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.

Detecting pH of Sub-Micrometer Aerosol Particles Using Fluorescent Probes.

Acidity is one of the most fundamental properties of atmospheric aerosol particles, influencing both chemical processes and environmental impacts. A couple of methods for measuring the pH of aerosol particles have been developed, yet no approach is currently available for quantifying the pH of suspending submicron particles. We developed an aerosol fluorescence cell (AFC) for quantifying the pH of aerosol particles in a continuous flow. Particles containing fluorescent pH probes (fluorescein and Oregon green 488) were injected into the AFC. Ratiometric analysis of pH for these particles was conducted by alternatively exciting them with two wavelengths of diode lasers (450 and 488 nm). The employment of the two types of fluorescent probes allowed the measurement of pH in the range of 2-7. The pH measurement by the AFC for submicron particles was compared with that measured by using pH indicator papers, providing a reasonably good agreement. Measurement of size-selected particles suggested that the AFC approach is applicable to particles of 80 nm in diameter. In combination with recent developments for analyzing renebulized water-soluble matter samples, we suggest that the AFC method can be applied not only for laboratory standards but also for atmospherically relevant samples in the future.

Water Solubility Distribution of Organic Matter Accounts for the Discrepancy in Hygroscopicity among Sub- and Supersaturated Humidity Regimes.

Water uptake properties of organic matter (OM) are critical for aerosol direct and indirect effects. OM contains various chemical species that have a wide range of water solubility. However, the role of water solubility on water uptake by OM has poorly been investigated. We experimentally retrieved water solubility distributions of water-soluble OM (WSOM) from combustion of mosquito coil and tropical peat using the 1-octanol-water partitioning method. In addition, hygroscopic growth and cloud condensation nuclei (CCN) activity of solubility-segregated WSOM were measured. The dominant fraction of WSOM from mosquito coil smoldering was highly soluble (water solubility (S) > 10-2 g cm-3), while that from peat combustion contained ∼40% of less-soluble species (S < 10-3 g cm-3). The difference in water solubility distributions induced changes in the roles of less water-soluble fractions (S < 10-3 g cm-3) on CCN activity. Namely, the less water-soluble fraction from mosquito coil combustion fully dissolved at the point of critical supersaturation, while that for tropical peat smoldering was limited by water solubility. The present result suggests that water solubility distributions of OM, rather than its bulk chemical property, need to be quantified for understanding the water uptake process.

Global Importance of Hydroxymethanesulfonate in Ambient Particulate Matter: Implications for Air Quality.

Sulfur compounds are an important constituent of particulate matter, with impacts on climate and public health. While most sulfur observed in particulate matter has been assumed to be sulfate, laboratory experiments reveal that hydroxymethanesulfonate (HMS), an adduct formed by aqueous phase chemical reaction of dissolved HCHO and SO2, may be easily misinterpreted in measurements as sulfate. Here we present observational and modeling evidence for a ubiquitous global presence of HMS. We find that filter samples collected in Shijiazhuang, China, and examined with ion chromatography within 9 days show as much as 7.6 µg m-3 of HMS, while samples from Singapore examined 9-18 months after collection reveal ~0.6 µg m-3 of HMS. The Shijiazhuang samples show only minor traces of HMS 4 months later, suggesting that HMS had decomposed over time during sample storage. In contrast, the Singapore samples do not clearly show a decline in HMS concentration over 2 months of monitoring. Measurements from over 150 sites, primarily derived from the IMPROVE network across the United States, suggest the ubiquitous presence of HMS in at least trace amounts as much as 60 days after collection. The degree of possible HMS decomposition in the IMPROVE observations is unknown. Using the GEOS-Chem chemical transport model, we estimate that HMS may account for 10% of global particulate sulfur in continental surface air and over 25% in many polluted regions. Our results suggest that reducing emissions of HCHO and other volatile organic compounds may have a co-benefit of decreasing particulate sulfur.

Microbial communities in the tropical air ecosystem follow a precise diel cycle.

