Global variability in atmospheric new particle formation mechanisms.

A key challenge in aerosol pollution studies and climate change assessment is to understand how atmospheric aerosol particles are initially formed1,2. Although new particle formation (NPF) mechanisms have been described at specific sites3-6, in most regions, such mechanisms remain uncertain to a large extent because of the limited ability of atmospheric models to simulate critical NPF processes1,7. Here we synthesize molecular-level experiments to develop comprehensive representations of 11 NPF mechanisms and the complex chemical transformation of precursor gases in a fully coupled global climate model. Combined simulations and observations show that the dominant NPF mechanisms are distinct worldwide and vary with region and altitude. Previously neglected or underrepresented mechanisms involving organics, amines, iodine oxoacids and HNO3 probably dominate NPF in most regions with high concentrations of aerosols or large aerosol radiative forcing; such regions include oceanic and human-polluted continental boundary layers, as well as the upper troposphere over rainforests and Asian monsoon regions. These underrepresented mechanisms also play notable roles in other areas, such as the upper troposphere of the Pacific and Atlantic oceans. Accordingly, NPF accounts for different fractions (10-80%) of the nuclei on which cloud forms at 0.5% supersaturation over various regions in the lower troposphere. The comprehensive simulation of global NPF mechanisms can help improve estimation and source attribution of the climate effects of aerosols.

Volatility Basis Set Distributions and Viscosity of Organic Aerosol Mixtures: Insights from Chemical Characterization Using Temperature-Programmed Desorption-Direct Analysis in Real-Time High-Resolution Mass Spectrometry.

Quantitative assessment of gas-particle partitioning of individual components within complex atmospheric organic aerosol (OA) mixtures is critical for predicting and comprehending the formation and evolution of OA particles in the atmosphere. This investigation leverages previously documented data obtained through a temperature-programmed desorption-direct analysis in real-time, high-resolution mass spectrometry (TPD-DART-HRMS) platform. This methodology facilitates the bottom-up construction of volatility basis set (VBS) distributions for constituents found in three biogenic secondary organic aerosol (SOA) mixtures produced through the ozonolysis of α-pinene, limonene, and ocimene. The apparent enthalpies (ΔH*, kJ mol-1) and saturation mass concentrations (CT*, µg·m-3) of individual SOA components, determined as a function of temperature (T, K), facilitated an assessment of changes in VBS distributions and gas-particle partitioning with respect to T and atmospheric total organic mass loadings (tOM, µg·m-3). The VBS distributions reveal distinct differences in volatilities among monomers, dimers, and trimers, categorized into separate volatility bins. At the ambient temperature of T = 298 K, only monomers efficiently partition between gas and particle phases across a broad range of atmospherically relevant tOM values of 1-100 µg·m-3. Partitioning of dimers and trimers becomes notable only at T > 360 K and T > 420 K, respectively. The viscosity of SOA mixtures is assessed using a bottom-up calculation approach, incorporating the input of elemental formulas, ΔH*, CT*, and particle-phase mass fractions of the SOA components. Through this approach, we are able to accurately estimate the variations in SOA viscosity that result from the evaporation of its components. These variations are, in turn, influenced by atmospherically relevant changes in tOM and T. Comparison of the calculated SOA viscosity and diffusivity values with literature reported experimental results shows close agreement, thereby validating the employed calculation approach. These findings underscore the significant potential for TPD-DART-HRMS measurements in enabling the untargeted analysis of organic molecules within OA mixtures. This approach facilitates quantitative assessment of their gas-particle partitioning and allows for the estimation of their viscosity and condensed-phase diffusion, thereby contributing valuable insights to atmospheric models.

Tethered balloon system and High-Resolution Mass Spectrometry Reveal Increased Organonitrates Aloft Compared to the Ground Level.

Atmospheric particles play critical roles in climate. However, significant knowledge gaps remain regarding the vertically resolved organic molecular-level composition of atmospheric particles due to aloft sampling challenges. To address this, we use a tethered balloon system at the Southern Great Plains Observatory and high-resolution mass spectrometry to, respectively, collect and characterize organic molecular formulas (MF) in the ground level and aloft (up to 750 m) samples. We show that organic MF uniquely detected aloft were dominated by organonitrates (139 MF; 54% of all uniquely detected aloft MF). Organonitrates that were uniquely detected aloft featured elevated O/C ratios (0.73 ± 0.23) compared to aloft organonitrates that were commonly observed at the ground level (0.63 ± 0.22). Unique aloft organic molecular composition was positively associated with increased cloud coverage, increased aloft relative humidity (∼40% increase compared to ground level), and decreased vertical wind variance. Furthermore, 29% of extremely low volatility organic compounds in the aloft sample were truly unique to the aloft sample compared to the ground level, emphasizing potential oligomer formation at higher altitudes. Overall, this study highlights the importance of considering vertically resolved organic molecular composition (particularly for organonitrates) and hypothesizes that aqueous phase transformations and vertical wind variance may be key variables affecting the molecular composition of aloft organic aerosol.

