Organic Aerosol Volatility Research Articles

Intrinsic Chemical Drivers of Organic Aerosol Volatility: From Experimental Insights to Model Predictions

AbstractAccurately predicting the volatilities of molecules in aerosols is challenging but crucial for understanding the atmospheric effects of aerosols. We used negative and positive ion electrospray ionization Fourier‐transform ion cyclotron resonance mass spectrometry (FT‐ICR MS) to identify differences in the molecular compositions of gas and particle phase samples from urban atmosphere. We aimed to identify intrinsic chemical parameters that determine and predict the organic aerosol volatility. We found higher average molecular weights, carbon mass percentages, and double bond equivalents (DBE) but lower average O/C ratios and oxygen mass percentages in the particle phase than the gas phase. We identified DBE, which display a significant negative correlation with volatility, as a key parameter. We proposed to improve the previous model for predicting organic aerosol volatility by incorporating DBE as a new variant; and the result showed that this subsequently improved the accuracy of the model, particularly for compounds with minimal or no heteroatoms (0–2) such as hydrocarbons (CH). The revised model offers insights into the contributions of DBE, carbon, nitrogen, oxygen, and sulfur atoms to the volatilities of diverse organic molecules in aerosols and could be applied to improve our understanding of the phase distributions of volatile organic compounds in the ambient air.

Molecular-Level Insights into the Relationship between Volatility of Organic Aerosol Constituents and PM2.5 Air Pollution Levels: A Study with Ultrahigh-Resolution Mass Spectrometry.

Volatility of organic aerosols (OAs) significantly influences new particle formation and the occurrence of particulate air pollution. However, the relationship between the volatility of OA and the level of particulate air pollution (i.e., particulate matter concentration) is not well understood. In this study, we compared the chemical composition (identified by an ultrahigh-resolution Orbitrap mass spectrometer) and volatility (estimated based on a predeveloped parametrization method) of OAs in urban PM2.5 (particulate matter with aerodynamic diameter ≤ 2.5 μm) samples from seven German and Chinese cities, where the PM2.5 concentration ranged from a light (14 μg m-3) to heavy (319 μg m-3) pollution level. A large fraction (71-98%) of compounds in PM2.5 samples were attributable to intermediate-volatility organic compounds (IVOCs) and semivolatile organic compounds (SVOCs). The fraction of low-volatility organic compounds (LVOCs) and extremely low-volatility organic compounds (ELVOCs) decreased from clean (28%) to heavily polluted urban regions (2%), while that of IVOCs increased from 34 to 62%. We found that the average peak area-weighted volatility of organic compounds in different cities showed a logarithmic correlation with the average PM2.5 concentration, indicating that the volatility of urban OAs increases with the increase of air pollution level. Our results provide new insights into the relationship between OA volatility and PM pollution levels and deepen the understanding of urban air pollutant evolution.

Quantitative Characterization of the Volatility Distribution of Organic Aerosols in a Polluted Urban Area: Intercomparison Between Thermodenuder and Molecular Measurements

AbstractTo quantify the volatility of organic aerosols (OA), a comprehensive campaign was conducted in the Chinese megacity. Volatility distributions of OA and particle‐phase organic nitrate (pON) were estimated based on five methods: (a) empirical method and (b) kinetic model based on the measurement of a thermodenuder (TD) coupled with an aerosol mass spectrometer; (c) Formula‐based SIMPOL model‐driven method; (d) Element‐based estimations using molecular formula measurements of OA; and (e) gas/particle partitioning. Our results demonstrate that the ambient OA volatility distribution shows good agreement between the two heating methods and the formula‐based method when assuming ambient OA was mainly composed of organic nitrate (pON), organic sulfate and acid groups using the SIMPOL model. However, the element‐based method tends to overestimate the volatility of OA compared to the above three methods, suggesting large uncertainties in the parameterizations or in the representativeness of the molecular measurements that need further refinement. The volatility of ambient OA is generally lower than that of the laboratory‐derived secondary OA, emphasizing the impact of aging. A large fraction at the higher and lower volatility ranges (approximately log C* ≤ −9 and ≥2 μg m−3) was found for pON, implying the importance of both extremely low volatile and semi‐volatile species. Overall, this study evaluates different methods for volatility estimation and gives new insight into the volatility of OA and pON in urban areas.