The atmosphere is vastly underexplored as a habitable ecosystem for microbial organisms. In this study, we investigated 795 time-resolved metagenomes from tropical air, generating 2.27 terabases of data. Despite only 9 to 17% of the generated sequence data currently being assignable to taxa, the air harbored a microbial diversity that rivals the complexity of other planetary ecosystems. The airborne microbial organisms followed a clear diel cycle, possibly driven by environmental factors. Interday taxonomic diversity exceeded day-to-day and month-to-month variation. Environmental time series revealed the existence of a large core of microbial taxa that remained invariable over 13 mo, thereby underlining the long-term robustness of the airborne community structure. Unlike terrestrial or aquatic environments, where prokaryotes are prevalent, the tropical airborne biomass was dominated by DNA from eukaryotic phyla. Specific fungal and bacterial species were strongly correlated with temperature, humidity, and CO2 concentration, making them suitable biomarkers for studying the bioaerosol dynamics of the atmosphere.

A Significant Portion of Water-Soluble Organic Matter in Fresh Biomass Burning Particles Does Not Contribute to Hygroscopic Growth: An Application of Polarity Segregation by 1-Octanol-Water Partitioning Method.

The importance of water-soluble organic matter (WSOM) on the hygroscopic growth of particles is recognized, yet roles of different categories of WSOM are under debate. We segregated WSOM from Indonesian biomass burning particles by the 1-octanol-water partitioning method. The method is based on the 1-octanol-water partition coefficient (KOW), which correlates with water solubility. The segregated WSOM was analyzed using the humidified tandem differential mobility analyzer (HTDMA) and time-of-flight aerosol chemical speciation monitor (ToF-ACSM). Both the hygroscopicity parameter κ and the fractional contribution of m/z 44 (f44), which serves as a metric for degree of oxygenation, increased with polarity. This result experimentally evidenced that highly polar/water-soluble OM is highly hygroscopic/oxygenated. Positive matrix factorization (PMF) identified three factors from the ToF-ACSM data. Deconvolution of κ by PMF factors demonstrated that the less polar fractions, which occupy approximately 20-60% of WSOM dependent on the biomass type, almost do not contribute to water uptake under subsaturated conditions. This result highlights that categorization of WSOM will be needed to understand how hygroscopic growth of aerosol particles is regulated.

Polarity-Dependent Chemical Characteristics of Water-Soluble Organic Matter from Laboratory-Generated Biomass-Burning Revealed by 1-Octanol-Water Partitioning.

Polarity distribution of water-soluble organic matter (WSOM) is an important factor in determining the hygroscopic and cloud nucleation abilities of organic aerosol particles. We applied a novel framework to quantitatively classify WSOM based on the 1-octanol-water partition coefficient (KOW), which often serves as a proxy of polarity. In this study, WSOM was generated in a laboratory biomass-burning experiment by smoldering of Indonesian peat and vegetation samples. The fractionated WSOM was analyzed using a UV-visible spectrophotometer, spectrofluorometer, and time-of-flight aerosol chemical speciation monitor. Several deconvolution methods, including positive matrix factorization, parallel factor analysis, and least-squares analysis, were applied to the measured spectra, resulting in three classes of WSOM. The highly polar fraction of WSOM, which predominantly exists in the range of log KOW < 0, is highly oxygenated and exhibits similar optical properties as those of light-absorbing humic-like substances (HULIS, termed after the humic substances due to the similarity in chemical characteristics). WSOM in the least-polar fraction, which mainly distributes in log KOW > 1, mostly consists of hydrocarbon-like and high molecular weight species. In between the most- and least-polar fraction, WSOM in the marginally polar fraction likely contains aromatic compounds. The analyses have also suggested the existence of HULIS with different polarities. Comparison with previous studies indicates that only WSOM in the highly polar fraction (log KOW < 0) likely contributes to water uptake.

Light-Absorbing Brown Carbon Aerosol Constituents from Combustion of Indonesian Peat and Biomass.

Light-absorbing brown carbon (BrC) constituents of organic aerosol (OA) have been shown to significantly absorb ultraviolet (UV) and visible light and thus impact radiative forcing. However, molecular identification of the BrC constituents is still limited. In this study, we characterize BrC constituents at the molecular level in (i) aerosols emitted by combustion of peat, fern/leaf, and charcoal from Indonesia and (ii) ambient aerosols collected in Singapore during the 2015 haze episode. Aerosols were analyzed using ultra performance liquid chromatography instrument interfaced to a diode array detector and electrospray ionization high-resolution quadrupole time-of-flight mass spectrometer operated in the negative ion mode. In the laboratory-generated aerosols, we identified 41 compounds that can potentially absorb near-UV and visible wavelengths, such as oxygenated-conjugated compounds, nitroaromatics, and S-containing compounds. The sum of BrC constituents in peat, fern/leaf, and charcoal burning aerosols are 16%, 35%, and 28% of the OA mass, respectively, giving an average contribution of 24%. On average, the BrC constituents account for 0.4% of the ambient OA mass; however, large uncertainties in mass closure remain because of the lack of authentic standards. This study highlights the potential of light-absorbing BrC OA constituents from peat, fern/leaf, and charcoal burning and their importance in the atmosphere.

