontal wind with the height. Large erroneous negative fluxes can also be caused by drizzling/precipitating clouds. We anticipate that the application of the current technique will lead to a more realistic representation of aerosol mass budgets and bidirectional mixing rates.

Assessment of vehicle exhaust PM emissions using high-resolution on-road measurements in Seoul, Korea

In megacities, road traffic is a major source of particulate matter (PM), requiring a critical understanding of effective air pollution control. Despite existing methods to determine PM emission factors (EFs) of vehicles, accurate estimation of PM emissions under real driving conditions remains challenging. We aimed to assess the EFs of organic aerosol (OA) and equivalent black carbon (eBC) from vehicles through on-road measurements in Seoul, Korea, to understand real-world PM emissions. We used a mobile laboratory equipped with an aerosol mass spectrometer and an aethalometer to measure the composition of PM. On-road measurements were conducted in vehicle tunnels, urban roadways, and residential areas, and the characteristics of measurement points were compared and analyzed. Our results showed that concentrations of OA increased proportionally with the influence of vehicle exhaust, while oxidation states of the OA decreased. Mobile measurements revealed spatial heterogeneities in aerosols, highlighting distinct characteristics of fresh OA on vehicle roads and elevated oxidation state values in residential areas. Active nitrate formation near vehicles led to elevated NO3 concentrations on roads compared to residential areas. Our study shows that mobile PM measurements, including OA and eBC, are valuable for the direct evaluation of emission inventories. However, given that the calculated EFs may not be applicable to other cities due to differences in vehicle composition and traffic conditions, the development of city-specific EFs will be necessary in the future. Furthermore, it is recommended to integrate this methodology with conventional emission inventories to identify vehicle-type-specific emissions.Graphical

Microphysical Analysis of Maritime and Continental Aerosols: Determination of Hygroscopic Growth Factors Using OPAC Data and Modeling Approaches

Study’s Excerpt/Novelty This study presents an application of mass-based hygroscopicity models to analyze microphysical properties of atmospheric aerosols from continental and maritime sources using data from the Optical Properties of Aerosols and Clouds (OPAC). By examining hygroscopic growth factors and effective radii at eight different relative humidities, the research highlights the significant variation in growth factors between maritime and continental aerosols, with maritime clean aerosols exhibiting a substantially higher growth factor at 99% RH. The study's robust statistical analysis, confirmed by R² values greater than 90% and significance levels below 0.05, demonstrates the model's efficacy for atmospheric modeling and remote sensing applications. Full Abstract The interplay of marine and continental sources governed the atmospheric aerosols over coastal areas. The transport of aerosols from continental sources into sea surfaces through deposition or diffusion is what causes the fast reduction of continental aerosols. A mass based based hygroscopicity models were applied to the data extracted from the Optical Properties of Aerosols and Clouds (OPAC). The microphysical properties obtained were radii, density, refractive index, mass, volume, and sphericity of the atmospheric aerosols of continental and maritime aerosols at eight different relative humidity of 0%, 50%, 70%, 80%, 90%, 95%, 98%, and 99%. Using the microphysical properties, hygroscopic growth factors, and effective radii of the mixtures, mass growth factor Gm and diameter growth factor DG were determined, and also the parameter Km for mass based of the aerosols were determined using multiple regression analysis with SPSS 16.0 at each relative humidity. The results show that Gm for maritime clean is higher than other aerosols, with a value of 34.46 at 99% RH, while the lowest value is for continental average, with a value of 5.03 at 99% RH. Also, R2 for the model is greater than 90%. The significance and P-values are less than 0.05; therefore, the model is good for atmospheric modeling and remote sensing.

