Chemical evolution of secondary organic aerosol from OH-initiated heterogeneous oxidation

The heterogeneous oxidation of laboratory Secondary Organic Aerosol (SOA) particles by OH radicals was investigated. SOA particles, produced by reaction of α-pinene and O<sub>3</sub>, were exposed to OH radicals in a flow tube, and particle chemical composition, size, and hygroscopicity were measured to assess modifications due to oxidative aging. Aerosol Mass Spectrometer (AMS) mass spectra indicated that the degree of oxidation of 200 nm diameter SOA particles was significantly enhanced due to OH-initiated oxidation, as evidenced by the increase in the fraction of <i>m/z</i> 44 fragment of total organic mass concentration (F44). F44 values of the SOA particles, initially in the range F44=0.04–0.07, increased by up to ΔF44~0.01 under equivalent atmospheric aging timescales of 2 weeks, assuming a 24-h average OH concentration of 10<sup>6</sup> cm<sup>−3</sup>. Particle O/C ratios calculated from F44 values, initially in the range O/C=0.25–0.35, rose by a maximum of ΔO/C~0.04 units for 2 weeks of aging. Particle densities also increased with heterogeneous oxidation, consistent with the observed increase in the degree of oxidation. Minor reductions in particle size, with volume losses of up to 10%, were observed due to volatilization of oxidation products. The SOA particles activated more readily to form cloud droplets with an increase in the κ hygroscopicity parameter of up to a factor of two for the equivalent of 2 weeks of OH atmospheric exposure. These results indicate that OH heterogeneous oxidation of typical SOA needs to be considered as an atmospheric organic aerosol aging mechanism, most likely of higher relative importance away from VOC source regions, where other aging mechanisms are less dominant

A study of the phase transition behavior of mixed ammonium sulfate ? malonic acid aerosols

International audienceThis is a study into the phase transitions of aerosol composed of the ternary system ammonium sulfate (AS) ? malonic acid (MA) ? water using infrared extinction spectroscopy. Twelve compositions were studied in both deliquescence and efflorescence mode experiments. The presence of a MA fraction, by dry mass, (fMA) of 0.1 in an AS aerosol altered the relative humidity at which the phase transitions occur in an atmospherically significant manner. For compositions with 0.25fMAfMA=0.9, the crystallization relative humidity of MA was lowered from RH=6% to less than 1%. Similarly, at fMA=0.4, the AS component did not crystallize. The atmospheric implications of the results are discussed

A study of the phase transition behavior of internally mixed ammonium sulfate - malonic acid aerosols

International audienceThis is a study into the phase transitions of aerosol composed of the ternary system ammonium sulfate (AS) - malonic acid (MA) - water using infrared extinction spectroscopy. Twelve compositions were studied in both deliquescence and efflorescence mode experiments. The presence of a MA fraction, by dry mass, (fMA) of 0.1 in an AS aerosol altered the relative humidity at which the phase transitions occur in an atmospherically significant manner. For compositions with 0.25fMAfMA=0.9, the crystallization relative humidity of MA was lowered from RH=6% to less than 1%. Similarly, at fMA=0.4, the AS component did not crystallize. The atmospheric implications of the results are discussed

Analysis of cloud condensation nuclei composition and growth kinetics using a pumped counterflow virtual impactor and aerosol mass spectrometer

We present a new method of determining the size and composition of CCN-active aerosol particles. Method utility is illustrated through a series of ambient measurements. A continuous-flow thermal-gradient diffusion chamber (TGDC), pumped counterflow virtual impactor (PCVI), and Aerodyne time-of-flight mass spectrometer (AMS) are operated in series. Ambient particles are sampled into the TGDC, where a constant supersaturation is maintained, and CCN-active particles grow to ~2.5 ± 0.5 μm. The output flow from the TGDC is directed into the PCVI, where a counterflow of dry N<sub>2</sub> gas opposes the particle-laden flow, creating a region of zero axial velocity. This stagnation plane can only be traversed by particles with sufficient momentum, which depends on their size. Particles that have activated in the TGDC cross the stagnation plane and are entrained in the PCVI output flow, while the unactivated particles are diverted to a pump. Because the input gas is replaced by the counterflow gas with better than 99 % efficiency at the stagnation plane, the output flow consists almost entirely of dry N<sub>2</sub> and water evaporates from the activated particles. In this way, the system yields an ensemble of CCN-active particles whose chemical composition and size are analyzed using the AMS. Measurements of urban aerosol in downtown Toronto identified an external mixture of CCN-active particles consisting almost entirely of ammonium nitrate and ammonium sulfate, with CCN-inactive particles of the same size consisting of a mixture of ammonium nitrate, ammonium sulfate, and organics. We also discuss results from the first field deployment of the TGDC-PCVI-AMS system, conducted from mid-May to mid-June 2007 in Egbert, Ontario, a semirural site ~80 km north of Toronto influenced both by clean air masses from the north and emissions from the city. Organic-dominated particles sampled during a major biogenic event exhibited higher CCN activity and/or faster growth kinetics than urban outflow from Toronto, despite the latter having a higher inorganic content and higher O:C ratio. During both events, particles were largely internally mixed

