Particle-phase Water Research Articles

Effect of Relative Humidity on Secondary Brown Carbon Formation in Aqueous Droplets.

Atmospheric brown carbon (BrC) is a significant contributor to particulate light absorption. Reactions between small aldehydes and reduced nitrogen species have been shown to produce secondary BrC in atmospheric droplets. These reactions can be substantially accelerated upon droplet evaporation. Despite aqueous droplets undergoing continuous water evaporation and uptake in response to the surrounding relative humidity (RH), secondary BrC formation in these droplets under various RH conditions remains poorly understood. In this work, we investigate BrC formation from reactions of two aqueous-phase precursors, glyoxal and methylglyoxal, with ammonium sulfate or glycine in aqueous droplets after drying at a range of RH (30-90%). Our results illustrate, for the first time, that BrC production varies as a function of RH. For all four chemical reaction systems being investigated, mass absorption efficiencies (MAE, m2/g C) of aqueous aerosol products (from 270 to 512 nm wavelength range) generally increase with reducing RH to reach a maximum at ∼55-65% RH and subsequently decrease, caused by further drying. Chemical characterization using high-resolution aerosol mass spectrometry shows that the formation of nitrogen-containing organic species also follows a similar variation with RH. Our observations reveal that the acceleration of BrC production from evaporation of water may be diminished by other factors, such as limited particle-phase water content, phase transition, and volatility of reactants and products. Overall, our results highlight that intermediate RH conditions in the atmosphere may be more efficient in secondary BrC formation, indicating that the effect of RH needs to be included in atmospheric models for a more accurate representation of light-absorbing aerosol formation in aqueous droplets.

Compositional evolution of particle-phase reaction products and water in the heterogeneous OH oxidation of model aqueous organic aerosols

Abstract. Organic compounds present at or near the surface of aqueous droplets can be efficiently oxidized by gas-phase OH radicals, which alter the molecular distribution of the reaction products within the droplet. A change in aerosol composition affects the hygroscopicity and leads to a concomitant response in the equilibrium amount of particle-phase water. The variation in the aerosol water content affects the aerosol size and physicochemical properties, which in turn governs the oxidation kinetics and chemistry. To attain better knowledge of the compositional evolution of aqueous organic droplets during oxidation, this work investigates the heterogeneous OH-radical-initiated oxidation of aqueous methylsuccinic acid (C5H8O4) droplets, a model compound for small branched dicarboxylic acids found in atmospheric aerosols, at a high relative humidity of 85 % through experimental and modeling approaches. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (Direct Analysis in Real Time, DART) coupled with a high-resolution mass spectrometer reveal two major products: a five carbon atom (C5) hydroxyl functionalization product (C5H8O5) and a C4 fragmentation product (C4H6O3). These two products likely originate from the formation and subsequent reactions (intermolecular hydrogen abstraction and carbon–carbon bond scission) of tertiary alkoxy radicals resulting from the OH abstraction occurring at the methyl-substituted carbon site. Based on the identification of the reaction products, a kinetic model of oxidation (a two-product model) coupled with the Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model is built to simulate the size and compositional changes of aqueous methylsuccinic acid droplets during oxidation. Model results show that at the maximum OH exposure, the droplets become slightly more hygroscopic after oxidation, as the mass fraction of water is predicted to increase from 0.362 to 0.424; however, the diameter of the droplets decreases by 6.1 %. This can be attributed to the formation of volatile fragmentation products that partition to the gas phase, leading to a net loss of organic species and associated particle-phase water, and thus a smaller droplet size. Overall, fragmentation and volatilization processes play a larger role than the functionalization process in determining the evolution of aerosol water content and droplet size at high-oxidation stages.

Effects of Relative Humidity and Particle Phase Water on the Heterogeneous OH Oxidation of 2-Methylglutaric Acid Aqueous Droplets.

Organic aerosols can exist as aqueous droplets, with variable water content depending on their composition and environmental conditions (e.g., relative humidity (RH)). Recent laboratory studies have revealed that oxidation kinetics in highly concentrated droplets can be much slower than those in dilute solutions. However, it remains unclear whether aerosol phase water affects the formation of reaction products physically and/or chemically. In this work, we investigate the role of aerosol phase water on the heterogeneous chemistry of aqueous organic droplets consisting of 2-methylglutaric acid (2-MGA), measuring the reaction kinetics and the reaction products upon heterogeneous OH oxidation over a range of RH. An atmospheric pressure soft ionization source (direct analysis in real time, DART) coupled with a high-resolution mass spectrometer is used to obtain real-time molecular information on the reaction products. Aerosol mass spectra show that the same reaction products are formed at all measured RH. At a given reaction extent of the parent 2-MGA, the aerosol composition is independent of RH. These results suggest the aerosol phase water does not alter reaction mechanisms significantly. Kinetic measurements find that the effective OH uptake coefficient, γeff, decreases with decreasing RH below 72%. Isotopic exchange measurements performed using aerosol optical tweezers reveal water diffusion coefficients in the 2-MGA droplets to be 3.0 × 10-13 to 8.0 × 10-13 m2 s-1 over the RH range of 47-58%. These values are comparable to those of other viscous organic aerosols (e.g., citric acid), indicating that 2-MGA droplets are likely to be viscous at low humidity. Smaller γeff at low RH is likely attributed to the slower diffusion of reactants within the droplets. Taken together, the observed relationship between the γeff and RH is likely attributed to changes in aerosol viscosity rather than changes in reaction mechanisms.

