Changes in organic aerosol composition with aging inferred from aerosol mass spectra

Organic aerosols (OA) can be separated with factor analysis of aerosol mass spectrometer (AMS) data into hydrocarbon-like OA (HOA) and oxygenated OA (OOA). We develop a new method to parameterize H:C of OOA in terms of f_(43)(ratio of m/z 43, mostly C_2H_3O^+, to total signal in the component mass spectrum). Such parameterization allows for the transformation of large database of ambient OOA components from the f_(44) (mostly CO^+_2, likely from acid groups) vs. f_(43) space ("triangle plot") (Ng et al., 2010) into the Van Krevelen diagram (H:C vs. O:C) (Van Krevelen, 1950). Heald et al. (2010) examined the evolution of total OA in the Van Krevelen diagram. In this work total OA is deconvolved into components that correspond to primary (HOA and others) and secondary (OOA) organic aerosols. By deconvolving total OA into different components, we remove physical mixing effects between secondary and primary aerosols which allows for examination of the evolution of OOA components alone in the Van Krevelen space. This provides a unique means of following ambient secondary OA evolution that is analogous to and can be compared with trends observed in chamber studies of secondary organic aerosol formation. The triangle plot in Ng et al. (2010) indicates that f_(44) of OOA components increases with photochemical age, suggesting the importance of acid formation in OOA evolution. Once they are transformed with the new parameterization, the triangle plot of the OOA components from all sites occupy an area in Van Krevelen space which follows a ΔH:C/ΔO:C slope of ~ −0.5. This slope suggests that ambient OOA aging results in net changes in chemical composition that are equivalent to the addition of both acid and alcohol/peroxide functional groups without fragmentation (i.e. C-C bond breakage), and/or the addition of acid groups with fragmentation. These results provide a framework for linking the bulk aerosol chemical composition evolution to molecular-level studies

Elemental composition and oxidation of chamber organic aerosol

Recently, graphical representations of aerosol mass spectrometer (AMS) spectra and elemental composition have been developed to explain the oxidative and aging processes of secondary organic aerosol (SOA). It has been shown previously that oxygenated organic aerosol (OOA) components from ambient and laboratory data fall within a triangular region in the f_(44) vs. f_(43) space, where f_(44) and f_(43) are the ratios of the organic signal at m/z 44 and 43 to the total organic signal in AMS spectra, respectively; we refer to this graphical representation as the "triangle plot." Alternatively, the Van Krevelen diagram has been used to describe the evolution of functional groups in SOA. In this study we investigate the variability of SOA formed in chamber experiments from twelve different precursors in both "triangle plot" and Van Krevelen domains. Spectral and elemental data from the high-resolution Aerodyne aerosol mass spectrometer are compared to offline species identification analysis and FTIR filter analysis to better understand the changes in functional and elemental composition inherent in SOA formation and aging. We find that SOA formed under high- and low-NO_x conditions occupy similar areas in the "triangle plot" and Van Krevelen diagram and that SOA generated from already oxidized precursors allows for the exploration of areas higher on the "triangle plot" not easily accessible with non-oxidized precursors. As SOA ages, it migrates toward the top of the triangle along a path largely dependent on the precursor identity, which suggests increasing organic acid content and decreasing mass spectral variability. The most oxidized SOA come from the photooxidation of methoxyphenol precursors which yielded SOA O/C ratios near unity. α-pinene ozonolysis and naphthalene photooxidation SOA systems have had the highest degree of mass closure in previous chemical characterization studies and also show the best agreement between AMS elemental composition measurements and elemental composition of identified species within the uncertainty of the AMS elemental analysis. In general, compared to their respective unsaturated SOA precursors, the elemental composition of chamber SOA follows a slope shallower than −1 on the Van Krevelen diagram, which is indicative of oxidation of the precursor without substantial losss of hydrogen, likely due to the unsaturated nature of the precursors. From the spectra of SOA studied here, we are able to reproduce the triangular region originally constructed with ambient OOA compents with chamber aerosol showing that SOA becomes more chemically similar as it ages. Ambient data in the middle of the triangle represent the ensemble average of many different SOA precursors, ages, and oxidative processes

