Particle wall-loss correction methods in smog chamber experiments

The interaction of particles with the chamber walls has been a significant source of uncertainty when analyzing results of secondary organic aerosol (SOA) formation experiments performed in Teflon chambers. A number of particle wall-loss correction methods have been proposed including the use of a size-independent loss rate constant, the ratio of suspended organic mass to that of a conserved tracer (e.g., sulfate seeds), and a size-dependent loss rate constant, etc. For complex experiments such as the chemical aging of SOA, the results of the SOA quantification analysis can be quite sensitive to the adopted correction method due to the evolution of the particle size distribution and the duration of these experiments. We evaluated the performance of several particle wall-loss correction methods for aging experiments of α-pinene ozonolysis products. Determining the loss rates from seed loss periods is necessary for this system because it is not clear when chemical reactions have been completed. Results from the OA&thinsp;∕&thinsp;sulfate ratio and the size-independent correction methods can be influenced significantly by the size dependence of the particle wall-loss process. Coagulation can also affect the particle size distribution, especially for particles with diameter less than 100&thinsp;nm, thus introducing errors in the results of the wall-loss correction. The corresponding loss rate constants may vary from experiment to experiment, and even during a specific experiment. Friction between the Teflon chamber walls and non-conductive surfaces can significantly increase particle wall-loss rates and the chamber may require weeks to recover to its original condition. Experimental procedures are proposed for the characterization of particle losses during different stages of these experiments and the evaluation of corresponding particle wall-loss correction.</p

Simulating the oxygen content of ambient organic aerosol with the 2D volatility basis set

A module predicting the oxidation state of organic aerosol (OA) has been developed using the two-dimensional volatility basis set (2D-VBS) framework. This model is an extension of the 1D-VBS framework and tracks saturation concentration and oxygen content of organic species during their atmospheric lifetime. The host model, a one-dimensional Lagrangian transport model, is used to simulate air parcels arriving at Finokalia, Greece during the Finokalia Aerosol Measurement Experiment in May 2008 (FAME-08). Extensive observations were collected during this campaign using an aerosol mass spectrometer (AMS) and a thermodenuder to determine the chemical composition and volatility, respectively, of the ambient OA. Although there are several uncertain model parameters, the consistently high oxygen content of OA measured during FAME-08 (O:C = 0.8) can help constrain these parameters and elucidate OA formation and aging processes that are necessary for achieving the high degree of oxygenation observed. The base-case model reproduces observed OA mass concentrations (measured mean = 3.1 μg m&lt;sup&gt;&amp;minus;3&lt;/sup&gt;, predicted mean = 3.3 μg m&lt;sup&gt;&amp;minus;3&lt;/sup&gt;) and O:C (predicted O:C = 0.78) accurately. A suite of sensitivity studies explore uncertainties due to (1) the anthropogenic secondary OA (SOA) aging rate constant, (2) assumed enthalpies of vaporization, (3) the volatility change and number of oxygen atoms added for each generation of aging, (4) heterogeneous chemistry, (5) the oxidation state of the first generation of compounds formed from SOA precursor oxidation, and (6) biogenic SOA aging. Perturbations in most of these parameters do impact the ability of the model to predict O:C well throughout the simulation period. By comparing measurements of the O:C from FAME-08, several sensitivity cases including a high oxygenation case, a low oxygenation case, and biogenic SOA aging case are found to unreasonably depict OA aging, keeping in mind that this study does not consider possibly important processes like fragmentation that may offset mass gains and affect the prediction bias. On the other hand, many of the cases chosen for this study predict average O:C estimates that are consistent with the observations, illustrating the need for more thorough experimental characterizations of OA parameters including the enthalpy of vaporization and oxidation state of the first generation of SOA products. The ability of the model to predict OA concentrations is less sensitive to perturbations in the model parameters than its ability to predict O:C. In this sense, quantifying O:C with a predictive model and constraining it with AMS measurements can reduce uncertainty in our understanding of OA formation and aging

Positive matrix factorization of organic aerosol: insights from a chemical transport model

