Extremely Low Volatile Organic Compounds Research Articles

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.

The search for sparse data in molecular datasets: Application of active learning to identify extremely low volatile organic compounds

The formation of aerosol particles in the atmosphere is driven by the gas to particle conversion of extremely low volatile organic compounds (ELVOC), organic compounds with a particularly low saturation vapor pressure (pSat). Identifying ELVOCs and their chemical structures is both experimentally and theoretically challenging: Measuring the very low pSat of ELVOCs is extremely difficult, and computing pSat for these often large molecules is computationally costly. Moreover, ELVOCs are underrepresented in available datasets of atmospheric organic species, which reduces the value of statistical models built on such data. We propose an active learning (AL) approach to efficiently identify ELVOCs in a data pool of atmospheric organic species with initially unknown pSat. We assess the performance of our AL approach by comparing it to traditional machine learning regression methods, as well as ELVOC classification based on molecular properties. AL proves to be a highly efficient method for ELVOC identification with limitations on the type of ELVOC it can identify. We also show that traditional machine learning or molecular property-based methods can be adequate tools depending on the available data and desired degree of efficiency.

Volatility of aerosol particles from NO3 oxidation of various biogenic organic precursors

Abstract. Secondary organic aerosol (SOA) is formed through the oxidation of volatile organic compounds (VOCs), which can be of both natural and anthropogenic origin. While the hydroxyl radical (OH) and ozone (O3) are the main atmospheric oxidants during the day, the nitrate radical (NO3) becomes more important during the nighttime. Yet, atmospheric nitrate chemistry has received less attention compared to OH and O3. The Nitrate Aerosol and Volatility Experiment (NArVE) aimed to study the NO3-induced SOA formation and evolution from three biogenic VOCs (BVOCs), namely isoprene, α-pinene, and β-caryophyllene. The volatility of aerosol particles was studied using isothermal evaporation chambers, temperature-dependent evaporation in a volatility tandem differential mobility analyzer (VTDMA), and thermal desorption in a filter inlet for gases and aerosols coupled to a chemical ionization mass spectrometer (FIGAERO-CIMS). Data from these three setups present a cohesive picture of the volatility of the SOA formed in the dark from the three biogenic precursors. Under our experimental conditions, the SOA formed from NO3 + α-pinene was generally more volatile than SOA from α-pinene ozonolysis, while the NO3 oxidation of isoprene produced similar although slightly less volatile SOA than α-pinene under our experimental conditions. β-Caryophyllene reactions with NO3 resulted in the least volatile species. Four different parameterizations for estimating the saturation vapor pressure of the oxidation products were tested for reproducing the observed evaporation in a kinetic modeling framework. Our results show that the SOA from nitrate oxidation of α-pinene or isoprene is dominated by low-volatility organic compounds (LVOCs) and semi-volatile organic compounds (SVOCs), while the corresponding SOA from β-caryophyllene consists primarily of extremely low-volatility organic compounds (ELVOCs) and LVOCs. The parameterizations yielded variable results in terms of reproducing the observed evaporation, and generally the comparisons pointed to a need for re-evaluating the treatment of the nitrate group in such parameterizations. Strategies for improving the predictive power of the volatility parameterizations, particularly in relation to the contribution from the nitrate group, are discussed.

Identification of highly oxygenated organic molecules and their role in aerosol formation in the reaction of limonene with nitrate radical