Impact of Biomass Burning Organic Aerosol Volatility on Smoke Concentrations Downwind of Fires.

Biomass burning particulate matter (BBPM) affects regional air quality and global climate, with impacts expected to continue to grow over the coming years. We show that studies of North American fires have a systematic altitude dependence in measured BBPM normalized excess mixing ratio (NEMR; ΔPM/ΔCO), with airborne and high-altitude studies showing a factor of 2 higher NEMR than ground-based measurements. We report direct airborne measurements of BBPM volatility that partially explain the difference in the BBPM NEMR observed across platforms. We find that when heated to 40-45 °C in an airborne thermal denuder, 19% of lofted smoke PM1 evaporates. Thermal denuder measurements are consistent with evaporation observed when a single smoke plume was sampled across a range of temperatures as the plume descended from 4 to 2 km altitude. We also demonstrate that chemical aging of smoke and differences in PM emission factors can not fully explain the platform-dependent differences. When the measured PM volatility is applied to output from the High Resolution Rapid Refresh Smoke regional model, we predict a lower PM NEMR at the surface compared to the lofted smoke measured by aircraft. These results emphasize the significant role that gas-particle partitioning plays in determining the air quality impacts of wildfire smoke.

Impact of aging on the sources, volatility, and viscosity of organic aerosols in Chinese outflows

Abstract. To investigate the impact of aging on the sources, volatility, and viscosity of organic aerosol (OA) in Chinese outflows, a high-resolution time-of-flight aerosol mass spectrometer (HR-AMS) coupled with a thermodenuder (TD) was deployed in the spring of 2018 in Dongying, which is a regional receptor site of metropolitan emissions in the North China Plain (NCP). The average mass concentration of PM1 is 31.5±22.7 µg m−3, which is mainly composed of nitrate (33 %) and OA (25 %). The source apportionment results show that the OA is mainly contributed by oxygenated OA (OOA) from secondary sources, including background-OOA (33 %) representing a background concentration of OA (2.6 µg m−3) in the NCP area, and transported-OOA (33 %) oxidized from urban emissions. The other two factors include aged hydrocarbon-liked OA (aged-HOA, 28 %) from transported vehicle emissions and biomass burning OA (BBOA, 5 %) from local open burning. The volatility of total OA (average C*=3.2×10-4 µg m−3) in this study is generally lower than that reported in previous field studies, which is mainly due to the high OA oxidation level resulting from aging processes during transport. The volatilities of OA factors follow the order of background-OOA (average C*=2.7×10-5 µg m−3) < transported-OOA (3.7×10-4µgm-3)< aged-HOA (8.1×10-4µgm-3)< BBOA (0.012 µg m−3). Extremely low volatilities in ambient air indicate that oligomers may exist in aged plumes. The viscosity estimation suggests that the majority of ambient OA in this study behaves as semisolid (60 %), liquifies at higher relative humidity (RH) (21 %), and solidifies (19 %) during noon when the RH is low and the oxidation level is high. Finally, the estimated mixing time of molecules in 200 nm OA varies dramatically from minutes at night to years in the afternoon, emphasizing the need to consider its dynamic kinetic limits when modeling OA. In general, the overall results of this study improve our understanding of the impact of aging on OA volatility and viscosity.

Brown carbon absorptivity in fresh wildfire smoke: associations with volatility and chemical compound groups

Brown carbon light absorptivity is associated with organic aerosol volatility and elemental carbon concentrations.

