Aqueous production of secondary organic aerosol from fossil-fuel emissions in winter Beijing haze.

Secondary organic aerosol (SOA) produced by atmospheric oxidation of primary emitted precursors is a major contributor to fine particulate matter (PM2.5) air pollution worldwide. Observations during winter haze pollution episodes in urban China show that most of this SOA originates from fossil-fuel combustion but the chemical mechanisms involved are unclear. Here we report field observations in a Beijing winter haze event that reveal fast aqueous-phase conversion of fossil-fuel primary organic aerosol (POA) to SOA at high relative humidity. Analyses of aerosol mass spectra and elemental ratios indicate that ring-breaking oxidation of POA aromatic species, leading to functionalization as carbonyls and carboxylic acids, may serve as the dominant mechanism for this SOA formation. A POA origin for SOA could explain why SOA has been decreasing over the 2013-2018 period in response to POA emission controls even as emissions of volatile organic compounds (VOCs) have remained flat.

Accounting for Cloud Nucleation Activation Mechanism of Secondary Organic Matter from α-Pinene Oxidation Using Experimentally Retrieved Water Solubility Distributions.

Activation of cloud droplets of aerosol particles from biogenic precursors plays a critical role in Earth's climate system. However, the molecular-level understanding of the cloud condensation nuclei (CCN) activation process for secondary organic matter (SOM) is still lacking. Here, we reduced the gap by segregating SOM from α-pinene based on water solubility. The chemical composition and CCN activity of the solubility-segregated fractions of SOM were measured. The results demonstrated for the first time by laboratory experiment that highly oxygenated compounds such as hydroperoxides and highly oxygenated organic molecules are important contributors for the CCN activity of α-pinene SOM. Meanwhile, relatively less water-soluble species were also abundant. Analysis based on the Köhler theory demonstrated that less water-soluble compounds in SOM remain undissolved during the cloud activation process, suggesting that the traditional single-parameter parameterization for CCN activation would not be sufficient for representing the process. In combination with the recent developments in SOM formation chemistry, the present study helps in understanding the interactions between the biosphere and climate.

Chemical Signatures of Seasonally Unique Anthropogenic Influences on Organic Aerosol Composition in the Central Amazon.

Urbanization and fires perturb the quantities and composition of fine organic aerosol in the central Amazon, with ramifications for radiative forcing and public health. These disturbances include not only direct emissions of particulates and secondary organic aerosol (SOA) precursors but also changes in the pathways through which biogenic precursors form SOA. The composition of ambient organic aerosol is complex and incompletely characterized, encompassing millions of potential structures relatively few of which have been synthesized and characterized. Through analysis of submicron aerosol samples from the Green Ocean Amazon (GoAmazon2014/5) field campaign by two-dimensional gas chromatography coupled with machine learning, ∼1300 unique compounds were traced and characterized over two seasons. Fires and urban emissions produced chemically and interseasonally distinct impacts on product signatures, with only ∼50% of compounds observed in both seasons. Seasonally unique populations point to the importance of aqueous processing in Amazonian aerosol aging, but further mechanistic insights are impeded by limited product identity knowledge. Less than 10% of compounds were identifiable at an isomer-specific level. Overall, the findings (i) provide compositional characterization of anthropogenic influence on submicron organic aerosol in the Amazon, (ii) identify key season-to-season differences in chemical signatures, and (iii) highlight high-priority knowledge gaps in current speciated knowledge.

Size Dependence of Liquid-Liquid Phase Separation by in Situ Study of Flowing Submicron Aerosol Particles.

Liquid-liquid phase separation (LLPS) of atmospheric particles impacts a range of atmospheric processes. Driven by thermodynamics, LLPS occurs in mixed organic-inorganic particles when high inorganic salt concentrations exclude organic compounds, which develop into a separate phase. The effect of particle size on the thermodynamic and kinetic drivers of LLPS, however, remains incompletely understood. Here, the size dependence was studied for the separation relative humidity (SRH) of LLPS. Submicron organic-inorganic aerosol particles of ammonium sulfate mixed with 1,2,6-hexanetriol and polyethylene glycol (PEG) were studied. In a flow configuration, upstream size selection was coupled to a downstream fluorescence aerosol flow tube (F-AFT) at 293 ± 1 K. For both mixed particle types, the SRH values for submicron particle diameters of 260-410 nm agreed with previous measurements reported in the literature for supermicron particles. For smaller particles, the SRH values decreased by approximately 5% RH for diameters of 130-260 nm for PEG-sulfate particles and of 70-190 nm for hexanetriol-sulfate particles. From these observations, the nucleation rate in the hexanetriol-sulfate system was constrained, implying an activation barrier to nucleation of +1.4 to +2.0 × 10-19 J at 70% RH and 293 K. Quantifying the activation barrier is an approach for predicting size-dependent LLPS in the atmosphere.