Abstract. Nighttime NO3-initiated oxidation of biogenic volatile organic compounds (BVOCs) such as monoterpenes is important for the atmospheric formation and growth of secondary organic aerosol (SOA), which has significant impact on climate, air quality, and human health. In such SOA formation and growth, highly oxygenated organic molecules (HOM) may be crucial, but their formation pathways and role in aerosol formation have yet to be clarified. Among monoterpenes, limonene is of particular interest for its high emission globally and high SOA yield. In this work, HOM formation in the reaction of limonene with nitrate radical (NO3) was investigated in the SAPHIR chamber (Simulation of Atmospheric PHotochemistry In a large Reaction chamber). About 280 HOM products were identified, grouped into 19 monomer families, 11 dimer families, and 3 trimer families. Both closed-shell products and open-shell peroxy radicals (RO2⚫) were observed, and many of them have not been reported previously. Monomers and dimers accounted for 47 % and 47 % of HOM concentrations, respectively, with trimers making up the remaining 6 %. In the most abundant monomer families, C10H15−17NO6−14, carbonyl products outnumbered hydroxyl products, indicating the importance of RO2⚫ termination by unimolecular dissociation. Both RO2⚫ autoxidation and alkoxy–peroxy pathways were found to be important processes leading to HOM. Time-dependent concentration profiles of monomer products containing nitrogen showed mainly second-generation formation patterns. Dimers were likely formed via the accretion reaction of two monomer RO2⚫, and HOM-trimers via the accretion reaction between monomer RO2⚫ and dimer RO2⚫. Trimers are suggested to play an important role in new particle formation (NPF) observed in our experiment. A HOM yield of 1.5%-0.7%+1.7% was estimated considering only first-generation products. SOA mass growth could be reasonably explained by HOM condensation on particles assuming irreversible uptake of ultra-low volatility organic compounds (ULVOCs), extremely low volatility organic compounds (ELVOCs), and low volatility organic compounds (LVOCs). This work provides evidence for the important role of HOM formed via the limonene +NO3 reaction in NPF and growth of SOA particles.

Influence of emission size distribution and nucleation on number concentrations over Greater Paris

Abstract. With the growing evidence that high particle number concentrations may impact health, modelling their emissions and understanding formation processes is necessary, especially in cities where many people are exposed. As emission inventories of particle numbers and size distribution over cities are usually not available, a methodology is defined to estimate them from PM2.5 emissions and ratios of PM1 / PM2.5 and PM0.1 / PM2.5 by activity sector. In this methodology, a fitting parameter αem is used to redistribute the number concentrations in the lowest emission diameter range. This parameter is chosen by comparing measured and simulated number concentrations during non-nucleation days. The emission size distribution is then finely discretised by conserving both mass and number in each of the size ranges where emissions are specified. The methodology is applied over Greater Paris during the MEGAPOLI campaign (July 2009). Three-dimensional simulations are performed using the chemistry transport model Polair3D/Polyphemus coupled to the aerosol module SSH-aerosol to represent the evolution of particles by condensation, evaporation, coagulation, and nucleation, with a sectional approach for the size distribution. The model is first compared to measurements during non-nucleation days, and the influence over the month of July 2009 of three different nucleation parameterisations is assessed, i.e. binary (sulfuric acid, water), ternary (sulfuric acid, ammonia, water), and heteromolecular (extremely low-volatility organic compounds (ELVOCs) from monoterpenes and sulfuric acid). The modelled number concentrations compare very well to measurements, with an average normalised mean error of 42 % for the daily number concentrations of particles larger than 10 nm and 37 % for the number concentrations of particles larger than 100 nm. The influence of the binary nucleation is low, and the ternary nucleation scheme leads to better simulated number concentrations (in terms of bias and error) at only one site out of three, but it systematically reduces the model to measurement correlation, suggesting that ternary nucleation may not be the dominant process in new particle formation. However, the relative bias and error, as well as the correlation at suburban sites, are systematically improved using the heteromolecular nucleation scheme involving sulfuric acid and ELVOCs from monoterpenes. This suggests that heteromolecular nucleation may be important in cities, especially at suburban sites in summer, and that a better characterisation of the emissions of ELVOC precursors from traffic is needed.