Development and Application of the SmartAQ High-Resolution Air Quality and Source Apportionment Forecasting System for European Urban Areas

Air pollution forecasting systems are useful tools for the reduction in human health risks and the eventual improvement of atmospheric quality on regional or urban scales. The SmartAQ (Smart Air Quality) forecasting system combines state-of-the-art meteorological and chemical transport models to provide detailed air pollutant concentration predictions at a resolution of 1 × 1 km2 for the urban area of interest for the next few days. The Weather Research and Forecasting (WRF) mesoscale numerical weather prediction model is used to produce meteorological fields and the PMCAMx (Particulate Matter Comprehensive Air quality Model with extensions) chemical transport model for the simulation of air pollution. SmartAQ operates automatically in real time and provides, in its current configuration, a three-day forecast of the concentration of tens of gas-phase air pollutants (NOx, SO2, CO, O3, volatile organic compounds, etc.), the complete aerosol size/composition distribution, and the source contributions for all primary and secondary pollutants. The system simulates the regional air quality in Europe at medium spatial resolution and can focus, using high resolution, on any urban area of the continent. The city of Patras in Greece is used for the first SmartAQ application, taking advantage of the available Patras’ dense low-cost sensor network for PM2.5 (particles smaller than 2.5 μm) concentration measurements. Advantages of SmartAQ include (a) a high horizontal spatial resolution of 1 × 1 km2 for the simulated urban area; (b) advanced treatment of the organic aerosol volatility and chemistry; (c) use of an updated emission inventory that includes not only the traditional sources (industry, transport, agriculture, etc.), but also biomass burning from domestic heating and cooking; (d) forecasting of not only the pollutant concentrations, but also of the sources contributions for each one of them using the Particulate matter Source Apportionment Technology (PSAT) algorithm.

Volatility of Springtime ambient organic aerosol derived with thermodenuder aerosol mass spectrometry in Seoul, Korea

The volatilities of ambient organic aerosol (OA) components are important to forecasting OA formation with models. However, providing the OA volatility distribution inputs for models is challenging, and models often rely on measurements from chamber experiments. We measured the volatility of submicron ambient OA in Seoul during May/June of 2019 by connecting a thermodenuder to an Aerodyne Time-of-Flight Aerosol Mass Spectrometer (AMS). We calculated a volatility basis set (VBS) of the organic aerosol with a thermodenuder mass transfer model and data from the thermodenuder set to various temperatures (30–200 °C). We found a large discrepancy between the measured ambient VBS and a reference VBS used in air quality models, with the ambient organics being less volatile. The results suggest that a modeling study that tries to account for this discrepancy may be needed to identify the impact it has on modeling outcomes. Chamber experiments aiming to determine VBSs for specific chemical systems should address limitations caused by wall losses and incomplete modeling parameters.

Organic aerosol volatility and viscosity in the North China Plain: contrast between summer and winter

Abstract. Volatility and viscosity have substantial impacts on gas–particle partitioning, formation and evolution of aerosol and hence the predictions of aerosol-related air quality and climate effects. Here aerosol volatility and viscosity at a rural site (Gucheng) and an urban site (Beijing) in the North China Plain (NCP) in summer and winter were investigated by using a thermodenuder coupled with a high-resolution aerosol mass spectrometer. The effective saturation concentration (C*) of organic aerosol (OA) in summer was smaller than that in winter (0.55 µg m−3 vs. 0.71–0.75 µg m−3), indicating that OA in winter in the NCP is more volatile due to enhanced primary emissions from coal combustion and biomass burning. The volatility distributions varied and were largely different among different OA factors. In particular, we found that hydrocarbon-like OA (HOA) contained more nonvolatile compounds compared to coal-combustion-related OA. The more oxidized oxygenated OA (MO-OOA) showed overall lower volatility than less oxidized OOA (LO-OOA) in both summer and winter, yet the volatility of MO-OOA was found to be relative humidity (RH) dependent showing more volatile properties at higher RH. Our results demonstrated the different composition and chemical formation pathways of MO-OOA under different RH levels. The glass transition temperature (Tg) and viscosity of OA in summer and winter are estimated using the recently developed parameterization formula. Our results showed that the Tg of OA in summer in Beijing (291.5 K) was higher than that in winter (289.7–290.0 K), while it varied greatly among different OA factors. The viscosity suggested that OA existed mainly as solid in winter in Beijing (RH = 29 ± 17 %), but as semisolids in Beijing in summer (RH = 48 ± 25 %) and Gucheng in winter (RH = 68 ± 24 %). These results have the important implication that kinetically limited gas–particle partitioning may need to be considered when simulating secondary OA formation in the NCP.