Analytical optical methods for measuring organic peroxides and hydroperoxides: An evaluation

Hydrogen peroxide, organic peroxides and hydroperoxides exhibit high reactivity and play a pivotal role in atmospheric chemistry. These compounds are formed during the oxidation of volatile organic compounds in both gaseous and aqueous phases, particularly under low NOx conditions. Their significant contribution to the mass of secondary organic aerosols (SOA) is well-documented, and they are believed to have significant health implications. Several spectrophotometric methods have been employed to measure SOA-bound peroxides in laboratory samples, but systematic comparisons are lacking. In this study, we have assessed the advantages and limitations of these methods, including the traditional and microwave-assisted iodometric methods, the 4-nitrophenyl boronic acid assay (NPBA), and the Fenton reaction-assisted ferrous-xylenol (FOX2) assay. Besides, a comprehensive evaluation of these methodologies was conducted for the first time across a substantial cohort of commercial peroxides and hydroperoxides, employing diverse solvents (namely, water, 1-propanol, acetonitrile, methanol and chloroform) to provide broader insights compared to previous work. Ultimately, the four methods were applied and compared for peroxide determination in laboratory-generated SOA resulting from gas-phase ozonolysis of α-pinene. This study opens new opportunities for future mechanistic investigation into SOA formation and reactivity.

Impact of biomass burning on air quality: A case study of the agricultural region in South Korea

Various combustion processes occur concurrently during biomass burning events, emitting a complex mixture of particulate and gaseous pollutants into the atmosphere. These emissions undergo chemical transformations facilitated by factors such as solar radiation and cloud formation, thereby altering the composition of aerosols. Additionally, these pollutants can affect the region of origin and neighboring countries, presenting regional and global environmental challenges. Therefore, precise evaluation of the particulate and gaseous pollutants emitted during biomass burning is essential to formulate effective management strategies. This study aimed to assess the concentration and chemical characteristics of particulate matter emitted during biomass burning in South Korea. On June 7, 2021, a research flight was conducted utilizing a High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and a Single Particle Soot Photometer (SP2) for airborne measurements over South Korea inland areas. For data analysis based on administrative regions, the flight path was divided into four major areas (Areas A, B, C, and D). During the research flight, evidence of biomass burning events was observed primarily in Area C. A positive matrix factorization (PMF) analysis categorized the organic aerosols (OA) into five factors: biomass burning OA (BBOA), hydrocarbon-like OA (HOA1, HOA2), low-oxidized oxygenated OA (LO-OOA), and more-oxidized OOA (MO-OOA). Across all areas, MO-OOA accounted for the highest proportion of aerosols, whereas BBOA dominated in Area C at 23.8%, indicating the significant influence of biomass burning in this region. Instead of running a PMF analysis with all measurement data, a BBOA formula was derived from the previous study and this one. This allows us to estimate BBOA concentration without running PMF.

Separation of polyphenols by HILIC methods with diode array detection, charged aerosol detection and mass spectrometry: Application to grapevine extracts rich in stilbenoids

The characterization of plant extracts is usually accomplished by reverse-phase liquid chromatography, but the development of new complementary approaches, such as HILIC, offers an orthogonal method. In this study, five HILIC stationary phases were evaluated to assess their ability to retain polyphenols. They were selected to cover the main different HILIC mechanisms: bare silica; silica with ethylene bridge; neutral amide; amino; zwitterionic. A total of 31 polyphenol standards were used for the screening, including 9 stilbenes, 8 flavonoids, 6 anthocyanins, and 8 phenolic acids. Three different detections were tested: diode array detector, charged aerosol detector and mass spectrometry.Results indicated that silica supports were not suitable for retaining polyphenols, with no or low retention observed except for anthocyanins. The effectiveness of stationary phases in retention of phenolics following the order related to increased retention: zwitterionic, amide, and amino.The choice of mobile phase also influenced retention. Mobile phases containing TFA as pH modifier limited retention, while formic acid was found to be more effective for polyphenol retention. Ammonium buffers also improved retention but often compromised peak shape. pH changes mainly impacted ionizable compounds, such as phenolic acids, by increasing their retention when they were ionized.DAD was wellsuited for detecting polyphenols that possess aromatic rings, though peak wavelengths depend on the structures of the polyphenols. CAD, while less sensitive than DAD and MS, provided an almost similar response for structurally related compounds, even with gradient elution. MS was the preferred detector for quantification when resolution between compounds was challenging, as it is often the case with natural extracts.The study successfully demonstrated that best HILIC conditions were obtained using an amino stationary phase composed of a polyethylenimine and formic acid-based mobile phase. These conditions were successfully applied to the analysis of stilbenoid-rich extracts from different parts of the vine. The elution order of stilbenoids followed the degree of polymerization. With CAD, the chromatographic profile was more representative of sample composition. It was demonstrated for the first time the interest of a combination of HILIC and CAD for analyzing stilbenes, offering a complementary approach to the classic RP analysis.