Formation of extremely low-volatility organic compounds from styrene ozonolysis: Implication for nucleation

Styrene is a highly reactive compound with the dual nature of aromatics and olefins. This work presents evidence for formation of extremely low-volatility organic compounds (ELVOCs) from styrene ozonolysis. The molecules of ELVOCs were analyzed using a high-resolution orbitrap mass spectrometer. The results show that ELVOCs were oligomers characterized by stabilized Criegee radicals (SCIs) as chain units. The addition of C6H5CHOO (SCI1) or CH2OO (SCI2) can dramatically decrease the oligomers' volatility. At low relative humidity (RH), ELVOCs are mainly formed from the reaction of RO2 radical, C6H5OO·, with SCI1 and SCI2; however, ELVOCs are primarily produced by the reaction between benzoic acid and SCI1 at high RH. Ambient particles were also collected to propose the probable oligomers from styrene-SCI. Our results suggest that styrene-SCI derived ELVOCs may act as nucleating agents, potentially providing an experimental basis for nucleation events that frequently occur in urban areas.

Simulation of the effects of low-volatility organic compounds on aerosol number concentrations in Europe

Abstract. PMCAMx-UF, a three-dimensional chemical transport model focusing on the simulation of the ultrafine particle size distribution and composition has been extended with the addition of reactions of chemical aging of semivolatile anthropogenic organic vapors, the emissions and chemical aging of intermediate-volatility organic compounds (IVOCs), and the production of extremely low-volatility organic compounds (ELVOCs) by monoterpenes. The model is applied in Europe to quantify the effect of these processes on particle number concentrations. The model predictions are evaluated against both ground measurements collected during the PEGASOS 2012 summer campaign across many stations in Europe and airborne observations by a zeppelin measuring above Po Valley, Italy. PMCAMx-UF reproduces the ground level daily average concentrations of particles with a diameter larger than 100 nm (N100) with normalized mean error (NME) of 45 % and normalized mean bias (NMB) close to 10 %. For the same simulation, PMCAMx-UF tends to overestimate the concentration of particles with a diameter larger than 10 nm (N10) with a daily NMB of 23 % and a daily NME of 63 %. The model was able to reproduce more than 75 % of the N10 and N100 airborne observations (zeppelin) within a factor of 2. According to the PMCAMx-UF predictions, the ELVOC production by monoterpenes leads to surprisingly small changes of the average number concentrations over Europe. The total number concentration decreased due to the ELVOC formation by 0.2 %, N10 decreased by 1.1 %, N50 (particles with a diameter larger than 50 nm) increased by 3 %, and N100 increased by 4 % due to this new secondary organic aerosol (SOA) source. This small change is due to the nonlinearity of the system, with increases predicted in some areas and decreases in others, but also the cancelation of the effects of the various processes like accelerated growth and accelerated coagulation. Locally, the effects can be significant. For example, an increase in N100 by 20 %–50 % is predicted over Scandinavia and significant increases (10 %–20 %) are predicted over some parts of central Europe. The ELVOCs contributed on average around 0.5 µg m−3 and accounted for 10 %–15 % of the PM2.5 OA. The addition of IVOC emissions and their aging reactions led to a surprising reduction of the total number of particles (Ntot) and N10 by 10 %–15 % and 5 %–10 %, respectively, and to an increase in the concentration of N100 by 5 %–10 %. These were due to the accelerated coagulation and reduced nucleation rates.

Chemical characterisation of benzene oxidation products under high- and low-NO<sub><i>x</i></sub> conditions using chemical ionisation mass spectrometry