Factor analysis of aerosol mass spectrometer measurements (organic aerosol mass spectra) is often used to determine the sources of organic aerosol (OA). In this study we aim to gain insights regarding the ability of positive matrix factorization (PMF) to identify and quantify the OA sources accurately. We performed PMF and multilinear engine (ME-2) analysis on the predictions of a state-of-the-art chemical transport model (PMCAMx-SR, Particulate Matter Comprehensive Air Quality Model with extensions – source resolved) during a photochemically active period for specific sites in Europe in an effort to interpret the diverse factors usually identified by PMF analysis of field measurements. Our analysis used the predicted concentrations of 27 OA components, assuming that each of them is “chemically different” from the others. The PMF results based on the chemical transport model predictions are quite consistent (same number of factors and source types) with those of the analysis of AMS measurements. The estimated uncertainty of the contribution of fresh biomass burning is less than 30&thinsp;% and of the other primary sources less than 40&thinsp;%, when these sources contribute more than 20&thinsp;% to the total OA. The PMF uncertainty increases for smaller source contributions, reaching a factor of 2 or even 3 for sources which contribute less than 10&thinsp;% to the OA. One of the major questions in PMF analysis of AMS measurements concerns the sources of the two or more oxygenated OA (OOA) factors often reported in field studies. Our analysis suggests that these factors include secondary OA compounds from a variety of anthropogenic and biogenic sources and do not correspond to specific sources. Their characterization in the literature as low- and high-volatility factors is probably misleading, because they have overlapping volatility distributions. However, the average volatility of the one often characterized as a low-volatility factor is indeed lower than that of the other (high-volatility factor). Based on the analysis of the PMCAMx-SR predictions, the first oxygenated OA factor includes mainly highly aged OA transported from outside Europe, but also highly aged secondary OA from precursors emitted in Europe. The second oxygenated OA factor contains fresher secondary organic aerosol from volatile, semivolatile, and intermediate volatility anthropogenic and biogenic organic compounds. The exact contribution of these OA components to each OA factor depends on the site and the prevailing meteorology during the analysis period.</p

Contribution of intermediate-volatility organic compounds from on-road transport to secondary organic aerosol levels in Europe

Atmospheric organic compounds with an effective saturation concentration (C∗) at 298 K between 103 and 106 µg m−3 are called intermediate-volatility organic compounds (IVOCs), and they have been identified as important secondary organic aerosol (SOA) precursors. In this work, we simulate IVOCs emitted from on-road diesel and gasoline vehicles over Europe with a chemical transport model (CTM), utilizing a new approach in which IVOCs are treated as lumped species that preserve their chemical characteristics. This approach allows us to assess both the overall contribution of IVOCs to SOA formation and the role of specific compounds. For the simulated early-summer period, the highest concentrations of SOA formed from the oxidation of on-road IVOCs (SOA-iv) are predicted for major European cities, like Paris, Athens, and Madrid. In these urban environments, on-road SOA-iv can account for up to a quarter of the predicted total SOA. Over Europe, unspeciated cyclic alkanes in the IVOC range are estimated to account for up to 72 % of the total on-road SOA-iv mass, with compounds with 15 to 20 carbons being the most prominent precursors. The sensitivity of the predicted SOA-iv concentrations to the selected parameters of the new lumping scheme is also investigated. Active multigenerational aging of the secondary aerosol products has the most significant effect as it increases the predicted SOA-iv concentrations by 67 %.</p

Size-resolved CCN distributions and activation kinetics of aged continental and marine aerosol