Uptake and release of gaseous species accompanying the reactions of isoprene photo-oxidation products with sulfate particles.

Gaseous species produced via the HO2 reaction pathways of isoprene photo-oxidation were reacted with liquid, partially neutralized sulfate aerosol particles at 293 ± 1 K and <5% relative humidity. Isoprene-derived epoxydiols (IEPOX) were taken up for all neutralizations so long as the liquid phase was maintained. By comparison, isoprene-derived hydroperoxides (ISOPOOH) were taken up only for low neutralization (i.e., high acidity). The release of product molecules to the gas phase increased for low neutralization, corresponding to the release of at least 60 product molecules for the uptake of 100 reactant molecules at the lowest neutralization. A major reaction pathway was hydroperoxide cleavage in the particle phase to produce volatile products. Product species larger than the C5 chain of isoprene were also released to the gas phase, implying that some accretion products in the particle phase were sufficiently volatile to partition to the gas phase. The study results show that the dependence of reactive uptake on neutralization varies by species. Furthermore, in addition to functionalization and accretion, decomposition and re-volatilization should be considered in mass balance formulations of reactive uptake by atmospheric particles.

Physical state and acidity of inorganic sulfate can regulate the production of secondary organic material from isoprene photooxidation products.

The production of secondary organic material (SOM) by the reactive uptake of isoprene photooxidation products was investigated using partially to wholly neutralized sulfuric acid particles. The experiments were performed at a relative humidity (RH) of <5% and a temperature of 20 °C. The extent X of neutralization was adjusted from that of sulfuric acid (X = 0) to that of ammonium sulfate (X = 1). Significant SOM production was observed only for X < 0.7. The threshold of 0.7 corresponded to the transition point of the sulfate particles from aqueous to solid for <5% RH. The phase transition of inorganic sulfate therefore regulated the particle-phase reactions that produce isoprene SOM, at least for the investigated conditions. For aqueous particles, a decreasing extent of neutralization was associated with increasing production of SOM, including increased production of oligomers and organosulfates. These results can underpin treatments of phase-dependent SOM production within chemical transport models, thereby improving the accuracy of simulations of biogenic-anthropogenic interactions in the atmosphere and the associated impacts of aerosol particles on climate and air quality.

Uptake of epoxydiol isomers accounts for half of the particle-phase material produced from isoprene photooxidation via the HO2 pathway.

The oxidation of isoprene is a globally significant source of secondary organic material (SOM) of atmospheric particles. The relative importance of different parallel pathways, however, remains inadequately understood and quantified. SOM production from isoprene photooxidation was studied under hydroperoxyl-dominant conditions for <5% relative humidity and at 20 °C in the presence of highly acidic to completely neutralized sulfate particles. Isoprene photooxidation was separated from SOM production by using two continuously mixed flow reactors connected in series and operated at steady state. Two online mass spectrometers separately sampled the gas and particle phases in the reactor outflow. The loss of specific gas-phase species as contributors to the production of SOM was thereby quantified. The produced SOM mass concentration was directly proportional to the loss of isoprene epoxydiol (IEPOX) isomers from the gas phase. IEPOX isomers lost from the gas phase accounted for (46 ± 11)% of the produced SOM mass concentration. The IEPOX isomers comprised (59 ± 21)% (molecular count) of the loss of monitored gas-phase species. The implication is that for the investigated reaction conditions the SOM production pathways tied to IEPOX isomers accounted for half of the SOM mass concentration.

Phase transitions and phase miscibility of mixed particles of ammonium sulfate, toluene-derived secondary organic material, and water.