Abstract. Aromatic hydrocarbons are a class of volatile organic compounds associated with anthropogenic activity and make up a significant fraction of urban volatile organic compound (VOC) emissions that contribute to the formation of secondary organic aerosol (SOA). Benzene is one of the most abundant species emitted from vehicles, biomass burning and industry. An iodide time-of-flight chemical ionisation mass spectrometer (ToF-CIMS) and nitrate ToF-CIMS were deployed at the Jülich Plant Atmosphere Chamber as part of a series of experiments examining benzene oxidation by OH under high- and low-NOx conditions, where a range of organic oxidation products were detected. The nitrate scheme detects many oxidation products with high masses, ranging from intermediate volatile organic compounds (IVOCs) to extremely low volatile organic compounds (ELVOCs), including C12 dimers. In comparison, very few species with C≥6 and O≥8 were detected with the iodide scheme, which detected many more IVOCs and semi-volatile organic compounds (SVOCs) but very few ELVOCs and low volatile organic compounds (LVOCs). A total of 132 and 195 CHO and CHON oxidation products are detected by the iodide ToF-CIMS in the low- and high-NOx experiments respectively. Ring-breaking products make up the dominant fraction of detected signal and 21 and 26 of the products listed in the Master Chemical Mechanism (MCM) were detected. The time series of highly oxidised (O≥6) and ring-retaining oxidation products (C6 and double-bond equivalent = 4) equilibrate quickly, characterised by a square form profile, compared to MCM and ring-breaking products which increase throughout oxidation, exhibiting sawtooth profiles. Under low-NOx conditions, all CHO formulae attributed to radical termination reactions of first-generation benzene products, and first-generation auto-oxidation products are observed. Several N-containing species that are either first-generation benzene products or first-generation auto-oxidation products are also observed under high-NOx conditions. Hierarchical cluster analysis finds four clusters, of which two describe photo-oxidation. Cluster 2 shows a negative dependency on the NO2/NOx ratio, indicating it is sensitive to NO concentration and thus likely to contain NO addition products and alkoxy-derived termination products. This cluster has the highest average carbon oxidation state (OSC‾) and the lowest average carbon number. Where nitrogen is present in a cluster member of cluster 2, the oxygen number is even, as expected for alkoxy-derived products. In contrast, cluster 1 shows no dependency on the NO2/NOx ratio and so is likely to contain more NO2 addition and peroxy-derived termination products. This cluster contains fewer fragmented species, as the average carbon number is higher and OSC‾ lower than cluster 2, and more species with an odd number of oxygen atoms. This suggests that clustering of time series which have features pertaining to distinct chemical regimes, for example, NO2/NOx perturbations, coupled with a priori knowledge, can provide insight into identification of potential functionality.

Aerosol light absorption and the role of extremely low volatility organic compounds

Abstract. A month-long set of summertime measurements in a remote area in the Mediterranean is used to quantify aerosol absorption and the role of black and brown carbon. The suite of instruments included a high-resolution aerosol mass spectrometer (HR-ToF-AMS) and a scanning mobility particle sizer (SMPS), both coupled to a thermodenuder and an Aethalometer, a photoacoustic extinctiometer (PAX405), and a single particle soot photometer (SP2). The average refractory black carbon (rBC) concentration during the campaign was 0.14 µg m−3, representing 3 % of the fine aerosol mass. The measured light absorption was two or more times higher than that of fresh black carbon (BC). Mie theory indicated that the absorption enhancement due to the coating of BC cores by nonrefractory material could explain only part of this absorption enhancement. The role of brown carbon (BrC) and other non-BC light-absorbing material was then investigated. A good correlation (R2=0.76) between the unexplained absorption and the concentration of extremely low volatility organic compounds (ELVOCs) mass was found.