Modeling the Effects of Dimerization and Bulk Diffusion on the Evaporative Behavior of Secondary Organic Aerosol Formed from α-Pinene and 1,3,5-Trimethylbenzene

Author(s): Morino, Y; Sato, K; Jathar, SH; Tanabe, K; Inomata, S; Fujitani, Y; Ramasamy, S; Cappa, CD | Abstract: Volatility determines the gas-particle partitioning of organic compounds. Volatility is thus a key property needed to understand the behavior of organic aerosol (OA) in the atmosphere. Various studies have been conducted to experimentally measure and numerically simulate distributions of OA volatility. The observed OA evaporation rates have generally been slower than the rates assuming instantaneous gas-particle equilibrium and volatility estimated from secondary organic aerosol (SOA) formation experiments. Particle-phase diffusion and/or low-volatility compounds, such as oligomers and highly oxygenated molecules, could limit the evaporation of OA, though the relative contributions of these factors are still uncertain. In this study, we conducted model simulations using a volatility basis set framework with the consideration of kinetic gas-particle partitioning, formation and dissociation of dimers, and particle-phase diffusion to reproduce observed evaporative behaviors of SOA formed from α-pinene ozonolysis and 1,3,5-trimethylbenzene (TMB)/NOx photooxidation. Based on simulations constrained by various volatility distributions derived from chemical analysis or heating experiments, we found that both dimerization and slow particle-phase diffusion contributed to the observed slow evaporation under dry conditions. In contrast, particle-phase diffusion did not practically inhibit SOA evaporation under humid conditions. The similarity of the fitted parameters, including dimer formation/dissociation rates and bulk diffusivity, for SOA from α-pinene and 1,3,5-TMB under dry conditions suggested that these processes are important for both monoterpene and aromatic SOA. Evaporation rates of SOA from α-pinene in this study were slower than the rates reported in previous experimental studies. This difference could be partly explained by differences in the experimental setups, including the treatment of organic vapors.

Evaluating Organic Aerosol Sources and Evolution with a Combined Molecular Composition and Volatility Framework Using the Filter Inlet for Gases and Aerosols (FIGAERO).

ConspectusThe complex array of sources and transformations of organic carbonaceous material that comprises an important fraction of atmospheric fine particle mass, known as organic aerosol, has presented a long running challenge for accurate predictions of its abundance, distribution, and sensitivity to anthropogenic activities. Uncertainties about changes in atmospheric aerosol particle sources and abundance over time translate to uncertainties in their impact on Earth's climate and their response to changes in air quality policy. One limitation in our understanding of organic aerosol has been a lack of comprehensive measurements of its molecular composition and volatility, which can elucidate sources and processes affecting its abundance. Herein we describe advances in the development and application of the Filter Inlet for Gases and Aerosols (FIGAERO) coupled to field-deployable High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometers (HRToF-CIMS). The FIGAERO HRToFCIMS combination broadly probes gas and particulate OA molecular composition by using programmed thermal desorption of particles collected on a Teflon filter with subsequent detection and speciation of desorbed vapors using inherently quantitative selected-ion chemical ionization. The thermal desorption provides a means to obtain quantitative insights into the volatility of particle components and thus the physicochemical nature of the organic material that will govern its evolution in the atmosphere.In this Account, we discuss the design and operation of the FIGAERO, when coupled to the HRToF-CIMS, for quantitative characterization of the molecular-level composition and effective volatility of organic aerosol in the laboratory and field. We provide example insights gleaned from its deployment, which improve our understanding of organic aerosol sources and evolution. Specifically, we connect thermal desorption profiles to the effective equilibrium saturation vapor concentration and enthalpy of vaporization of detected components. We also show how application of the FIGAERO HRToF-CIMS to environmental simulation chamber experiments and the field provide new insights and constraints on the chemical mechanisms governing secondary organic aerosol formation and dynamic evolution. We discuss the associated challenges of thermal decomposition during desorption and calibration of both the volatility axis and signal. We also illustrate how the FIGAERO HRToF-CIMS can provide additional insights into organic aerosol through isothermal evaporation experiments as well as for detection of ultrafine particulate composition. We conclude with a description of future opportunities and needs for its ability to further organic aerosol science.