The phase states of atmospheric particles influence their roles in physicochemical processes related to air quality and climate. The phases of particles containing secondary organic materials (SOMs) are still uncertain, especially for SOMs produced from aromatic precursor gases. In this work, efflorescence and deliquescence phase transitions, as well as phase separation, in particles composed of toluene-derived SOM, ammonium sulfate, and water were studied by hygroscopic tandem differential mobility analysis (HTDMA) and optical microscopy. The SOM was produced in the Harvard Environmental Chamber by photo-oxidation of toluene at chamber relative humidities of <5 and 40%. The efflorescence and deliquescence relative humidities (ERH and DRH, respectively, studied by HTDMA) of ammonium sulfate decreased as the SOM organic fraction ε in the particle increased, dropping from DRH = 80% and ERH = 31% for ε = 0.0 to DRH = 58% and ERH = 0% for ε = 0.8. For ε < 0.2, the DRH and ERH to first approximation did not change with the organic volume fraction. This observation is consistent with independent behaviors for ε < 0.2 of water-infused toluene-derived SOM and aqueous ammonium sulfate, suggesting phase immiscibility between the two. Optical microscopy of particles prepared for ε = 0.12 confirmed phase separation for RH < 85%. For ε from 0.2 to 0.8, the DRH and ERH values steadily decreased, as studied by HTDMA. This result is consistent with one-phase mixing of ammonium sulfate, SOM, and water. Optical microscopy for particles of ε = 0.8 confirmed this result. Within error, increased exposure times of the aerosol in the HTDMA from 0.5 to 30 s affected neither the ERH(ε) nor DRH(ε) curves, implying an absence of kinetic effects on the observations over the studied time scales. For ε > 0.5, the DRH values of ammonium sulfate in mixtures with SOM produced at <5% RH were offset by -3 to -5% RH compared to the results for SOM produced at 40% RH, suggesting differences in SOM chemistry. The observed miscibility gap (i.e., phase separation) between toluene-derived SOM and aqueous ammonium sulfate across a limited range of organic volume fractions differentiates this SOM from previous reports for isoprene-derived SOM of full miscibility and for α-pinene-derived SOM of nearly full immiscibility with aqueous ammonium sulfate.

Viscosity of α-pinene secondary organic material and implications for particle growth and reactivity.

Particles composed of secondary organic material (SOM) are abundant in the lower troposphere. The viscosity of these particles is a fundamental property that is presently poorly quantified yet required for accurate modeling of their formation, growth, evaporation, and environmental impacts. Using two unique techniques, namely a "bead-mobility" technique and a "poke-flow" technique, in conjunction with simulations of fluid flow, the viscosity of the water-soluble component of SOM produced by α-pinene ozonolysis is quantified for 20- to 50-µm particles at 293-295 K. The viscosity is comparable to that of honey at 90% relative humidity (RH), similar to that of peanut butter at 70% RH, and at least as viscous as bitumen at ≤30% RH, implying that the studied SOM ranges from liquid to semisolid or solid across the range of atmospheric RH. These data combined with simple calculations or previous modeling studies are used to show the following: (i) the growth of SOM by the exchange of organic molecules between gas and particle may be confined to the surface region of the particles for RH ≤ 30%; (ii) at ≤30% RH, the particle-mass concentrations of semivolatile and low-volatility organic compounds may be overpredicted by an order of magnitude if instantaneous equilibrium partitioning is assumed in the bulk of SOM particles; and (iii) the diffusivity of semireactive atmospheric oxidants such as ozone may decrease by two to five orders of magnitude for a drop in RH from 90% to 30%. These findings have possible consequences for predictions of air quality, visibility, and climate.

Phase of atmospheric secondary organic material affects its reactivity.