Widespread 2013-2020 decreases and reduction challenges of organic aerosol in China.

High concentrations of organic aerosol (OA) occur in Asian countries, leading to great health burdens. Clean air actions have resulted in significant emission reductions of air pollutants in China. However, long-term nation-wide trends in OA and their causes remain unknown. Here, we present both observational and model evidence demonstrating widespread decreases with a greater reduction in primary OA than in secondary OA (SOA) in China during the period of 2013 to 2020. Most of the decline is attributed to reduced residential fuel burning while the interannual variability in SOA may have been driven by meteorological variations. We find contrasting effects of reducing NOx and SO2 on SOA production which may have led to slight overall increases in SOA. Our findings highlight the importance of clean energy replacements in multiple sectors on achieving air-quality targets because of high OA precursor emissions and fluctuating chemical and meteorological conditions.

Modeling Novel Aqueous Particle and Cloud Chemistry Processes of Biomass Burning Phenols and Their Potential to Form Secondary Organic Aerosols.

Phenols emitted from biomass burning contribute significantly to secondary organic aerosol (SOA) formation through the partitioning of semivolatile products formed from gas-phase chemistry and multiphase chemistry in aerosol liquid water and clouds. The aqueous-phase SOA (aqSOA) formed via hydroxyl radical (•OH), singlet molecular oxygen (1O2*), and triplet excited states of organic compounds (3C*), which oxidize dissolved phenols in the aqueous phase, might play a significant role in the evolution of organic aerosol (OA). However, a quantitative and predictive understanding of aqSOA has been challenging. Here, we develop a stand-alone box model to investigate the formation of SOA from gas-phase •OH chemistry and aqSOA formed by the dissolution of phenols followed by their aqueous-phase reactions with •OH, 1O2*, and 3C* in cloud droplets and aerosol liquid water. We investigate four phenolic compounds, i.e., phenol, guaiacol, syringol, and guaiacyl acetone (GA), which represent some of the key potential sources of aqSOA from biomass burning in clouds. For the same initial precursor organic gas that dissolves in aerosol/cloud liquid water and subsequently reacts with aqueous phase oxidants, we predict that the aqSOA formation potential (defined as aqSOA formed per unit dissolved organic gas concentration) of these phenols is higher than that of isoprene-epoxydiol (IEPOX), a well-known aqSOA precursor. Cloud droplets can dissolve a broader range of soluble phenols compared to aqueous aerosols, since the liquid water contents of aerosols are orders of magnitude smaller than cloud droplets. Our simulations suggest that highly soluble and reactive multifunctional phenols like GA would predominantly undergo cloud chemistry within cloud layers, while gas-phase chemistry is likely to be more important for less soluble phenols. But in the absence of clouds, the condensation of low-volatility products from gas-phase oxidation followed by their reversible partitioning to organic aerosols dominates SOA formation, while the SOA formed through aqueous aerosol chemistry increases with relative humidity (RH), approaching 40% of the sum of gas and aqueous aerosol chemistry at 95% RH for GA. Our model developments of biomass-burning phenols and their aqueous chemistry can be readily implemented in regional and global atmospheric chemistry models to investigate the aqueous aerosol and cloud chemistry of biomass-burning organic gases in the atmosphere.

Interventions and imaging in patients with anatomic variations of cerebral circulation: a pictorial review.

The cerebral arterial system shows a wide spectrum of variations. Minor degrees of anatomic differences can be seen in almost all patients. Recognition of these anatomic variants is essential for the following: evaluating collateral circulation; some anatomic variants may mimic pathology; increased risk for aneurysm formation with some variants (e.g. fenestration, persistent trigeminal artery); dealing with pathologies that can arise with these variations; and for preoperative planning. The anterior and posterior groups of intracranial circulation show numerous anastomoses that play a major role in maintaining adequate blood supply to the cerebral parenchyma. This review focuses on the imaging features of these variants as seen on computed tomography and magnetic resonance imaging with relevant digital subtraction angiography imaging. We also present some case illustrations where understanding of these variants contributed to providing appropriate management.