We present size-segregated measurements of cloud condensation nucleus (CCN) activity of aged aerosol sampled at Finokalia, Crete, during the Finokalia Aerosol Measurement Experiment of summer 2007 (FAME07). From analysis of the data, hygroscopicity and activation kinetics distributions are derived. The CCN are found to be highly hygroscopic, (expressed by a size- and time- averaged hygroscopicity parameter &amp;kappa; &amp;sim; 0.22), with the majority of particles activating at ~0.5–0.6 % supersaturation. Air masses originating from Central-Eastern Europe tend to be associated with higher CCN concentrations and slightly lower hygroscopicity (&amp;kappa; &amp;sim; 0.18) than for other airmass types. The particles were always well mixed, as reflected by the high activation ratios and narrow hygroscopicity distribution widths. Smaller particles (~40 nm) were found to be more hygroscopic (~0.1κ units higher) than the larger ones (~100 nm). The particles with diameters less than 80 nm exhibited a diurnal hygroscopicity cycle (with κ peaking at ~14 h local time), consistent with photochemical aging and volatilization of less hygroscopic material from the aerosol. Use of bulk chemical composition and the aerosol number distribution results in excellent CCN closure when applying Köhler theory in its simplest form. Using asymptotic and threshold droplet growth analysis, the "aged" organics present in the aerosol were found not to suppress or delay the water uptake kinetics of particles in this environment

A simple model to estimate atmospheric concentrations of aerosol chemical species based on snow core chemistry at Summit, Greenland

A simple model is presented to estimate atmospheric concentrations of chemical species that exist primarily as aerosols based on snow core/ice core chemistry at Summit, Greenland. The model considers the processes of snow, fog, and dry deposition. The deposition parameters for each of the processes are estimated for SO42− and Ca2+ and are based on experiments conducted during the 1993 and 1994 summer field seasons. The seasonal mean atmospheric concentrations are estimated based on the deposition parameters and snow cores obtained during the field seasons. The ratios of the estimated seasonal mean airborne concentration divided by the measured mean concentration ( ) for SO42− over the 1993 and 1994 field seasons are 0.85 and 0.95, respectively. The ratios for Ca2+ are 0.45 and 0.90 for the 1993 and 1994 field seasons. The uncertainties in the estimated atmospheric concentrations range from 30% to 40% and are due to variability in the input parameters. The model estimates the seasonal mean atmospheric SO42− and Ca2+ concentrations to within 15% and 55%, respectively. Although the model is not directly applied to ice cores, the application of the model to ice core chemical signals is briefly discussed

Insights into the morphology of multicomponent organic and inorganic aerosols from molecular dynamics simulations

We explore the morphologies of multicomponent nanoparticles through atomistic molecular dynamics simulations under atmospherically relevant conditions. The particles investigated consist of both organic (cis-pinonic acid – CPA, 3-methyl-1,2,3-butanetricarboxylic acid – MBTCA, n-C20H42, n-C24H50, n-C30H62 or mixtures thereof) and inorganic (sulfate, ammonium and water) compounds. The effects of relative humidity, organic mass content and type of organic compound present in the nanoparticle are investigated. Phase separation is predicted for almost all simulated nanoparticles either between organics and inorganics or between hydrophobic and hydrophilic constituents. For oxygenated organics, our simulations predict an enrichment of the nanoparticle surface in organics, often in the form of islands depending on the level of humidity and organic mass fraction, giving rise to core–shell structures. In several cases the organics separate from the inorganics, especially from the ions. For particles containing water-insoluble linear alkanes, separate hydrophobic and hydrophilic domains are predicted to develop. The surface partitioning of organics is enhanced as the humidity increases. The presence of organics in the interior of the nanoparticle increases as their overall mass fraction in the nanoparticle increases, but this also depends on the humidity conditions. Apart from the organics–inorganics and hydrophobics–hydrophilics separation, our simulations predict a third type of separation (layering) between CPA and MBTCA molecules under certain conditions.</p