The interconversion of atmospheric organic particles among solid, semisolid, and liquid phases is of keen current scientific interest, especially for particles of secondary organic material (SOM). Herein, the influence of phase on ammonia uptake and subsequent particle-phase reactions was investigated for aerosol particles of adipic acid and α-pinene ozonolysis SOM. The nitrogen content of the particles was monitored by online mass spectrometry for increasing ammonia exposure. Solid and semisolid adipic acid particles were inert to the ammonia uptake for low RH (< 5%). For the solid particles, ammonia exposure at high relative humidity (RH; > 94%) induced a first-order deliquescence phase transition into aqueous particles. Solid particles exposed to supersaturated (RH > 100%) conditions and cycled back to high RH (> 94%), thereby becoming acidic metastable particles, underwent a gradual second-order transition upon ammonia exposure to form aqueous, partially neutralized particles. For α-pinene SOM, ammonia exposure at low RH increased the particle-phase ammonium content by a small amount. Mass spectrometric observations suggest a mechanism of neutralization and co-condensation of acidic gas-phase species, consistent with a highly viscous semisolid upon which adsorption occurs. At high RH the ammonium content increased greatly, indicative of rapid diffusion and absorption in a liquid environment. The mass spectra indicated the production of organonitrogen compounds, possibly by particle-phase reactive chemistry. The present results demonstrate that phase can be a key regulator of the reactivity of atmospheric SOM particles.

Using elemental ratios to predict the density of organic material composed of carbon, hydrogen, and oxygen.

A governing equation was developed to predict the density ρ(org) of organic material composed of carbon, oxygen, and hydrogen using the elemental ratios O:C and H:C as input parameters: ρ(org) = 1000 [(12 + 1(H:C) + 16(O:C)]/[7.0 + 5.0(H:C) + 4.15(O:C)] valid for 750 < ρ(org) < 1900 kg m(-3). Comparison of the actual to predicted ρ(org) values shows that the developed equation has an accuracy of 12% for more than 90% of the 31 atmospherically relevant compounds used in the training set. The equation was further validated for secondary organic material (SOM) produced by isoprene photo-oxidation and by α-pinene ozonolysis. Depending on the conditions of SOM production, ρ(org/SOM) ranged from 1230 to 1460 kg m(-3), O:C ranged from 0.38 to 0.72, and H:C ranged from 1.40 to 1.86. Atmospheric chemistry models that simulate particle production and growth can employ the developed equation to simulate particle physical properties. The equation can also extend atmospheric measurements presented as van Krevelen diagrams to include estimates of the material density of particles and their components. Use of the equation, however, is restricted to particle components having negligible quantities of additional elements, most notably nitrogen.

Cloud condensation nuclei (CCN) activity and oxygen-to-carbon elemental ratios following thermodenuder treatment of organic particles grown by α-pinene ozonolysis.

The effects of thermodenuder treatment on the cloud condensation nuclei (CCN) activity and elemental composition of organic particles grown by α-pinene ozonolysis were investigated. The secondary organic material (SOM) was produced in a continuous-flow chamber, with steady-state organic particle mass concentrations M(org) ranging from 1.4 to 37 µg m(-3). Particles exiting in the outflow were heated to temperatures T of up to 100 °C in a thermodenuder. The oxygen-to-carbon (O:C) and hydrogen-to-carbon (H:C) ratios were measured by on-line mass spectrometry. The observed elemental ratios were fit by a linear function, given by (H:C) = -0.8 (O:C) +1.8 for 0.38 < O:C < 0.50. This fit included the dependence on both M(org) and T, meaning that the single variable of post-thermodenuder M(org) was sufficient as an accurate predictor for O:C(M(org)(T)) and H:C(M(org)(T)). This result suggests that equilibrium partitioning theory largely governed the initial volatilization in the thermodenuder. By comparison, the CCN activity had a different dependence on thermodenuder treatment. At 25 °C, the CCN activity was independent of M(org), having an effective hygroscopicity parameter κ(org) of 0.103 ± 0.002. At 100 °C, however, κ(org) varied from 0.105 for M(org) = 1.4 µg m(-3) to 0.079 for M(org) = 37 µg m(-3), indicating that for high mass concentration the CCN activity decreased with heat treatment. The interpretation is that the oligomer fraction of the SOM increased at elevated T, both because of particle-phase reactions that produced oligomers under those conditions and because of the relative enrichment of lower-volatility oligomers in the SOM accompanying the evaporation of higher-volatility monomers from the SOM. Oligomers have high effective molecular weights and thereby significantly influence CCN activity. The production rates of different types of oligomers depend on the types and concentrations of functional groups present in the SOM, which in turn are strongly influenced by M(org). We conclude with a hypothesis, which is supported by a detailed molecular kinetic model, that the changes in κ(org) at high T were more significant at high compared to low M(org) because particle-phase SOM at high M(org) contained a mix of functional groups favorable to oligomerization, such as carbonyl groups.