Evaluating the Importance of Nitrate‐Containing Aerosols for the Asian Tropopause Aerosol Layer

AbstractThe Asian Summer Monsoon (ASM) convection transports aerosols and their precursors from the boundary layer to the upper troposphere and lower stratosphere (UTLS). This process forms an annually recurring aerosol layer near the tropopause. Recent observations have revealed a distinct property of the aerosol layer over the ASM region, it is nitrate‐rich. We present a newly implemented aerosol formation algorithm that enhances the representation of nitrate aerosol in the Community Aerosol and Radiation Model for Atmospheres (CARMA) coupled with the Community Earth System Model (CESM). The simulated aerosol chemical composition, as well as vertical distributions of aerosol size and mass, are evaluated using in situ and remote sensing observations. The simulated concentrations (ammonium, nitrate, and sulfate) and size distributions are generally within the error bars of data. We find nitrate, organics, and sulfate contribute significantly to the UTLS aerosol concentration between 15°–45°N and 0°–160°E. The two key formation mechanisms of nitrate‐containing aerosols in the ATAL are ammonium neutralization to form ammonium nitrate in regions where convection is active, and condensation of nitric acid in regions of cold temperature. Furthermore, including nitrate formation in the model doubles the surface area density in the tropical tropopause region between 15°–45°N and 0°–160°E, which alters the chlorine partitioning and subsequently impacts the rate of ozone depletion.

Online characterization of primary and secondary emissions of particulate matter and acidic molecules from a modern fleet of city buses

Abstract. The potential impact of transitioning from conventional fossil fuel to a non-fossil-fuel vehicle fleet was investigated by measuring primary emissions via extractive sampling of bus plumes and assessing secondary mass formation using the Gothenburg Potential Aerosol Mass (Go:PAM) reactor from 76 in-use transit buses. Online chemical characterization of gaseous and particulate emissions from these buses was conducted using chemical ionization mass spectrometry (CIMS) with acetate as the reagent ion, coupled with the Filter Inlet for Gases and AEROsols (FIGAERO). Acetate reagent ion chemistry selectively ionizes acidic compounds, including organic and inorganic acids, as well as nitrated and sulfated organics. A significant reduction (48 %–98 %) in fresh particle emissions was observed in buses utilizing compressed natural gas (CNG), biodiesels like rapeseed methyl ester (RME) and hydrotreated vegetable oil (HVO), and hybrid-electric HVO (HVOHEV) compared to diesel (DSL). However, secondary particle formation from photooxidation of emissions was substantial across all the fuel types. The median ratio of particle mass emission factors of aged to fresh emissions increased in the following order: DSL buses at 4.0, HVO buses at 6.7, HVOHEV buses at 10.5, RME buses at 10.8, and CNG buses at 84. Of the compounds that can be identified by CIMS, fresh gaseous emissions from all Euro V/EEV (Enhanced Environmentally friendly Vehicle) buses, regardless of fuel type, were dominated by nitrogen-containing compounds such as nitrous acid (HONO), nitric acid (HNO3), and isocyanic acid (HNCO), alongside small monoacids (C1−C3). Notably, the emission of nitrogen-containing compounds was lower in Euro VI buses equipped with more advanced emission control technologies. Secondary gaseous organic acids correlated strongly with gaseous HNO3 signals (R2=0.85–0.99) in Go:PAM, but their moderate to weak correlations with post-photooxidation secondary particle mass suggest that they are not reliable tracers of secondary organic aerosol formation from bus exhaust. Our study highlights that non-regulated compounds and secondary pollutant formation, not currently addressed in legislation, are crucial considerations in the evaluation of environmental impacts of future fuel and engine technology shifts.