Notable impact of wildfires in the western United States on weather hazards in the central United States.

Increased wildfire events constitute a significant threat to life and property in the United States. Wildfire impact on severe storms and weather hazards is another pathway that threatens society, and our understanding of which is very limited. Here, we use unique modeling developments to explore the effects of wildfires in the western US (mainly California and Oregon) on precipitation and hail in the central US. We find that the western US wildfires notably increase the occurrences of heavy precipitation rates by 38% and significant severe hail (≥2 in.) by 34% in the central United States. Both heat and aerosols from wildfires play an important role. By enhancing surface high pressure and increasing westerly and southwesterly winds, wildfires in the western United States produce (1) stronger moisture and aerosol transport to the central United States and (2) larger wind shear and storm-relative helicity in the central United States. Both the meteorological environment more conducive to severe convective storms and increased aerosols contribute to the enhancements of heavy precipitation rates and large hail. Moreover, the local wildfires in the central US also enhance the severity of storms, but their impact is notably smaller than the impact of remote wildfires in California and Oregon because of the lessened severity of the local wildfires. As wildfires are projected to be more frequent and severe in a warmer climate, the influence of wildfires on severe weather in downwind regions may become increasingly important.

Empirical Analysis of Apnea Syndrome Using an Artificial Intelligence-Based Granger Panel Model Approach.

Sleep apnea is a serious sleep disorder that occurs when a person's breathing is interrupted during sleep. People with untreated sleep apnea stop breathing repeatedly during their sleep. This study provides an empirical analysis of apnea syndrome using the AI-based Granger panel model approach. Data were collected from the MIT-BIH polysomnographic database (SLPDB). The panel is composed of eighteen patients, while the implementation was done using MATLAB software. The results show that, for the eighteen patients with sleep apnea, there was a significant relationship between ECG-blood pressure (BP), ECG-EEG, and EEG-blood pressure (BP). The study concludes that the long-term interaction between physiological signals can help the physician to understand the risks associated with these interactions. The study would assist physicians to understand the mechanisms underlying obstructive sleep apnea early and also to select the right treatment for the patients by leveraging the potential of artificial intelligence. The researchers were motivated by the need to reduce the morbidity and mortality arising from sleep apnea using AI-enabled technology.

The striking effect of vertical mixing in the planetary boundary layer on new particle formation in the Yangtze River Delta.

New particle formation (NPF) induces a sharp increase in ultrafine particle number concentrations and potentially acts as an important source of cloud condensation nuclei (CCN). As the densely populated area of China, the Yangtze River Delta (YRD) region shows a high frequency of observed NPF events at the ground level, especially in spring. Although recent observational studies suggested a possible connection between NPF at the higher altitudes and ground level, the role played by vertical mixing, particularly in the planetary boundary layer (PBL) is not fully understood. Here we integrate measurements in Nanjing on 15-20 April 2018, and the NPF-explicit Weather Research and Forecast coupled with chemistry (WRF-Chem) model simulations to better understand the governing mechanisms of the NPF and CCN. Our results indicate that newly formed particles at the boundary layer top could be transported downward by vertical mixing as the PBL develops. A numerical sensitivity simulation created by eliminating aerosol vertical mixing suppresses both the downward transport of particles formed at a higher altitude and the dilution of particles at the ground level. The resulting higher Fuchs surface area at the ground level, together with the lack of downward transport, yields a sharp weakening of NPF strength and delayed start of NPF therein. The aerosol vertical mixing, therefore, leads to a more than double increase of surface CN10-40 and a one third decrease of boundary layer top CN10-40. Additionally, the continuous growth of nucleated ultrafine particles at the boundary layer top is strongly steered by the upward transport of condensable gases, with close to half increase of particle number concentrations in Aitken mode and CCN at a supersaturation rate of 0.75%. The findings may bridge the gap in understanding the complex interaction between PBL dynamics and NPF events, reducing the uncertainty in assessing the climate impact of aerosols.

Carotid Plaque Imaging: Strategies beyond Stenosis.