Molecular insights into new particle formation in Barcelona, Spain

Abstract. Atmospheric aerosols contribute some of the greatest uncertainties to estimates of global radiative forcing and have significant effects on human health. New particle formation (NPF) is the process by which new aerosols of sub-2 nm diameter form from gas-phase precursors and contributes significantly to particle numbers in the atmosphere, accounting for approximately 50 % of cloud condensation nuclei globally. Here, we study summertime NPF in urban Barcelona in north-eastern Spain utilising particle counting instruments down to 1.9 nm and a Nitrate Chemical Ionisation Atmospheric Pressure interface Time of Flight Mass Spectrometer (CI-APi-ToF). The rate of formation of new particles is seen to increase linearly with sulfuric acid concentration, although particle formation rates fall short of chamber studies of H2SO4–DMA–H2O while exceeding those of H2SO4–BioOxOrg–H2O nucleation, although a role of highly oxygenated molecules (HOMs) cannot be ruled out. The sulfuric acid dimer : monomer ratio is significantly lower than that seen in experiments involving sulfuric acid and dimethylamine (DMA) in chambers, indicating that stabilisation of sulfuric acid clusters by bases is weaker in this dataset than in chambers, either due to rapid evaporation due to high summertime temperatures or limited pools of stabilising amines. Such a mechanism cannot be verified in these data, as no higher-order H2SO4–amine clusters nor H2SO4–HOM clusters were measured. The high concentrations of HOMs arise from isoprene, alkylbenzene, monoterpene and polycyclic aromatic hydrocarbon (PAH) oxidation, with alkylbenzenes providing greater concentrations of HOMs due to significant local sources. The concentration of these HOMs shows a dependence on temperature. The organic compounds measured primarily fall into the semivolatile organic compound (SVOC) volatility class arising from alkylbenzene and isoprene oxidation. Low-volatility organic compounds (LVOCs) largely arise from oxidation of alkylbenzenes, PAHs and monoterpenes, whereas extremely low-volatility organic compounds (ELVOCs) arise from primarily PAH and monoterpene oxidation. New particle formation without growth past 10 nm is also observed, and on these days oxygenated organic concentrations are lower than on days with growth by a factor of 1.6, and thus high concentrations of low-volatility oxygenated organics which primarily derive from traffic-emitted volatile organic compounds (VOCs) appear to be a necessary condition for the growth of newly formed particles in Barcelona. These results are consistent with prior observations of new particle formation from sulfuric acid–amine reactions in both chambers and the real atmosphere and are likely representative of the urban background of many European Mediterranean cities. A role for HOMs in the nucleation process cannot be confirmed or ruled out, and there is strong circumstantial evidence of the participation of HOMs across multiple volatility classes in particle growth.

Volatility Dependence of the Aerosol Size Distributions of Nonpolar Organic Compounds: A Case Study in Shanghai

AbstractThe aerosol size distribution of organic compounds is one of the fundamental characteristics that regulates their atmospheric deposition and environmental fate. In this study, we characterized the organic components (mostly nonpolar organic compounds) in size‐resolved particles, with a focus on polycyclic aromatic hydrocarbons (PAHs), oxygenated PAHs (O‐PAHs), n‐alkanes, and polybrominated diphenyl ethers (PBDEs), in the urban Shanghai atmosphere during a 1‐year sampling period using gas chromatography (GC) coupled to tandem mass spectrometry (GC‐MS/MS) and two‐dimensional GC with a flame ionization detector (GC × GC‐FID). These compounds ranged from volatile organic compounds (VOCs) to extremely low volatility organic compounds (ELVOCs). We related their aerosol size distributions with their volatilities. On average, high positive correlations (p < 0.01) were observed between the size distribution characteristics (e.g., geometric mean diameter [GMD] and mass fraction in coarse particles) and volatility (logarithmic value of the saturation mass concentration, log C*) for the compounds that we examined. A higher ambient temperature tends to increase the slope of the regression line between size distribution and volatility (log C*). Further dry deposition modeling of size‐resolved particles showed a positive correlation (p < 0.01) between the bulk dry deposition velocity and GMD and between the bulk dry deposition velocity and volatility of the target compounds, indicating that low‐volatility organic compounds have a lower dry deposition velocity and are more likely to be transported to remote areas if they do not have a short half‐life in the atmosphere.

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.