Increase of High Molecular Weight Organosulfate With Intensifying Urban Air Pollution in the Megacity Beijing

AbstractOrganosulfates (OSs), a key component of secondary organic aerosols (SOA), account for up to one third of organic matter in the atmosphere. However, high molecular weight (HMW, 500–800 Da) OSs in ambient aerosols are poorly characterized at a molecular level, due to experimental difficulties. With Fourier transform‐ion cyclotron resonance mass spectrometry (FT‐ICRMS), we are able to identify more than 8,000 OSs in wintertime aerosols in Beijing. We found that both the number and signal magnitudes of HMW OSs with low H/C and O/C ratios and degrees of unsaturation were greatly enhanced during hazy days, indicating that most HMW OSs were freshly formed during stagnant air pollution episodes. They are most likely to be the oxidation products of semivolatility to low‐volatility precursors (e.g., polycyclic aromatic hydrocarbons and fatty acids) and have showed a strong influence of anthropogenic emissions. The molecular corridor analysis suggests that the high abundance of HMW aromatic‐like and aliphatic OSs considerably decreases the volatility of organic aerosols in the urban atmosphere.

Resolving ambient organic aerosol formation and aging pathways with simultaneous molecular composition and volatility observations.

Organic aerosol (OA) constitutes a significant fraction of atmospheric fine particle mass. However, the precursors and chemical processes responsible for a majority of OA are rarely conclusively identified. We use online observations of hundreds of simultaneously measured molecular components obtained from 15 laboratory OA formation experiments with constraints on their effective saturation vapor concentrations to attribute the VOC precursors and subsequent chemical pathways giving rise to the vast majority of OA mass measured in two forested regions. We find that precursors and chemical pathways regulating OA composition and volatility are dynamic over hours to days, with their variations driven by coupled interactions between multiple oxidants. The extent of physical and photochemical aging, and its modulation by NOx, were key to a uniquely comprehensive combined composition-volatility description of OA. Our findings thus provide some of the most complete mechanistic-level guidance to the development of OA descriptions in air quality and Earth system models.

Measuring and modeling the primary organic aerosol volatility from a modern non-road diesel engine

Primary organic aerosol (POA) in diesel exhaust is semi-volatile and partitions mass between the gas and particle phases. POA volatility is not well understood for alternative fuels, varying engine loads, and for engines that feature modern emissions controls. In this study, we performed filter-based measurements of diesel exhaust from a modern-day non-road diesel engine for two different fuels (conventional diesel and soy-based biodiesel), two different engine loads (idle and 50% load), and with and without an emissions control device. Filters were analyzed offline to determine the POA volatility in two different ways: positive artifact on quartz filters at varying dilution ratios and speciation of alkanes. The POA volatility determined from our data suggests that POA mass emissions from diesel exhaust may be reduced by a factor of five with dilution to atmospherically relevant concentrations. These results are generally consistent with previous literature on POA volatility from non-road diesel engines but not with that from on-road diesel vehicles. POA volatility may hence need to be treated separately for non- and on-road sources in atmospheric models. Surprisingly, the POA volatility did not appear to vary under different combinations of fuel, engine load, and emissions control experiments performed, suggesting that POA might be dominated by unburned lubricating oil and its oxidation products. The POA volatility estimated from the speciation of alkanes was found to agree well with that determined from the dilution experiments. A kinetic model was used to calculate the gas/particle partitioning of POA in the dilution system. The modeling suggests that residence times in the dilution tunnel need to be on the order of minutes to allow the POA in the diluted exhaust to achieve gas/particle equilibrium. The use of short residence times (less than tens of seconds), similar to those used in conventional dilution systems, may bias the measurement of POA mass emissions in such systems and is of particular concern for emissions from cleaner, more modern combustion sources. The precise magnitude and direction of the bias depends on the exhaust temperature before dilution, tailpipe seed concentrations, dilution ratio, and residence times in the dilution tunnel. We recommend that kinetic models such as those used in this work be used, instead of using equilibrium assumptions, to inform the design and operation of the dilution tunnels as well to interpret the POA volatility from measurements made with those dilution tunnels.