Molecular Composition and Volatility of Organic Aerosol in the Southeastern U.S.: Implications for IEPOX Derived SOA.

We present measurements as part of the Southern Oxidant and Aerosol Study (SOAS) during which atmospheric aerosol particles were comprehensively characterized. We present results utilizing a Filter Inlet for Gases and AEROsol coupled to a chemical ionization mass spectrometer (CIMS). We focus on the volatility and composition of isoprene derived organic aerosol tracers and of the bulk organic aerosol. By utilizing the online volatility and molecular composition information provided by the FIGAERO-CIMS, we show that the vast majority of commonly reported molecular tracers of isoprene epoxydiol (IEPOX) derived secondary organic aerosol (SOA) is derived from thermal decomposition of accretion products or other low volatility organics having effective saturation vapor concentrations <10(-3) μg m(-3). In addition, while accounting for up to 30% of total submicrometer organic aerosol mass, the IEPOX-derived SOA has a higher volatility than the remaining bulk. That IEPOX-SOA, and more generally bulk organic aerosol in the Southeastern U.S. is comprised of effectively nonvolatile material has important implications for modeling SOA derived from isoprene, and for mechanistic interpretations of molecular tracer measurements. Our results show that partitioning theory performs well for 2-methyltetrols, once accretion product decomposition is taken into account. No significant partitioning delays due to aerosol phase or viscosity are observed, and no partitioning to particle-phase water or other unexplained mechanisms are needed to explain our results.

Impacts of Sulfate Seed Acidity and Water Content on Isoprene Secondary Organic Aerosol Formation.

The effects of particle-phase water and the acidity of pre-existing sulfate seed particles on the formation of isoprene secondary organic aerosol (SOA) was investigated. SOA was generated from the photo-oxidation of isoprene in a flow tube reactor at 70% relative humidity (RH) and room temperature in the presence of three different sulfate seeds (effloresced and deliquesced ammonium sulfate and ammonium bisulfate) under low NOx conditions. High OH exposure conditions lead to little isoprene epoxydiol (IEPOX) SOA being generated. The primary result is that particle-phase water had the largest effect on the amount of SOA formed, with 60% more SOA formation occurring with deliquesced ammonium sulfate seeds as compared to that on effloresced ones. The additional organic material was highly oxidized. Although the amount of SOA formed did not exhibit a dependence on the range of seed particle acidity examined, perhaps because of the low amount of IEPOX SOA, the levels of high-molecular-weight material increased with acidity. While the uptake of organics was partially reversible under drying, the results nevertheless indicate that particle-phase water enhanced the amount of organic aerosol material formed and that the RH cycling of sulfate particles may mediate the extent of isoprene SOA formation in the atmosphere.

Secondary organic aerosol formation from toluene in an atmospheric hydrocarbon mixture: Water and particle seed effects

Abstract Atmospherically relevant secondary organic aerosol (SOA) concentrations from toluene, in an urban hydrocarbon environment, with oxides of nitrogen in natural sunlight, were studied in a large outdoor chamber with different initial humidity and types of initial seed aerosols. Ammonium sulfate particles (38 μg m −3 ) in the presence of an atmospheric hydrocarbon mixture and NOx in sunlight under a dry atmosphere (%RH = 6 to 10%) show reduced SOA formation when compared to similar gas phase conditions with lower ammonium sulfate (7 μg m −3 ) and higher relative humidities (%RH 40 to 90%). No post particle nucleation (particles in the 6 to 10 nm range) was observed in either seeded system. When initial background particles levels were below 0.5 μg m −3 particle nucleation was observed. A new condensed aromatic kinetic chemical mechanism was developed to simulate experimental data. A particle water phase was highly related to SOA formation. Reasonable fits to the gas and total SOA concentrations emphasize the important impact of different initial particle seed levels and particle phase water when simulating SOA formation from aromatic compounds like toluene.

Air–water exchange of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) at a coastal site in Izmir Bay, Turkey

The air–water exchange of polychlorinated biphenyl (PCB) and organochlorine pesticides (OCPs) were investigated using paired air–water samples ( n = 16) collected in July and February–March, 2005 from Guzelyali Port in Izmir Bay, Turkey. Atmospheric PCBs and OCPs were mainly in gas-phase in both periods. However, their dissolved and particle-phase water concentrations were comparable. For PCBs, 3 and 4-Cl congeners were dominant while chlorpyrifos, endosulfans and HCHs were the most abundant OCPs for all samples. Especially in summer, calculated net gas-exchange PCB fluxes were mainly volatilization from the water ranging from − 0.2 (volatilization, PCB-101) to − 30.0 (volatilization, PCB-31) ng m − 2 day − 1 . For OCPs, net flux ranged from − 0.03 (volatilization, cis-nonachlor) to 1568 (deposition, endosulfan I) ng m − 2 day − 1 and they have seasonal variations with generally deposition in winter and volatilization in summer. However, endosulfan I, II, endosulfan sulfate, α- and γ-HCH deposited in both periods. The calculated residence times of PCBs and OCPs in the water column indicated that the gas-exchange in the Bay is at least as or a more important mechanism than advection. Annual gaseous absorption and volatilization fluxes were calculated and were used along with the estimated dry deposition fluxes and wet deposition fluxes measured recently at a suburban site in Izmir to determine the relative contributions of different atmospheric mechanisms to the pollutant inventory of the Bay water column. Results suggested that the relative contributions of all studied mechanisms to the water column PCB and OCP inventories were significant.