Partitioning of Organonitrates in the Production of Secondary Organic Aerosols from α-Pinene Photo-Oxidation.

The chemical pathways for the production of secondary organic aerosols (SOA) are influenced by the concentration of nitrogen oxides (NOx), including the production of organonitrates (ON). Herein, a series of experiments conducted in an environmental chamber investigated the production and partitioning of total organonitrates from α-pinene photo-oxidation from <1 to 24 ppb NOx. Gas-phase and particle-phase organonitrates (gON and pON, respectively) were measured by laser-induced fluorescence (LIF). The composition of the particle phase and the particle mass concentration were simultaneously characterized by online aerosol mass spectrometry. The LIF and MS measurements of pON concentrations had a Pearson correlation coefficient of 0.91 from 0.3 to 1.1 µg m-3. For 1-6 ppb NOx, the yield of SOA particle mass concentration increased from 0.02 to 0.044 with NOx concentration. For >6 ppb NOx, the yield steadily dropped, reaching 0.034 at 24 ppb NOx. By comparison, the yield of pON steadily increased from 0.002 to 0.022 across the range of investigated NOx concentrations. The yield of gON likewise increased from 0.005 to 0.148. The gas-to-particle partitioning ratio (pON/(pON + gON)) depended strongly on the NOx concentration, changing from 0.27 to 0.13 as the NOx increased from <1 to 24 ppb. In the atmosphere, there is typically a cross-over point between clean and polluted conditions that strongly affects SOA production, and the results herein quantitatively identify 6 ppb NOx as that point for α-pinene photo-oxidation under these study conditions, including the production and partitioning of organonitrates. The trends in SOA yield and partitioning ratio as a function of NOx occur because of the changes in pON volatility.

Phase Behavior of Internal Mixtures of Hydrocarbon-like Primary Organic Aerosol and Secondary Aerosol Based on Their Differences in Oxygen-to-Carbon Ratios.

The phase behavior, the number and type of phases, in atmospheric particles containing mixtures of hydrocarbon-like organic aerosol (HOA) and secondary organic aerosol (SOA) is important for predicting their impacts on air pollution, human health, and climate. Using a solvatochromic dye and fluorescence microscopy, we determined the phase behavior of 11 HOA proxies (O/C = 0-0.29) each mixed with 7 different SOA materials generated in environmental chambers (O/C 0.4-1.08), where O/C represents the average oxygen-to-carbon atomic ratio. Out of the 77 different HOA + SOA mixtures studied, we observed two phases in 88% of the cases. The phase behavior was independent of relative humidity over the range between 90% and <5%. A clear trend was observed between the number of phases and the difference between the average O/C ratios of the HOA and SOA components (ΔO/C). Using a threshold ΔO/C of 0.265, we were able to predict the phase behavior of 92% of the HOA + SOA mixtures studied here, with one-phase particles predicted for ΔO/C < 0.265 and two-phase particles predicted for ΔO/C ≥ 0.265. The threshold ΔO/C value provides a relatively simple and computationally inexpensive framework for predicting the number of phases in internal SOA and HOA mixtures in atmospheric models.

River Winds and Transport of Forest Volatiles in the Amazonian Riparian Ecoregion.