Atherosclerosis at the carotid bifurcation in the neck is common and the result of turbulent hemodynamics in the bulb. Carotid bulb plaques cause disabling strokes. Carotid vessel wall imaging characterizes the atherosclerotic plaque, documents disease progression, and assesses lesion severity by plaque morphology in addition to the degree of stenosis. This in turn optimizes treatment selection for the individual patient. The aim of vessel wall imaging in patients of stroke is to distinguish stable plaques that may be conserved with best medical management from unstable or vulnerable plaques that require more aggressive medical treatment, carotid stenting, or carotid endarterectomy. Growing evidence suggests that depending on luminal stenosis measurements alone for management decisions will result in underestimating a number of plaques whose size may be small, but where the plaque morphology is unstable, there is a high likelihood of the patient developing a thromboembolic stroke in the near future. In today's context of aggressive management of even transient ischemic attacks and minor strokes, vessel wall imaging should be particularly performed in cryptogenic strokes without significant luminal narrowing on angiography to identify a subset of patients with nonstenotic but unstable atherosclerotic plaques that may be covert etiologies of stroke. If patients receiving the best medical management have recurrent strokes on the same side as a carotid plaque with "vulnerable" plaque features, they may deserve surgical or endovascular intervention even if they do not meet the conventional stenosis thresholds. Improved techniques for stroke imaging and consequent management have a remarkable effect in decreasing individual and public health burdens.

Rapid growth of anthropogenic organic nanoparticles greatly alters cloud life cycle in the Amazon rainforest.

Aerosol-cloud interactions remain uncertain in assessing climate change. While anthropogenic activities produce copious aerosol nanoparticles smaller than 10 nanometers, they are too small to act as efficient cloud condensation nuclei (CCN). The mechanisms responsible for particle growth to CCN-relevant sizes are poorly understood. Here, we present aircraft observations of rapid growth of anthropogenic nanoparticles downwind of an isolated metropolis in the Amazon rainforest. Model analysis reveals that the sustained particle growth to CCN sizes is predominantly caused by particle-phase diffusion-limited partitioning of semivolatile oxidation products of biogenic hydrocarbons. Cloud-resolving numerical simulations show that the enhanced CCN concentrations in the urban plume substantially alter the formation of shallow convective clouds, suppress precipitation, and enhance the transition to deep convective clouds. The proposed nanoparticle growth mechanism, expressly enabled by the abundantly formed semivolatile organics, suggests an appreciable impact of anthropogenic aerosols on cloud life cycle in previously unpolluted forests of the world.

Precursors and Pathways Leading to Enhanced Secondary Organic Aerosol Formation during Severe Haze Episodes.

Molecular analyses help to investigate the key precursors and chemical processes of secondary organic aerosol (SOA) formation. We obtained the sources and molecular compositions of organic aerosol in PM2.5 in winter in Beijing by online and offline mass spectrometer measurements. Photochemical and aqueous processing were both involved in producing SOA during the haze events. Aromatics, isoprene, long-chain alkanes or alkenes, and carbonyls such as glyoxal and methylglyoxal were all important precursors. The enhanced SOA formation during the severe haze event was predominantly contributed by aqueous processing that was promoted by elevated amounts of aerosol water for which multifunctional organic nitrates contributed the most followed by organic compounds having four oxygen atoms in their formulae. The latter included dicarboxylic acids and various oxidation products from isoprene and aromatics as well as products or oligomers from methylglyoxal aqueous uptake. Nitrated phenols, organosulfates, and methanesulfonic acid were also important SOA products but their contributions to the elevated SOA mass during the severe haze event were minor. Our results highlight the importance of reducing nitrogen oxides and nitrate for future SOA control. Additionally, the formation of highly oxygenated long-chain molecules with a low degree of unsaturation in polluted urban environments requires further research.

Impact of Urban Pollution on Organic-Mediated New-Particle Formation and Particle Number Concentration in the Amazon Rainforest.

A major challenge in assessing the impact of aerosols on climate change is to understand how human activities change aerosol loading and properties relative to the pristine/preindustrial baseline. Here, we combine chemical transport simulations and field measurements to investigate the effect of anthropogenic pollution from an isolated metropolis on the particle number concentration over the preindustrial-like Amazon rainforest through various new-particle formation (NPF) mechanisms and primary particle emissions. To represent organic-mediated NPF, we employ a state-of-the-art model that systematically simulates the formation chemistry and thermodynamics of extremely low volatility organic compounds, as well as their roles in NPF processes, and further update the model to improve organic NPF simulations under human-influenced conditions. Results show that urban pollution from the metropolis increases the particle number concentration by a factor of 5-25 over the downwind region (within 200 km from the city center) compared to background conditions. Our model indicates that NPF contributes over 70% of the total particle number in the downwind region except immediately adjacent to the sources. Among different NPF mechanisms, the ternary NPF involving organics and sulfuric acid overwhelmingly dominates. The improved understanding of particle formation mechanisms will help better quantify anthropogenic aerosol forcing from preindustrial times to the present day.