Seasonal characteristics of organic aerosol chemical composition and volatility in Stuttgart, Germany

Abstract. The chemical composition and volatility of organic aerosol (OA) particles were investigated during July–August 2017 and February–March 2018 in the city of Stuttgart, one of the most polluted cities in Germany. Total non-refractory particle mass was measured with a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS; hereafter AMS). Aerosol particles were collected on filters and analyzed in the laboratory with a filter inlet for gases and aerosols coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (FIGAERO-HR-ToF-CIMS; hereafter CIMS), yielding the molecular composition of oxygenated OA (OOA) compounds. While the average organic mass loadings are lower in the summer period (5.1±3.2 µg m−3) than in the winter period (8.4±5.6 µg m−3), we find relatively larger mass contributions of organics measured by AMS in summer (68.8±13.4 %) compared to winter (34.8±9.5 %). CIMS mass spectra show OOA compounds in summer have O : C of 0.82±0.02 and are more influenced by biogenic emissions, while OOA compounds in winter have O : C of 0.89±0.06 and are more influenced by biomass burning emissions. Volatility parametrization analysis shows that OOA in winter is less volatile with higher contributions of low-volatility organic compounds (LVOCs) and extremely low-volatility organic compounds (ELVOCs). We partially explain this by the higher contributions of compounds with shorter carbon chain lengths and a higher number of oxygen atoms, i.e., higher O : C in winter. Organic compounds desorbing from the particles deposited on the filter samples also exhibit a shift of signal to higher desorption temperatures (i.e., lower apparent volatility) in winter. This is consistent with the relatively higher O : C in winter but may also be related to higher particle viscosity due to the higher contributions of larger-molecular-weight LVOCs and ELVOCs, interactions between different species and/or particles (particle matrix), and/or thermal decomposition of larger molecules. The results suggest that whereas lower temperature in winter may lead to increased partitioning of semi-volatile organic compounds (SVOCs) into the particle phase, this does not result in a higher overall volatility of OOA in winter and that the difference in sources and/or chemistry between the seasons plays a more important role. Our study provides insights into the seasonal variation of the molecular composition and volatility of ambient OA particles and into their potential sources.

Assessing PM2.5 model performance for the conterminous U.S. with comparison to model performance statistics from 2007-2015

Previous studies have proposed that model performance statistics from earlier photochemical grid model (PGM) applications can be used to benchmark performance in new PGM applications. A challenge in implementing this approach is that limited information is available on consistently calculated model performance statistics that vary spatially and temporally over the U.S. Here, a consistent set of model performance statistics are calculated by year, season, region, and monitoring network for PM2.5 and its major components using simulations from versions 4.7.1-5.2.1 of the Community Multiscale Air Quality (CMAQ) model for years 2007–2015. The multi-year set of statistics is then used to provide quantitative context for model performance results from the 2015 simulation. Model performance for PM2.5 organic carbon in the 2015 simulation ranked high (i.e., favorable performance) in the multi-year dataset, due to factors including recent improvements in biogenic secondary organic aerosol and atmospheric mixing parameterizations in CMAQ. Model performance statistics for the Northwest region in 2015 ranked low (i.e., unfavorable performance) for many species in comparison to the 2007–2015 dataset. This finding motivated additional investigation that suggests a need for improved speciation of wildfire PM2.5 emissions and modeling of boundary layer dynamics near water bodies. Several limitations were identified in the approach of benchmarking new model performance results with previous results. Since performance statistics vary widely by region and season, a simple set of national performance benchmarks (e.g., one or two targets per species and statistic) as proposed previously are inadequate to assess model performance throughout the U.S. Also, trends in model performance statistics for sulfate over the 2007 to 2015 period suggest that model performance for earlier years may not be a useful reference for assessing model performance for recent years in some cases. Comparisons of results from the 2015 base case with results from five sensitivity simulations demonstrated the importance of parameterizations of NH3 surface exchange, organic aerosol volatility and production, and emissions of crustal cations for predicting PM2.5 species concentrations.