Volatile organic compounds (VOCs) emitted from forests are important chemical components that affect ecosystem functioning, atmospheric chemistry, and regional climate. Temperature differences between a forest and an adjacent river can induce winds that influence VOC fate and transport. Quantitative observations and scientific understanding, however, remain lacking. Herein, daytime VOC datasets were collected from the surface up to 500 m over the "Rio Negro" river in Amazonia. During time periods of river winds, isoprene, α-pinene, and ß-pinene concentrations increased by 50, 60, and 80% over the river, respectively. The concentrations at 500 m were up to 80% greater compared to those at 100 m because of the transport path of river winds. By comparison, the concentration of methacrolein, a VOC oxidation product, did not depend on river winds or height. The differing observations for primary emissions and oxidation products can be explained by the coupling of timescales among emission, reaction, and transport. This behavior was captured in large-eddy simulations with a coupled chemistry model. The observed and simulated roles of river winds in VOC fate and transport highlight the need for improved representation of these processes in regional models of air quality and chemistry-climate coupling.

Amazon boundary layer aerosol concentration sustained by vertical transport during rainfall.

The nucleation of atmospheric vapours is an important source of new aerosol particles that can subsequently grow to form cloud condensation nuclei in the atmosphere. Most field studies of atmospheric aerosols over continents are influenced by atmospheric vapours of anthropogenic origin (for example, ref. 2) and, in consequence, aerosol processes in pristine, terrestrial environments remain poorly understood. The Amazon rainforest is one of the few continental regions where aerosol particles and their precursors can be studied under near-natural conditions, but the origin of small aerosol particles that grow into cloud condensation nuclei in the Amazon boundary layer remains unclear. Here we present aircraft- and ground-based measurements under clean conditions during the wet season in the central Amazon basin. We find that high concentrations of small aerosol particles (with diameters of less than 50 nanometres) in the lower free troposphere are transported from the free troposphere into the boundary layer during precipitation events by strong convective downdrafts and weaker downward motions in the trailing stratiform region. This rapid vertical transport can help to maintain the population of particles in the pristine Amazon boundary layer, and may therefore influence cloud properties and climate under natural conditions.

Intermediate-scale horizontal isoprene concentrations in the near-canopy forest atmosphere and implications for emission heterogeneity.

The emissions, deposition, and chemistry of volatile organic compounds (VOCs) are thought to be influenced by underlying landscape heterogeneity at intermediate horizontal scales of several hundred meters across different forest subtypes within a tropical forest. Quantitative observations and scientific understanding at these scales, however, remain lacking, in large part due to a historical absence of canopy access and suitable observational approaches. Herein, horizontal heterogeneity in VOC concentrations in the near-canopy atmosphere was examined by sampling from an unmanned aerial vehicle (UAV) flown horizontally several hundred meters over the plateau and slope forests in central Amazonia during the morning and early afternoon periods of the wet season of 2018. Unlike terpene concentrations, the isoprene concentrations in the near-canopy atmosphere over the plateau forest were 60% greater than those over the slope forest. A gradient transport model constrained by the data suggests that isoprene emissions differed by 220 to 330% from these forest subtypes, which is in contrast to a 0% difference implemented in most present-day biosphere emissions models (i.e., homogeneous emissions). Quantifying VOC concentrations, emissions, and other processes at intermediate horizontal scales is essential for understanding the ecological and Earth system roles of VOCs and representing them in climate and air quality models.

Humidity Dependence of the Condensational Growth of α-Pinene Secondary Organic Aerosol Particles.

The influence of relative humidity (RH) on the condensational growth of organic aerosol particles remains incompletely understood. Herein, the RH dependence was investigated via a series of experiments for α-pinene ozonolysis in a continuously mixed flow chamber in which recurring cycles of particle growth occurred every 7 to 8 h at a given RH. In 5 h, the mean increase in the particle mode diameter was 15 nm at 0% RH and 110 nm at 75% RH. The corresponding particle growth coefficients, representing a combination of the thermodynamic driving force and the kinetic resistance to mass transfer, increased from 0.35 to 2.3 nm2 s-1. The chemical composition, characterized by O:C and H:C atomic ratios of 0.52 and 1.48, respectively, and determined by mass spectrometry, did not depend on RH. The Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) was applied to reproduce the observed size- and RH-dependent particle growth by optimizing the diffusivities Db within the particles of the condensing molecules. The Db values increased from 5 α-1 × 10-16 at 0% RH to 2 α-1 × 10-12 cm-2 s-1 at 75% RH for mass accommodation coefficients α of 0.1 to 1.0, highlighting the importance of particle-phase properties in modeling the growth of atmospheric aerosol particles.