Modelling organic aerosol concentrations and properties during ChArMEx summer campaigns of 2012 and 2013 in the western Mediterranean region

Abstract. In the framework of the Chemistry-Aerosol Mediterranean Experiment, a measurement site was set up at a remote site (Ersa) on Corsica Island in the northwestern Mediterranean Sea. Measurement campaigns performed during the summers of 2012 and 2013 showed high organic aerosol concentrations, mostly from biogenic origin. This work aims to represent the organic aerosol concentrations and properties (oxidation state and hydrophilicity) using the air-quality model Polyphemus with a surrogate approach for secondary organic aerosol (SOA) formation. Biogenic precursors are isoprene, monoterpenes and sesquiterpenes. In this work, the following model oxidation products of monoterpenes are added: (i) a carboxylic acid (MBTCA) to represent multi-generation oxidation products in the low-NOx regime, (ii) organic nitrate chemistry and (iii) extremely low-volatility organic compounds (ELVOCs) formed by ozonolysis. The model shows good agreement of measurements of organic concentrations for both 2012 and 2013 summer campaigns. The modelled oxidation property and hydrophilic organic carbon properties of the organic aerosols also agree reasonably well with the measurements. The influence of the different chemical processes added to the model on the oxidation level of organics is studied. Measured and simulated water-soluble organic carbon (WSOC) concentrations show that even at a remote site next to the sea, about 64 % of the organic carbon is soluble. The concentrations of WSOC vary with the origins of the air masses and the composition of organic aerosols. The marine organic emissions only contribute to a few percent of the organic mass in PM1, with maxima above the sea.

Volatility of source apportioned wintertime organic aerosol in the city of Athens

The volatility distribution of ambient organic aerosol (OA) and its components was measured during the winter of 2013 in the city of Athens combining a thermodenuder (TD) and a High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). Positive Matrix Factorization (PMF) analysis of both the ambient and the thermodenuder AMS-spectra resulted in a four-factor solution for the OA, namely: hydrocarbon-like OA (HOA), biomass burning OA (BBOA), cooking OA (COA), and oxygenated OA (OOA). The thermograms of the four factors were analyzed and the corresponding volatility distributions were estimated using the volatility basis set (VBS). All four factors included compounds with a wide range of effective volatilities from 10 to less than 10−4 μg m−3 at 298 K. Almost 40% of the HOA consisted of low-volatility organic compounds (LVOCs) with the semi-volatile compounds (SVOCs) representing roughly 30%, while the remaining 30% consisted of extremely low volatility organic compounds (ELVOCs). BBOA was more volatile than the HOA factor on average, with 10% ELVOCs, 40% LVOCs, and 50% SVOCs. 10% of the COA consisted of ELVOCs, another 65% LVOCs, and 50% SVOCs. Finally, the OOA was the least volatile factor and included 40% ELVOCs, 25% LVOCs, and 35% SVOCs. Combining the volatility distributions and the O:C ratios of the various factors, we placed our results in the 2D-VBS analysis framework of Donahue et al. (2012). HOA and BBOA are in the expected region but also include an ELVOC component. COA is in similar range as HOA, but on average is half an order of magnitude more volatile. The OOA in these wintertime conditions had a moderate O:C ratio and included both semi-volatile and extremely low volatility components. The above results are sensitive to the assumed values of the effective vaporization enthalpy and the accommodation coefficient. A reduction of the accommodation coefficient by an order of magnitude or the reduction of the vaporization enthalpy by 20 kJ mol−1 results in the increase of the average volatility by half an order of magnitude.

Molecular-Size-Separated Brown Carbon Absorption for Biomass-Burning Aerosol at Multiple Field Sites.

Biomass burning is a known source of brown carbon aerosol in the atmosphere. We collected filter samples of biomass-burning emissions at three locations in Canada and the United States with transport times of 10 h to >3 days. We analyzed the samples with size-exclusion chromatography coupled to molecular absorbance spectroscopy to determine absorbance as a function of molecular size. The majority of absorption was due to molecules >500 Da, and these contributed an increasing fraction of absorption as the biomass-burning aerosol aged. This suggests that the smallest molecular weight fraction is more susceptible to processes that lead to reduced light absorption, while larger-molecular-weight species may represent recalcitrant brown carbon. We calculate that these large-molecular-weight species are composed of more than 20 carbons with as few as two oxygens and would be classified as extremely low volatility organic compounds (ELVOCs).