High concentration of ultrafine particles in the Amazon free troposphere produced by organic new particle formation.

The large concentrations of ultrafine particles consistently observed at high altitudes over the tropics represent one of the world's largest aerosol reservoirs, which may be providing a globally important source of cloud condensation nuclei. However, the sources and chemical processes contributing to the formation of these particles remain unclear. Here we investigate new particle formation (NPF) mechanisms in the Amazon free troposphere by integrating insights from laboratory measurements, chemical transport modeling, and field measurements. To account for organic NPF, we develop a comprehensive model representation of the temperature-dependent formation chemistry and thermodynamics of extremely low volatility organic compounds as well as their roles in NPF processes. We find that pure-organic NPF driven by natural biogenic emissions dominates in the uppermost troposphere above 13 km and accounts for 65 to 83% of the column total NPF rate under relatively pristine conditions, while ternary NPF involving organics and sulfuric acid dominates between 8 and 13 km. The large organic NPF rates at high altitudes mainly result from decreased volatility of organics and increased NPF efficiency at low temperatures, somewhat counterbalanced by a reduced chemical formation rate of extremely low volatility organic compounds. These findings imply a key role of naturally occurring organic NPF in high-altitude preindustrial environments and will help better quantify anthropogenic aerosol forcing from preindustrial times to the present day.

Photolysis Controls Atmospheric Budgets of Biogenic Secondary Organic Aerosol.

Secondary organic aerosol (SOA) accounts for a large fraction of the tropospheric particulate matter. Although SOA production rates and mechanisms have been extensively investigated, loss pathways remain uncertain. Most large-scale chemistry and transport models account for mechanical deposition of SOA but not chemical losses such as photolysis. There is also a paucity of laboratory measurements of SOA photolysis, which limits how well photolytic losses can be modeled. Here, we show, through a combined experimental and modeling approach, that photolytic loss of SOA mass significantly alters SOA budget predictions. Using environmental chamber experiments at variable relative humidity between 0 and 60%, we find that SOA produced from several biogenic volatile organic compounds undergoes photolysis-induced mass loss at rates between 0 and 2.2 ± 0.4% of nitrogen dioxide (NO2) photolysis, equivalent to average atmospheric lifetimes as short as 10 h. We incorporate our photolysis rates into a regional chemical transport model to test the sensitivity of predicted SOA mass concentrations to photolytic losses. The addition of photolysis causes a ∼50% reduction in biogenic SOA loadings over the Amazon, indicating that photolysis exerts a substantial control over the atmospheric SOA lifetime, with a likely dependence upon the SOA molecular composition and thus production mechanisms.

Experience with FRED junior flow diverter in treatment of cerebral aneurysms at or distal to the circle of Willis.

This retrospective study was aimed at assessing our results of endovascular management using the FRED junior flow diverter in cerebral aneurysms at or distal to the circle of Willis. 12 patients with 15 small cerebral vessel aneurysms at or distal to the circle of Willis underwent endovascular treatment using the FRED junior flow diverter at two tertiary care centres in Mumbai, India. 12 of the 15 aneurysms were unruptured, one was treated in an acutely ruptured setting, while two, which had presented with SAH were initially treated with balloon assisted coiling and later treated in a staged manner with a flow diverter. Technical success was 100% in all 15 deployments. Deployments were made across angles ranging from 45° to 180°. There was no stroke/TIA/death in any of the cases, which were unruptured. The O'Kelly-Marotta (OKM) staging was used to analyze angiographic follow up (at least one post procedure angiogram) which was available in 8 patients (10 aneurysms). OKM D & C was seen in 80% of the aneurysms on follow up angiograms. The treatment of small vessel cerebral aneurysms at or distal to the Circle of Willis using a dedicated flow diverter (FRED Jr.) is both technically feasible and highly efficacious.

Endovascular Management of Vein of Galen Aneurysmal Malformations: A Retrospective Analysis over a 15-Year Period.