CCN activation experiments with adipic acid: effect of particle phase and adipic acid coatings on soluble and insoluble particles

Slightly soluble atmospherically relevant organic compounds may influence particle CCN activity and therefore cloud formation. Adipic acid is a frequently employed surrogate for such slightly soluble organic materials. The 11 published experimental studies on the CCN activity of adipic acid particles are not consistent with each other nor do they, in most cases, agree with the Köhler theory. The CCN activity of adipic acid aerosol particles was studied over a significantly wider range of conditions than in any previous single study. The work spans the conditions of the previous studies and also provides alternate methods for producing "wet" (deliquesced solution droplets) and dry adipic acid particles without the need to produce them by atomization of aqueous solutions. The experiments suggest that the scatter in the previously published CCN measurements is most likely due to the difficulty of producing uncontaminated adipic acid particles by atomization of solutions and possibly also due to uncertainties in the calibration of the instruments. The CCN activation of the small (<i>d</i><sub><i>m</i></sub><150 nm) initially dry particles is subject to a deliquescence barrier, while for the larger particles the activation follows the Köhler curve. Wet adipic acid particles follow the Köhler curve over the full range of particle diameters studied. In addition, the effect of adipic acid coatings on the CCN activity of both soluble and insoluble particles has also been studied. When a water-soluble core is coated by adipic acid, the CCN-hindering effect of particle phase is eliminated. An adipic acid coating on hydrophobic soot yields a CCN active particle. If the soot particle is relatively small (<i>d</i><sub>core</sub>≤102 nm), the CCN activity of the coated particles approaches the deliquescence line of adipic acid, suggesting that the total size of the particle determines CCN activation and the soot core acts as a scaffold

Density changes of aerosol particles as a result of chemical reaction

International audienceThis paper introduces the capability to study simultaneously changes in the density, the chemical composition, the mobility diameter, the aerodynamic diameter, and the layer thickness of multi-layered aerosol particles as they are being altered by heterogeneous chemical reactions. A vaporization-condensation method is used to generate aerosol particles composed of oleic acid outer layers of 2 to 30 nm on 101-nm polystyrene latex cores. The layer density is modified by reaction of oleic acid with ozone for variable exposure times. For increasing ozone exposure, the mobility diameter decreases while the vacuum aerodynamic diameter increases, which, for spherical particles, implies that particle density increases. The aerosol particles are confirmed as spherical based upon the small divergence of the particle beam in the aerosol mass spectrometer. The particle and layer densities are calculated by two independent methods, namely one based on the measured aerodynamic and mobility diameters and the other based on the measured mobility diameter and particle mass. The uncertainty estimates for density calculated by the second method are two to three times greater than those of the first method. Both methods indicate that the layer density increases from 0.89 to 1.12 g·cm?3 with increasing ozone exposure. Aerosol mass spectrometry shows that, concomitant with the increase in the layer density, the oxygen content of the reacted layer increases. Even after all of the oleic acid has reacted, the layer density and the oxygen content continue to increase slowly with prolonged ozone exposure, a finding which indicates continued chemical reactions of the organic products either with ozone or with themselves. The results of this paper provide new insights into the complex changes occurring for atmospheric particles during the aging processes caused by gas-phase oxidants

Laboratory Studies of Chemical and Photochemical Processes Relevant to Stratospheric Ozone

The purpose of this project is to reduce the uncertainty in several key gas-phase kinetic processes which impact our understanding of stratospheric ozone. The main emphasis of this work is on measuring rate coefficients and product channels for reactions of HOx and NOx species in the temperature range 200 K to 240 K relevant to the lower stratosphere. Other areas of study have included infrared spectroscopic studies of the HO radical, measurements of OH radical reactions with alternative fluorocarbons, and determination of the vapor pressures of nitric acid hydrates under stratospheric conditions. The results of these studies will improve models of stratospheric ozone chemistry and predictions of perturbations due to human influences