Multiple new-particle growth pathways observed at the US DOE Southern Great Plains field site

Abstract. New-particle formation (NPF) is a significant source of aerosol particles into the atmosphere. However, these particles are initially too small to have climatic importance and must grow, primarily through net uptake of low-volatility species, from diameters ∼ 1 to 30–100 nm in order to potentially impact climate. There are currently uncertainties in the physical and chemical processes associated with the growth of these freshly formed particles that lead to uncertainties in aerosol-climate modeling. Four main pathways for new-particle growth have been identified: condensation of sulfuric-acid vapor (and associated bases when available), condensation of organic vapors, uptake of organic acids through acid–base chemistry in the particle phase, and accretion of organic molecules in the particle phase to create a lower-volatility compound that then contributes to the aerosol mass. The relative importance of each pathway is uncertain and is the focus of this work. The 2013 New Particle Formation Study (NPFS) measurement campaign took place at the DOE Southern Great Plains (SGP) facility in Lamont, Oklahoma, during spring 2013. Measured gas- and particle-phase compositions during these new-particle growth events suggest three distinct growth pathways: (1) growth by primarily organics, (2) growth by primarily sulfuric acid and ammonia, and (3) growth by primarily sulfuric acid and associated bases and organics. To supplement the measurements, we used the particle growth model MABNAG (Model for Acid–Base chemistry in NAnoparticle Growth) to gain further insight into the growth processes on these 3 days at SGP. MABNAG simulates growth from (1) sulfuric-acid condensation (and subsequent salt formation with ammonia or amines), (2) near-irreversible condensation from nonreactive extremely low-volatility organic compounds (ELVOCs), and (3) organic-acid condensation and subsequent salt formation with ammonia or amines. MABNAG is able to corroborate the observed differing growth pathways, while also predicting that ELVOCs contribute more to growth than organic salt formation. However, most MABNAG model simulations tend to underpredict the observed growth rates between 10 and 20 nm in diameter; this underprediction may come from neglecting the contributions to growth from semi-to-low-volatility species or accretion reactions. Our results suggest that in addition to sulfuric acid, ELVOCs are also very important for growth in this rural setting. We discuss the limitations of our study that arise from not accounting for semi- and low-volatility organics, as well as nitrogen-containing species beyond ammonia and amines in the model. Quantitatively understanding the overall budget, evolution, and thermodynamic properties of lower-volatility organics in the atmosphere will be essential for improving global aerosol models.

Organic Nitrate Contribution to New Particle Formation and Growth in Secondary Organic Aerosols from α-Pinene Ozonolysis.

The chemical kinetics of organic nitrate production during new particle formation and growth of secondary organic aerosols (SOA) were investigated using the short-lived radioactive tracer (13)N in flow-reactor studies of α-pinene oxidation with ozone. Direct and quantitative measurements of the nitrogen content indicate that organic nitrates accounted for ∼40% of SOA mass during initial particle formation, decreasing to ∼15% upon particle growth to the accumulation-mode size range (>100 nm). Experiments with OH scavengers and kinetic model results suggest that organic peroxy radicals formed by α-pinene reacting with secondary OH from ozonolysis are key intermediates in the organic nitrate formation process. The direct reaction of α-pinene with NO3 was found to be less important for particle-phase organic nitrate formation. The nitrogen content of SOA particles decreased slightly upon increase of relative humidity up to 80%. The experiments show a tight correlation between organic nitrate content and SOA particle-number concentrations, implying that the condensing organic nitrates are among the extremely low volatility organic compounds (ELVOC) that may play an important role in the nucleation and growth of atmospheric nanoparticles.