Changes in PM2.5 concentrations and their sources in the US from 1990 to 2010

Significant reductions in emissions of SO2, NOx, volatile organic compounds (VOCs), and primary particulate matter (PM) took place in the US from 1990 to 2010. We evaluate here our understanding of the links between these emissions changes and corresponding changes in concentrations and health outcomes using a chemical transport model, the Particulate Matter Comprehensive Air Quality Model with Extensions (PMCAMx), for 1990, 2001, and 2010. The use of the Particle Source Apportionment Algorithm (PSAT) allows us to link the concentration reductions to the sources of the corresponding primary and secondary PM. The reductions in SO2 emissions (64 %, mainly from electric-generating units) during these 20 years have dominated the reductions in PM2.5, leading to a 45 % reduction in sulfate levels. The predicted sulfate reductions are in excellent agreement with the available measurements. Also, the reductions in elemental carbon (EC) emissions (mainly from transportation) have led to a 30 % reduction in EC concentrations. The most important source of organic aerosol (OA) through the years according to PMCAMx is biomass burning, followed by biogenic secondary organic aerosol (SOA). OA from on-road transport has been reduced by more than a factor of 3. On the other hand, changes in biomass burning OA and biogenic SOA have been modest. In 1990, about half of the US population was exposed to annual average PM2.5 concentrations above 20 µg m−3, but by 2010 this fraction had dropped to practically zero. The predicted changes in concentrations are evaluated against the observed changes for 1990, 2001, and 2010 in order to understand whether the model represents reasonably well the corresponding processes caused by the changes in emissions.This work was supported by the Center for Air, Climate, and Energy Solutions (CACES), which was supported under assistance agreement no. R835873 awarded by the U.S. Environmental Protection Agency and the Horizon-2020 Project REMEDIA of the European Union under grant agreement no. 874753.Peer ReviewedPostprint (published version

The role of sea-salt emissions and heterogeneous chemistry in the air quality of polluted coastal areas

International audienceOpen-ocean and surf-zone sea-salt aerosol (SSA) emissions algorithms are incorporated in the CAMx aerosol model and applied over an area with an extended Archipelago (Greece), with a fine grid nested over the highly populated Attica peninsula. The maximum indirect impact of SSA on PM10 mass (35%) is located over a marine area with moderate SSA production and elevated shipping emissions (central Aegean Sea) where SSA interacts with anthropogenic nitric acid forming sodium nitrate. SSA increases PM10 levels in the Athens city center up to 27% during stable onshore winds. Under such conditions both open-ocean and surf-zone mechanisms contribute to aerosol production over Attica. A hybrid scheme for gas-to-particle mass transfer is necessary for accurately simulating semi-volatile aerosol components when coarse SSA is included. Dynamically simulating mass transfer to the coarse particles leads to a quadrupling of predicted PM10 nitrate in the Athens city center and up to two orders of magnitude in its coarse mass in comparison to using a bulk equilibrium approach

CCN activity and droplet growth kinetics of fresh and aged monoterpene secondary organic aerosol

International audienceThe ability of secondary organic aerosol (SOA) produced from the ozonolysis of ?-pinene and monoterpene mixtures (?-pinene, ?-pinene, limonene and 3-carene) to become cloud droplets was investigated. Monoterpene SOA is quite active and would likely be a good source of cloud condensation nuclei (CCN) in the atmosphere. A static CCN counter and a Scanning Mobility CCN Analyser (a Scanning Mobility Particle Sizer coupled with a Continuous Flow counter) were used for the CCN measurements. A decrease in CCN activation diameter for ?-pinene SOA of approximately 3 nm h?1 was observed as the aerosol continued to react with oxidants. Hydroxyl radicals further oxidize the SOA particles thereby enhancing the particle CCN activity with time. The initial concentrations of ozone and monoterpene precursor (for concentrations lower than 40 ppb) do not appear to affect the activity of the resulting SOA. Köhler Theory Analysis (KTA) is used to infer the molar mass of the SOA sampled online and offline from atomized filter samples. KTA suggests that the aged aerosol (both from ?-pinene and the mixed monoterpene oxidation) is primarily water-soluble (around 70?80%), with an estimated average molar mass of 180±55 g mol?1 (consistent with existing SOA speciation studies). CCN activity measurements of the SOA mixed with (NH4)2SO4 suggest that the organic can depress surface tension by as much as 10 nM m?1 (with respect to pure water). The droplet growth kinetics of SOA samples are similar to (NH4)2SO4, except at low supersaturation, where SOA tends to grow more slowly. The CCN activity of ?-pinene and mixed monoterpene SOA can be modelled by a very simple implementation of Köhler theory, assuming complete dissolution of the particles, no dissociation into ions, molecular weight of 180 g mol?1, density of 1.5 g cm?3, and surface tension to within 10?15% of water