Synergistic Uptake by Acidic Sulfate Particles of Gaseous Mixtures of Glyoxal and Pinanediol.

The uptake of gaseous organic species by atmospheric particles can be affected by the reactive interactions among multiple co-condensing species, yet the underlying mechanisms remain poorly understand. Here, the uptake of unary and binary mixtures of glyoxal and pinanediol by neutral and acidic sulfate particles is investigated. These species are important products from the oxidation of volatile organic compounds (VOCs) under atmospheric conditions. The uptake to acidic aerosol particles greatly increased for a binary mixture of glyoxal and pinanediol compared to the unary counterparts. The strength of the synergism depended on the particle acidity and water content (i.e., relative humidity). The greater uptake was up to 2.5× to 8× at 10% relative humidity (RH) for glyoxal and pinanediol, respectively. At 50% RH, it was 2× and 1.2× for the two species. Possible mechanisms of acid-catalyzed cross reactions between the species are proposed to explain the synergistic uptake. The proposed mechanisms are applicable to a broader extent across atmospheric species having carbonyl and hydroxyl functionalities. The results thus suggest that synergistic uptake reactions can be expected to significantly influence the gas-particle partitioning of VOC oxidation products under atmospheric conditions and thus greatly affect their atmospheric transport and lifetime.

Natural and Anthropogenically Influenced Isoprene Oxidation in Southeastern United States and Central Amazon.

Anthropogenic emissions alter secondary organic aerosol (SOA) formation chemistry from naturally emitted isoprene. We use correlations of tracers and tracer ratios to provide new perspectives on sulfate, NOx, and particle acidity influencing isoprene-derived SOA in two isoprene-rich forested environments representing clean to polluted conditions-wet and dry seasons in central Amazonia and Southeastern U.S. summer. We used a semivolatile thermal desorption aerosol gas chromatograph (SV-TAG) and filter samplers to measure SOA tracers indicative of isoprene/HO2 (2-methyltetrols, C5-alkene triols, 2-methyltetrol organosulfates) and isoprene/NOx (2-methylglyceric acid, 2-methylglyceric acid organosulfate) pathways. Summed concentrations of these tracers correlated with particulate sulfate spanning three orders of magnitude, suggesting that 1 µg m-3 reduction in sulfate corresponds with at least ∼0.5 µg m-3 reduction in isoprene-derived SOA. We also find that isoprene/NOx pathway SOA mass primarily comprises organosulfates, ∼97% in the Amazon and ∼55% in Southeastern United States. We infer under natural conditions in high isoprene emission regions that preindustrial aerosol sulfate was almost exclusively isoprene-derived organosulfates, which are traditionally thought of as representative of an anthropogenic influence. We further report the first field observations showing that particle acidity correlates positively with 2-methylglyceric acid partitioning to the gas phase and negatively with the ratio of 2-methyltetrols to C5-alkene triols.

Unified Description of Diffusion Coefficients from Small to Large Molecules in Organic-Water Mixtures.

Diffusion coefficients in mixtures of organic molecules and water are needed for many applications, ranging from the environmental modeling of pollutant transport, air quality, and climate, to improving the stability of foods, biomolecules, and pharmaceutical agents for longer use and storage. The Stokes-Einstein relation has been successful for predicting diffusion coefficients of large molecules in organic-water mixtures from viscosity, yet it routinely underpredicts, by orders of magnitude, the diffusion coefficients of small molecules in organic-water mixtures. Herein, a unified description of diffusion coefficients of large and small molecules in organic-water mixtures, based on the fractional Stokes-Einstein relation, is presented. A fractional Stokes-Einstein relation is able to describe 98% of the observed diffusion coefficients from small to large molecules, roughly within the uncertainties of the measurements. The data set used in the analysis includes a wide range of radii of diffusing molecules, viscosities, and intermolecular interactions. As a case study, we show that the degradation of polycyclic aromatic hydrocarbons (PAHs) by O3 within organic-water particles in the planetary boundary layer is relatively short (≲1 day) when the viscosity of the particle is ≲102 Pa s. We also show that the degradation times predicted using the Stokes-Einstein relation and the fractional Stokes-Einstein relation can differ by up to a factor of 10 in this region of the atmosphere.