Detection of dimethylamine in the low pptv range using nitrate chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometry

Abstract. Amines are potentially important for atmospheric new particle formation, but their concentrations are usually low with typical mixing ratios in the pptv range or even smaller. Therefore, the demand for highly sensitive gas-phase amine measurements has emerged in the last several years. Nitrate chemical ionization mass spectrometry (CIMS) is routinely used for the measurement of gas-phase sulfuric acid in the sub-pptv range. Furthermore, extremely low volatile organic compounds (ELVOCs) can be detected with a nitrate CIMS. In this study we demonstrate that a nitrate CIMS can also be used for the sensitive measurement of dimethylamine (DMA, (CH3)2NH) using the NO3−•(HNO3)1 − 2• (DMA) cluster ion signal. Calibration measurements were made at the CLOUD chamber during two different measurement campaigns. Good linearity between 0 and ∼ 120 pptv of DMA as well as a sub-pptv detection limit of 0.7 pptv for a 10 min integration time are demonstrated at 278 K and 38 % RH.

Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: competition among oligomerization, functionalization, and fragmentation

Abstract. Organic aerosol is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical reactions. Understanding these reactions is important for a predictive understanding of atmospheric aging of aerosols and their impacts on climate, air quality, and human health. In this study, we investigate the chemical evolution of aqueous secondary organic aerosol (aqSOA) formed during reactions of phenolic compounds with two oxidants – the triplet excited state of an aromatic carbonyl (3C∗) and hydroxyl radical (•OH). Changes in the molecular composition of aqSOA as a function of aging time are characterized using an offline nanospray desorption electrospray ionization mass spectrometer (nano-DESI MS) whereas the real-time evolution of SOA mass, elemental ratios, and average carbon oxidation state (OSC) are monitored using an online aerosol mass spectrometer (AMS). Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation equivalent to ∼ 2 h irradiation under midday winter solstice sunlight in Northern California. At later reaction times functionalization (i.e., adding polar oxygenated functional groups to the molecule) and fragmentation (i.e., breaking of covalent bonds) become more important processes, forming a large variety of functionalized aromatic and open-ring products with higher OSC values. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated ring-opening molecules with carbon numbers (nC) below 6. The average nC of phenolic aqSOA decreases while average OSC increases over the course of photochemical aging. In addition, the saturation vapor pressures (C∗) of dozens of the most abundant phenolic aqSOA molecules are estimated. A wide range of C∗ values is observed, varying from < 10−20 µg m−3 for functionalized phenolic oligomers to > 10 µg m−3 for small open-ring species. The detection of abundant extremely low-volatile organic compounds (ELVOC) indicates that aqueous reactions of phenolic compounds are likely an important source of ELVOC in the atmosphere.

Characterization of the mass-dependent transmission efficiency of a CIMS

Abstract. Knowledge about mass discrimination effects in a chemical ionization mass spectrometer (CIMS) is crucial for quantifying, e.g., the recently discovered extremely low volatile organic compounds (ELVOCs) and other compounds for which no calibration standard exists so far. Here, we present a simple way of estimating mass discrimination effects of a nitrate-based chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometer. Characterization of the mass discrimination is achieved by adding different perfluorinated acids to the mass spectrometer in amounts sufficient to deplete the primary ions significantly. The relative transmission efficiency can then be determined by comparing the decrease of signals from the primary ions and the increase of signals from the perfluorinated acids at higher masses. This method is in use already for PTR-MS; however, its application to a CI-APi-TOF brings additional difficulties, namely clustering and fragmentation of the measured compounds, which can be treated with statistical analysis of the measured data, leading to self-consistent results. We also compare this method to a transmission estimation obtained with a setup using an electrospray ion source, a high-resolution differential mobility analyzer and an electrometer, which estimates the transmission of the instrument without the CI source. Both methods give different transmission curves, indicating non-negligible mass discrimination effects of the CI source. The absolute transmission of the instrument without the CI source was estimated with the HR-DMA method to plateau between the m∕z range of 127 and 568 Th at around 1.5 %; however, for the CI source included, the depletion method showed a steady increase in relative transmission efficiency from the m∕z range of the primary ion (mainly at 62 Th) to around 550 Th by a factor of around 5. The main advantages of the depletion method are that the instrument is used in the same operation mode as during standard measurements and no knowledge of the absolute amount of the measured substance is necessary, which results in a simple setup.