Characterization of submicron aerosol volatility in the regional atmosphere in Southern China

The volatility of atmospheric aerosols greatly influences the gas-particle partitioning, chemical mechanisms and lifetime of aerosols. Due to the complex composition, the volatility of organic aerosol is one of the major sources of uncertainty in measuring and modeling ambient aerosols. Despite high aerosol loading in the atmosphere in China, especially in winter, few field measurements were conducted targeting the volatility of ambient organic aerosol (OA). With the deployment of a thermodenuder-aerosol mass spectrometer (TD-AMS) system, the volatility of non-refractory submicron aerosols (NR-PM1) were measured on an island near the coastal line for the regional air in wintertime in southern China. NO3− and Cl− showed the highest volatility in the NR-PM1 chemical species, while SO42− showed the least volatility. Organic aerosol showed a moderate volatility, evaporating at a stable rate (0.57% °C−1) at temperatures lower than 150 °C and keeping a stable volatility when its loading increases, which could be an advantage for parameterization of OA in air quality models. Based on both positive matrix factorization and chemical mass balance modeling of OA composition, biomass burning OA was found to be the most volatile factor, followed by hydrocarbon-like OA and more-oxidized oxygenated OA. By summarizing the OA volatility measured in this study and in the literature, we found that the volatilities of different OA factors at different locations do not have a clear relationship with the OA oxidation state, possibly due to the vague understanding of local OA aging mechanisms and mixing states.

Improving new particle formation simulation by coupling a volatility-basis set (VBS) organic aerosol module in NAQPMS+APM

We developed a new modeling framework to simulate aerosol microphysics by incorporating a volatility basis-set (VBS) organic aerosol (OA) module into a three-dimensional (3-D) atmospheric transport model, namely, Nested Air Quality Prediction Modeling System with an Advanced Particle Microphysics (NAQPMS + APM). The new model calculates not only the condensation of sulfuric acid, nitrate, and ammonium and the coagulation of five types of particles (namely secondary, sea salt, dust, black carbon and organic carbon particles) but also the condensation of low-volatility organic vapors and the equilibrium partitioning of semi-volatile organic compounds. The new model was applied to simulate new particle formation (NPF) in summer in Beijing. The new model could noticeably improve the NPF simulation. On comparing the simulation with observation, the ion-mediated nucleation scheme was found to underestimate nucleation rates in summer in Beijing. By incorporating a nucleation formula involving the participation of organic compounds, NPF events could be reproduced satisfactorily. Reasonably calculating nucleation rates is essential for successfully simulating NPF. Accounting for the condensation of anthropogenic low-volatility organic vapors and the volatility of primary OA (POA) can improve the temporal variation of the number concentrations of particles in Aitken and accumulation modes. On a regional scale, anthropogenic low-volatility secondary organic gases (LV-SOGs) and the volatility of POA have large impacts on the aerosol number concentration and cloud condensation nuclei (CCN) concentration. Both anthropogenic LV-SOGs and volatility of POA must be considered to quantify the contribution of NPF to the aerosol number concentration and CCN concentration.

Organic carbon at a remote site of the western Mediterranean Basin: sources and chemistry during the ChArMEx SOP2 field experiment