Quantifying the Role of the Relative Humidity-Dependent Physical State of Organic Particulate Matter in the Uptake of Semivolatile Organic Molecules.

The uptake of gas-phase dicarboxylic acids to organic particulate matter (PM) was investigated to probe the role of the PM physical state in exchange processes between gas-phase semivolatile organic molecules and organic PM. A homologous series of probe molecules, specifically isotopically labeled 13C-dicarboxylic acids, was used in conjunction with aerosol mass spectrometry to obtain a quantitative characterization of the uptake to organic PM for different relative humidities (RHs). The PM was produced by the dark ozonolysis of unlabeled α-pinene. The uptake of 13C-labeled oxalic, malonic, and α-ketoglutaric acids increased stepwise by 5 to 15 times with increases in RH from 15 to 80%. The enhanced uptake with increasing RH was explained primarily by the higher molecular diffusivity in the particle phase, as associated with changes in the physical state of the organic PM from a nonliquid state to a progressively less-viscous liquid state. At high RH, the partitioning of the probe molecules to the particle phase was more associated with physicochemical interactions with the organic PM than that with the co-absorbed liquid water. Uptake of the probe molecules also increased with a decrease in volatility along the homologous series. This study quantitatively shows the key roles of the particle physical state in governing the interactions of organic PM with semivolatile organic molecules.

Influence of Particle Surface Area Concentration on the Production of Organic Particulate Matter in a Continuously Mixed Flow Reactor.

Organic particulate matter (PM) was produced at different particle surface area concentrations S in a continuously mixed flow reactor (CMFR). The apparent PM yield from the dark ozonolysis of α-pinene increased from 24.5 ± 0.7% to 57.1 ± 0.6% for an increase in S from 0.55 to 2.87 × 103 µm2·surface cm-3·volume. The apparent yield saturated for S > 2.1 × 103 µm2 cm-3. There was hysteresis in the apparent yield for experiments of increasing compared to decreasing S. The relative timescales of gas-particle interactions, gas-wall interactions, and thereby particle-wall cross interactions could explain the results. The PM carbon oxidation state and oxygen-to-carbon atomic ratio decreased from -0.19 to -0.47 and 0.62 to 0.51, respectively, for increasing S, suggesting that greater partitioning of semivolatile organic species into the PM contributed to the increased PM yield. A thorough understanding of the role of gas-wall interactions on apparent PM yield is essential for the extension of laboratory results into predictions of atmospheric PM production, and comparative results from CMFRs and batch reactors can be informative in this regard.

Radical Formation by Fine Particulate Matter Associated with Highly Oxygenated Molecules.

Highly oxygenated molecules (HOMs) play an important role in the formation and evolution of secondary organic aerosols (SOA). However, the abundance of HOMs in different environments and their relation to the oxidative potential of fine particulate matter (PM) are largely unknown. Here, we investigated the relative HOM abundance and radical yield of laboratory-generated SOA and fine PM in ambient air ranging from remote forest areas to highly polluted megacities. By electron paramagnetic resonance and mass spectrometric investigations, we found that the relative abundance of HOMs, especially the dimeric and low-volatility types, in ambient fine PM was positively correlated with the formation of radicals in aqueous PM extracts. SOA from photooxidation of isoprene, ozonolysis of α- and ß-pinene, and fine PM from tropical (central Amazon) and boreal (Hyytiälä, Finland) forests exhibited a higher HOM abundance and radical yield than SOA from photooxidation of naphthalene and fine PM from urban sites (Beijing, Guangzhou, Mainz, Shanghai, and Xi'an), confirming that HOMs are important constituents of biogenic SOA to generate radicals. Our study provides new insights into the chemical relationship of HOM abundance, composition, and sources with the yield of radicals by laboratory and ambient aerosols, enabling better quantification of the component-specific contribution of source- or site-specific fine PM to its climate and health effects.

Increasing Isoprene Epoxydiol-to-Inorganic Sulfate Aerosol Ratio Results in Extensive Conversion of Inorganic Sulfate to Organosulfur Forms: Implications for Aerosol Physicochemical Properties.