OBJECTIVES: This retrospective study was aimed at assessing our results of endovascular management in vein of Galen aneurysmal malformation (VGAM). MATERIALS AND METHODS: This is a retrospective study of 26 patients of VGAM who underwent endovascular treatment between 1998 and 2012. All patients underwent trans-arterial embolization. Of 26 patients, 23 were treated using n-butyl cyano acrylate (Glue), while 3 out of 26 patients were treated using the ethylene vinyl alcohol (EVOH) copolymer. RESULTS: Ages of the treated patients ranged from 1 day to 18 years of age. Of the patients treated, 17 were males and 9 were females. Around 15 of the VGAMs were of the mural variety and 11 were choroidal in nature. A good outcome was seen in 22/26 (85%) of the patients. Complications were seen in total in 7/26 patients (26.92%) of which 3/26 (12%) has a fatal outcome. CONCLUSION: Endovascular embolization for VGAMs is highly efficacious and has helped create a population of VGAM survivors in this condition, which until only a few decades ago caused high mortality and morbidity.

Urban pollution greatly enhances formation of natural aerosols over the Amazon rainforest.

One of the least understood aspects in atmospheric chemistry is how urban emissions influence the formation of natural organic aerosols, which affect Earth's energy budget. The Amazon rainforest, during its wet season, is one of the few remaining places on Earth where atmospheric chemistry transitions between preindustrial and urban-influenced conditions. Here, we integrate insights from several laboratory measurements and simulate the formation of secondary organic aerosols (SOA) in the Amazon using a high-resolution chemical transport model. Simulations show that emissions of nitrogen-oxides from Manaus, a city of ~2 million people, greatly enhance production of biogenic SOA by 60-200% on average with peak enhancements of 400%, through the increased oxidation of gas-phase organic carbon emitted by the forests. Simulated enhancements agree with aircraft measurements, and are much larger than those reported over other locations. The implication is that increasing anthropogenic emissions in the future might substantially enhance biogenic SOA in pristine locations like the Amazon.

Organosulfates in aerosols downwind of an urban region in central Amazon.

Organosulfates are formed in the atmosphere from reactions between reactive organic compounds (such as oxidation products of isoprene) and acidic sulfate aerosol. Here we investigated speciated organosulfates in an area typically downwind of the city of Manaus situated in the Amazon forest in Brazil during "GoAmazon2014/5" in both the wet season (February-March) and dry season (August-October). We observe products consistent with the reaction of isoprene photooxidation products and sulfate aerosols, leading to formation of several types of isoprene-derived organosulfates, which contribute 3% up to 42% of total sulfate aerosol measured by aerosol mass spectrometry. During the wet season the average contribution of summed organic sulfate concentrations to total sulfate was 19 ± 10% and similarly during the dry season the contribution was 19 ± 8%. This is the highest fraction of speciated organic sulfate to total sulfate observed at any reported site. Organosulfates appeared to be dominantly formed from isoprene epoxydiols (IEPOX), averaging 104 ± 73 ng m-3 (range 15-328 ng m-3) during the wet season, with much higher abundance 610 ± 400 ng m-3 (range 86-1962 ng m-3) during the dry season. The concentration of isoprene-derived organic sulfate correlated with total inorganic sulfate (R2 = 0.35 and 0.51 during the wet and dry seasons, respectively), implying the significant influence of inorganic sulfate aerosol for the heterogeneous reactive uptake of IEPOX. Organosulfates also contributed to organic matter in aerosols (3.5 ± 1.9% during the wet season and 5.1 ± 2.5% during the dry season). The present study shows that an important fraction of sulfate in aerosols in the Amazon downwind of Manaus consists of multifunctional organic chemicals formed in the atmosphere, and that increased SO2 emissions would substantially increase SOA formation from isoprene.

Parameterized Yields of Semivolatile Products from Isoprene Oxidation under Different NO x Levels: Impacts of Chemical Aging and Wall-Loss of Reactive Gases.

We developed a parametrizable box model to empirically derive the yields of semivolatile products from VOC oxidation using chamber measurements, while explicitly accounting for the multigenerational chemical aging processes (such as the gas-phase fragmentation and functionalization and aerosol-phase oligomerization and photolysis) under different NO x levels and the loss of particles and gases to chamber walls. Using the oxidation of isoprene as an example, we showed that the assumptions regarding the NO x-sensitive, multigenerational aging processes of VOC oxidation products have large impacts on the parametrized product yields and SOA formation. We derived sets of semivolatile product yields from isoprene oxidation under different NO x levels. However, we stress that these product yields must be used in conjunction with the corresponding multigenerational aging schemes in chemical transport models. As more mechanistic insights regarding SOA formation from VOC oxidation emerge, our box model can be expanded to include more explicit chemical aging processes and help ultimately bridge the gap between the process-based understanding of SOA formation from VOC oxidation and the bulk-yield parametrizations used in chemical transport models.