Abstract. The ChArMEx (Chemistry and Aerosols Mediterranean Experiments) SOP2 (special observation period 2) field campaign took place from 15 July to 5 August 2013 in the western Mediterranean Basin at Ersa, a remote site in Cape Corse. During the campaign more than 80 volatile organic compounds (VOCs), including oxygenated species, were measured by different online and offline techniques. At the same time, an exhaustive description of the chemical composition of fine aerosols was performed with an aerosol chemical speciation monitor (ACSM). Low levels of anthropogenic VOCs (typically tens to hundreds of parts per trillion for individual species) and black carbon (0.1–0.9 µg m−3) were observed, while significant levels of biogenic species (peaking at the ppb level) were measured. Furthermore, secondary oxygenated VOCs (OVOCs) largely dominated the VOC speciation during the campaign, while organic matter (OM) dominated the aerosol chemical composition, representing 55 % of the total mass of non-refractory PM1 on average (average of 3.74 ± 1.80 µg m−3), followed by sulfate (27 %, 1.83 ± 1.06 µg m−3), ammonium (13 %, 0.90 ± 0.55 µg m−3) and nitrate (5 %, 0.31 ± 0.18 µg m−3). Positive matrix factorization (PMF) and concentration field (CF) analyses were performed on a database containing 42 VOCs (or grouped VOCs), including OVOCs, to identify the covariation factors of compounds that are representative of primary emissions or chemical transformation processes. A six-factor solution was found for the PMF analysis, including a primary and secondary biogenic factor correlated with temperature and exhibiting a clear diurnal profile. In addition, three anthropogenic factors characterized by compounds with various lifetimes and/or sources have been identified (long-lived, medium-lived and short-lived anthropogenic factors). The anthropogenic nature of these factors was confirmed by the CF analysis, which identified potential source areas known for intense anthropogenic emissions (north of Italy and southeast of France). Finally, a factor characterized by OVOCs of both biogenic and anthropogenic origin was found. This factor was well correlated with submicron organic aerosol (OA) measured by an aerosol chemical speciation monitor (ACSM), highlighting the close link between OVOCs and organic aerosols; the latter is mainly associated (96 %) with the secondary OA fraction. The source apportionment of OA measured by ACSM led to a three-factor solution identified as hydrogen-like OA (HOA), semi-volatile oxygenated OA (SV-OOA) and low volatility OOA (LV-OOA) for averaged mass concentrations of 0.13, 1.59 and 1.92 µg m−3, respectively. A combined analysis of gaseous PMF factors with inorganic and organic fractions of aerosols helped distinguish between anthropogenic continental and biogenic influences on the aerosol- and gas-phase compositions.

Estimates of the organic aerosol volatility in a boreal forest using two independent methods

Abstract. The volatility distribution of secondary organic aerosols that formed and had undergone aging – i.e., the particle mass fractions of semi-volatile, low-volatility and extremely low volatility organic compounds in the particle phase – was characterized in a boreal forest environment of Hyytiälä, southern Finland. This was done by interpreting field measurements using a volatility tandem differential mobility analyzer (VTDMA) with a kinetic evaporation model. The field measurements were performed during April and May 2014. On average, 40 % of the organics in particles were semi-volatile, 34 % were low-volatility organics and 26 % were extremely low volatility organics. The model was, however, very sensitive to the vaporization enthalpies assumed for the organics (ΔHVAP). The best agreement between the observed and modeled temperature dependence of the evaporation was obtained when effective vaporization enthalpy values of 80 kJ mol−1 were assumed. There are several potential reasons for the low effective enthalpy value, including molecular decomposition or dissociation that might occur in the particle phase upon heating, mixture effects and compound-dependent uncertainties in the mass accommodation coefficient. In addition to the VTDMA-based analysis, semi-volatile and low-volatility organic mass fractions were independently determined by applying positive matrix factorization (PMF) to high-resolution aerosol mass spectrometer (HR-AMS) data. The factor separation was based on the oxygenation levels of organics, specifically the relative abundance of mass ions at m∕z 43 (f43) and m∕z 44 (f44). The mass fractions of these two organic groups were compared against the VTDMA-based results. In general, the best agreement between the VTDMA results and the PMF-derived mass fractions of organics was obtained when ΔHVAP = 80 kJ mol−1 was set for all organic groups in the model, with a linear correlation coefficient of around 0.4. However, this still indicates that only about 16 % (R2) of the variation can be explained by the linear regression between the results from these two methods. The prospect of determining of extremely low volatility organic aerosols (ELVOAs) from AMS data using the PMF analysis should be assessed in future studies.