Laboratory studies of chemical and photochemical processes relevant to stratospheric ozone

The purpose of this project is to reduce the uncertainty in several key gas-phase kinetic processes which impact our understanding of stratospheric ozone. The main emphasis of this work is on measuring rate coefficients and product channels for reactions of HO(sub x) and NO(sub x) species in the temperature range 200 K to 240 K relevant to the lower stratosphere. Other areas of study have included infrared spectroscopic studies of the HO2 radical, measurements of OH radical reactions with alternative fluorocarbons, and determination of the vapor pressures of nitric acid hydrates under stratospheric conditions. The results of these studies will improve models of stratospheric ozone chemistry and predictions of perturbations due to human influences. In this annual report, we focus on our recent accomplishments in the quantitative spectroscopy of the HO2 radical. This report details the measurements of the broadening coefficients for the v(sub 2) vibrational band. Further measurements of the vapor pressures of nitric acid hydrates relevant to the polar stratospheric cloud formation indicate the importance of metastable crystalline phases of H2SO4, HNO3, and H2O. Large particles produced from these metastable phases may provide a removal mechanism for HNO3 in the polar stratosphere

Deconvolution of FIGAERO-CIMS thermal desorption profiles using positive matrix factorisation to identify chemical and physical processes during particle evaporation

he measurements of aerosol particles with a filter inlet for gases and aerosols (FIGAERO) together with a chemical ionisation mass spectrometer (CIMS) yield the overall chemical composition of the particle phase. In addition, the thermal desorption profiles obtained for each detected ion composition contain information about the volatility of the detected compounds, which is an important property for understanding many physical properties like gas–particle partitioning. We coupled this thermal desorption method with isothermal evaporation prior to the sample collection to investigate the chemical composition changes during isothermal particle evaporation and particulate-water-driven chemical reactions in α-pinene secondary organic aerosol (SOA) of three different oxidative states. The thermal desorption profiles of all detected elemental compositions were then analysed with positive matrix factorisation (PMF) to identify the drivers of the chemical composition changes observed during isothermal evaporation. The keys to this analysis were to use the error matrix as a tool to weight the parts of the data carrying most information (i.e. the peak area of each thermogram) and to run PMF on a combined data set of multiple thermograms from different experiments to enable a direct comparison of the individual factors between separate measurements. The PMF was able to identify instrument background factors and separate them from the part of the data containing particle desorption information. Additionally, PMF allowed us to separate the direct desorption of compounds detected at a specific elemental composition from other signals with the same composition that stem from the thermal decomposition of thermally instable compounds with lower volatility. For each SOA type, 7–9 factors were needed to explain the observed thermogram behaviour. The contribution of the factors depended on the prior isothermal evaporation. Decreased contributions from the factors with the lowest desorption temperatures were observed with increasing isothermal evaporation time. Thus, the factors identified by PMF could be interpreted as volatility classes. The composition changes in the particles due to isothermal evaporation could be attributed to the removal of volatile factors with very little change in the desorption profiles of the individual factors (i.e. in the respective temperatures of peak desorption, Tmax). When aqueous-phase reactions took place, PMF was able to identify a new factor that directly identified the ions affected by the chemical processes. We conducted a PMF analysis of the FIGAERO–CIMS thermal desorption data for the first time using laboratory-generated SOA particles. But this method can be applied to, for example, ambient FIGAERO–CIMS measurements as well. There, the PMF analysis of the thermal desorption data identifies organic aerosol (OA) sources (such as biomass burning or oxidation of different precursors) and types, e.g. hydrocarbon-like (HOA) or oxygenated organic aerosol (OOA). This information could also be obtained with the traditional approach, namely the PMF analysis of the mass spectra data integrated for each thermogram. But only our method can also obtain the volatility information for each OA source and type. Additionally, we can identify the contribution of thermal decomposition to the overall signal

Particle mass yield in secondary organic aerosol formed by the dark ozonolysis of α-pinene