Acid-driven multiphase chemistry of isoprene epoxydiols (IEPOX), key isoprene oxidation products, with inorganic sulfate aerosol yields substantial amounts of secondary organic aerosol (SOA) through the formation of organosulfur compounds. The extent and implications of inorganic-to-organic sulfate conversion, however, are unknown. In this article, we demonstrate that extensive consumption of inorganic sulfate occurs, which increases with the IEPOX-to-inorganic sulfate concentration ratio (IEPOX/Sulfinorg), as determined by laboratory measurements. Characterization of the total sulfur aerosol observed at Look Rock, Tennessee, from 2007 to 2016 shows that organosulfur mass fractions will likely continue to increase with ongoing declines in anthropogenic Sulfinorg, consistent with our laboratory findings. We further demonstrate that organosulfur compounds greatly modify critical aerosol properties, such as acidity, morphology, viscosity, and phase state. These new mechanistic insights demonstrate that changes in SO2 emissions, especially in isoprene-dominated environments, will significantly alter biogenic SOA physicochemical properties. Consequently, IEPOX/Sulfinorg will play an important role in understanding the historical climate and determining future impacts of biogenic SOA on the global climate and air quality.

Lability of secondary organic particulate matter.

The energy flows in Earth's natural and modified climate systems are strongly influenced by the concentrations of atmospheric particulate matter (PM). For predictions of concentration, equilibrium partitioning of semivolatile organic compounds (SVOCs) between organic PM and the surrounding vapor has widely been assumed, yet recent observations show that organic PM can be semisolid or solid for some atmospheric conditions, possibly suggesting that SVOC uptake and release can be slow enough that equilibrium does not prevail on timescales relevant to atmospheric processes. Herein, in a series of laboratory experiments, the mass labilities of films of secondary organic material representative of similar atmospheric organic PM were directly determined by quartz crystal microbalance measurements of evaporation rates and vapor mass concentrations. There were strong differences between films representative of anthropogenic compared with biogenic sources. For films representing anthropogenic PM, evaporation rates and vapor mass concentrations increased above a threshold relative humidity (RH) between 20% and 30%, indicating rapid partitioning above a transition RH but not below. Below the threshold, the characteristic time for equilibration is estimated as up to 1 wk for a typically sized particle. In contrast, for films representing biogenic PM, no RH threshold was observed, suggesting equilibrium partitioning is rapidly obtained for all RHs. The effective diffusion rate Dorg for the biogenic case is at least 103 times greater than that of the anthropogenic case. These differences should be accounted for in the interpretation of laboratory data as well as in modeling of organic PM in Earth's atmosphere.

Isoprene photochemistry over the Amazon rainforest.

Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO2) to dominantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK + MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4-0.6. This result implies a ratio of the reaction rate of ISOPOO with HO2 to that with NO of approximately unity. A value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (<60 ppt). This abrupt shift in isoprene photooxidation, sparked by human activities, speaks to ongoing and possible future changes in the photochemistry active over the Amazon rainforest.

Influence of Particle Physical State on the Uptake of Medium-Sized Organic Molecules.

The uptake of medium-sized levoglucosan and 2,4-dinitrophenol to organic particles produced by α-pinene ozonolysis and to ammonium sulfate particles was studied from 10% to >95% relative humidity (RH). For aqueous sulfate particles, the water-normalized gas-particle partitioning coefficient of levoglucosan decreased from (1.0 ± 0.1) × 10-3 to (0.2 ± 0.1) × 10-3 (ng µg-1)particle/(ng m-3)gas from 40% to >95% RH, suggestive of a salting-in mechanism between levoglucosan and ionic ammonium sulfate solutions. For the organic particles, the levoglucosan partitioning coefficient increased from 10% to 40% RH and became invariant at (2.0 ± 0.4) × 10-3 (ng µg-1)/(ng m-3) above 40% RH. A kinetic limitation on uptake below 40% RH was implied, compared to a thermodynamic regime above 40% RH. The estimated diffusivity was 10-19±0.05 m2 s-1 at 40% RH. By comparison, the uptake of 2,4-dinitrophenol onto the organic particles was below detection limit, implying an upper limit on the partitioning coefficient of 6.8 × 10-6 (ng µg-1)/(ng m-3) at 80% RH. The results highlight that the molecular uptake of gases onto particles can be regulated by both kinetic and thermodynamic factors, either of which can limit the uptake of medium-sized organic molecules by atmospherically relevant particles.