Multiphase Reactions of Hydrocarbons Into an Air Quality Model With CAMx‐UNIPAR: Impacts of Humidity and NOx on Secondary Organic Aerosol Formation in the Southern USA

AbstractSecondary organic aerosol (SOA) mass in the Southern USA during winter‐spring 2022 was simulated by integrating Comprehensive Air quality Model with extensions (CAMx) with the UNIfied Partitioning‐Aerosol phase Reaction (UNIPAR) model, which predicts SOA formation via multiphase reactions of hydrocarbons. UNIPAR streamlines multiphase partitioning of oxygenated products and their heterogeneous reactions by using explicitly predicted products originating from 10 aromatics, 3 biogenics, and linear/branched alkanes (C9‐C24). UNIPAR simulations were compared with those using Secondary Organic Aerosol Partitioning (SOAP) model, which uses simple surrogate products for each precursor. Both UNIPAR and SOAP showed similar tendencies in SOA mass but slightly underpredicted against observations at given five ground sites. However, SOA compositions and their sensitivity to environmental variables (sunlight, humidity, NOx, and SO2) were different between two models. In CAMx‐UNIPAR, SOA originated predominantly from alkanes, terpenes, and isoprene, and was influenced by humidity, showing high SOA concentrations with wet‐inorganic salts, which accelerated aqueous reactions of reactive organic products. NO2 was positively correlated with biogenic SOA because elevated levels of nitrate radicals and hygroscopic nitrate aerosol effectively oxidized biogenic hydrocarbons at night and promoted SOA growth via organic heterogeneous chemistry, respectively. Anthropogenic SOA, which formed mainly via daytime oxidation with OH radicals, was weakly and negatively correlated with NO2 in cities. In CAMx‐UNIPAR, the sensitivity of SOA to aerosol acidity (neutral vs. acidic aerosol at cation/anion = 0.62) was dominated by isoprene SOA. The reduction of NOx emissions could effectively mitigate SOA burdens in the Southern USA where biogenic hydrocarbons are abundant.

Are the Reference Values for the Provocative Concentration of Methacholine Appropriate for Children?

Background: Preliminary data in a randomly selected pediatric cohort study in 8-year-olds suggested a rate of positivity to a methacholine challenge test that was unexpectedly high, roughly 30%. The current recommendation for a negative methacholine test is a 20% decrease in the forced expiratory volume in one second at a dose greater than 400 μg. This was derived from studies in adults using the obsolete English Wright nebulizer. One explanation for the high incidence of positivity in the study in 8-year-olds could be that children deposit more methacholine on a μg/kg basis than adults, due to differences in their breathing patterns. The purpose of this study was to determine if pediatric breathing patterns could result in a higher dose of methacholine depositing in the lungs of children based on μg/kg body weight compared with adults. Methods: An AeroEclipse Breath Actuated nebulizer delivered methacholine aerosol, generated from a 16 mg/mL solution, for one minute, using age-appropriate breathing patterns for a 70 kg adult and a 30 and 50 kg child produced by a breathing simulator. Predicted lung deposition was calculated from the collected dose of methacholine on a filter placed at the nebulizer outport, multiplied by the fraction of the aerosol mass contained in particles ≤5 μm. The dose of methacholine on the inspiratory filter was assayed by high performance liquid chromatography (HPLC). Particle size was measured using laser diffraction technology. Results: The mean (95% confidence intervals) predicted pulmonary dose of methacholine was 46.1 (45.4, 46.8), 48.6 (45.3, 51.9), and 36.1 (34.2, 37.9) μg/kg body weight for the 30 kg child, 50 kg child, and 70 kg adult, respectively. Conclusions: On a μg/kg body weight, the predicted pulmonary dose of methacholine was greater with the pediatric breathing patterns than with the adult pattern.