The yield of particle mass in secondary organic aerosol (SOA) formed by dark ozonolysis was measured for 0.3–22.8 ppbv of reacted α-pinene. Most experiments were conducted using a continuous-flow chamber, allowing nearly constant SOA concentration and chemical composition for several days. For comparison, some experiments were also conducted in batch mode. Reaction conditions were 25°C, 40% RH, dry (NH<sub>4</sub>)SO<sub>4</sub> seed particles, and excess 1-butanol. The organic particle loading was independently measured by an aerosol mass spectrometer and a scanning mobility particle sizer, and the two measurements agreed well. The observations showed that SOA formation occurred for even the lowest reacted α-pinene concentration of 0.3 ppbv. The particle mass yield was 0.09 at 0.15 μg m<sup>−3</sup>, increasing to 0.27 at 40 μg m<sup>−3</sup>. Compared to some results reported in the literature, the yields were 80 to 100% larger for loadings above 2 μg m<sup>−3</sup>. At lower loadings, the yields had an offset of approximately +0.07 from those reported in the literature. To as low as 0.15 μm<sup>−3</sup>, the yield curve had no inflection point toward null yield, implying the formation of one or several products having vapor pressures below this value. These observations of increased yields, especially for low loadings, are potentially important for accurate prediction by chemical transport models of organic particle concentrations in the ambient atmosphere

Characterization of submicron aerosol chemical composition and sources in the coastal area of Central Chile

Chemical characteristics and the sources of submicron particles (<1 mu m in diameter) were investigated in Valle Alegre, the coastal area of Central Chile. The chemical composition of particles was studied by using a Soot particle Aerosol Mass Spectrometer and Multi-Angle Absorption Photometer. Submicron particles were dominated by organics (42% of mass) and sulfate (39% of mass) while the mass fractions of ammonium, nitrate and black carbon were much smaller (13, 2 and 4% of mass, respectively). Additionally, several metals (V, Zn, Fe, Cd, Cu, K, Na and Mg) were detected in submicron particles and also some of their inorganic salts (e.g. NaCl+, MgCl2+, CaCl2+, KCl+ and KNO3+). The sources of particles were examined by using Positive Matrix Factorization (PMF). Organic aerosol (OA) was divided into five factors by using PMF; hydrocarbon-like OA (HOA), biomass burning OA (BBOA), low-volatility oxygenated OA (LV-OOA), semi-volatile OA (SV-OOA) and marine oxygenated OOA (MOOA), Oxygenated factors (LV-OOA; SV-OOA and MOOA) comprised 75% of total OA with LV-OOA being the dominant factor (38% of OA). Sulfate had two major sources in Valle Alegre; similar to 70% of sulfate was related to anthropogenic sources through the oxidation of gas phase SO2 whereas similar to 24% of sulfate was associated with biogenic origin related to the oxidation of dimethyl sulfide in the marine environment. Regarding total submicron particle mass (campaign-average 9.5 mu g m(-3)), the contribution of anthropogenic sources was at least as large as that of biogenic origin.Peer reviewe

Stratospheric aircraft exhaust plume and wake chemistry studies

This report documents progress to date in an ongoing study to analyze and model emissions leaving a proposed High Speed Civil Transport (HSCT) from when the exhaust gases leave the engine until they are deposited at atmospheric scales in the stratosphere. Estimates are given for the emissions, summarizing relevant earlier work (CIAP) and reviewing current propulsion research efforts. The chemical evolution and the mixing and vortical motion of the exhaust are analyzed to track the exhaust and its speciation as the emissions are mixed to atmospheric scales. The species tracked include those that could be heterogeneously reactive on the surfaces of the condensed solid water (ice) particles and on exhaust soot particle surfaces. Dispersion and reaction of chemical constituents in the far wake are studied with a Lagrangian air parcel model, in conjunction with a radiation code to calculate the net heating/cooling. Laboratory measurements of heterogeneous chemistry of aqueous sulfuric acid and nitric acid hydrates are also described. Results include the solubility of HCl in sulfuric acid which is a key parameter for modeling stratospheric processing. We also report initial results for condensation of nitric acid trihydrate from gas phase H2O and HNO3