Organic acids as cloud condensation nuclei: Laboratory studies of highly soluble and insoluble species

International audienceThe ability of sub-micron-sized organic acid particles to act as cloud condensation nuclei (CCN) has been examined at room temperature using a newly constructed continuous-flow, thermal-gradient diffusion chamber (TGDC). The organic acids studied were: oxalic, malonic, glutaric, oleic and stearic. The CCN properties of the highly soluble acids - oxalic, malonic and glutaric - match very closely Köhler theory predictions which assume full dissolution of the dry particle and a surface tension of the growing droplet equal to that of water. In particular, for supersaturations between 0.3 and 0.6, agreement between the dry particle diameter which gives 50% activation and that calculated from Köhler theory is to within 3nm on average. In the course of the experiments, considerable instability of glutaric acid particles was observed as a function of time and there is evidence that they fragment to some degree to smaller particles. Stearic acid and oleic acid, which are both highly insoluble in water, did not activate at supersaturations of 0.6% with dry diameters up to 140nm. Finally, to validate the performance of the TGDC, we present results for the activation of ammonium sulfate particles that demonstrate good agreement with Köhler theory if solution non-ideality is considered. Our findings support earlier studies in the literature that showed highly soluble organics to be CCN active but insoluble species to be largely inactive

Ozone decomposition kinetics on alumina: effects of ozone partial pressure, relative humidity and state of film oxidation

International audienceThe room temperature kinetics of gas-phase ozone loss via heterogeneous interactions with thin alumina films has been studied in real-time using 254 nm absorption spectroscopy to monitor ozone concentrations. The films were prepared from dispersions of fine alumina powder in methanol and their surface areas were determined by an in situ procedure using adsorption of krypton at 77 K. The alumina was found to lose reactivity with increasing ozone exposure. However, some of the lost reactivity could be recovered over timescales of days in an environment free of water, ozone and carbon dioxide. From multiple exposures of ozone to the same film it was found that the number of active sites is large, greater than 1.4×1014 active sites per cm2 of surface area, or comparable to the total number of surface sites. The films maintain some reactivity at this point, which is consistent with there being some degree of active site regeneration during the experiment and with ozone loss being catalytic to some degree. The initial uptake coefficients on fresh films were found to be inversely dependent on the starting ozone concentration varying from roughly 10?6 for ozone concentrations of 1014 molecules/cm3 to 10?5 at 1013 molecules/cm3. The initial uptake coefficients were not dependent on the relative humidity, up to 75%, within the precision of the experiment. The reaction mechanism is discussed, as well as the implications these results have for assessing the effect of mineral dust on atmospheric oxidant levels

Ozone decomposition kinetics on alumina: effects of ozone partial pressure, relative humidity and repeated oxidation cycles

International audienceThe room temperature kinetics of gas-phase ozone loss via heterogeneous interactions with thin alumina films has been studied in real-time using 254nm absorption spectroscopy to monitor ozone concentrations. The films were prepared from dispersions of fine alumina powder in methanol and their surface areas were determined by an in situ procedure using adsorption of krypton at 77K. The alumina was found to lose reactivity with increasing ozone exposure. However, some of the lost reactivity could be recovered over timescales of days in an environment free of water, ozone and carbon dioxide. From multiple exposures of ozone to the same film, it was found that the number of active sites is large, greater than 1.4x1014 active sites per cm2 of surface area or comparable to the total number of surface sites. The films maintain some reactivity at this point, which is consistent with there being some degree of active site regeneration during the experiment and with ozone loss being catalytic to some degree. The initial uptake coefficients on fresh films were found to be inversely dependent on the ozone concentration, varying from roughly 10-6 for ozone concentrations of 1014 molecules/cm3 to 10-5 at 1013 molecules/cm3. The initial uptake coefficients were not dependent on the relative humidity, up to 75%, within the precision of the experiment. The reaction mechanism is discussed, as well as the implications these results have for assessing the effect of mineral dust on atmospheric oxidant levels

Heterogeneous oxidation of saturated organic aerosols by hydroxyl radicals: Uptake kinetics and condensed-phase products

International audienceThe kinetics and reaction mechanism for the heterogeneous oxidation of saturated organic aerosols by gas-phase OH radicals were investigated under NOx-free conditions. The reaction of 150 nm diameter Bis(2-ethylhexyl) sebacate (BES) particles with OH was studied as a proxy for chemical aging of atmospheric aerosols containing saturated organic matter. An aerosol reactor flow tube combined with an Aerodyne time-of-flight aerosol mass spectrometer (ToF-AMS) and scanning mobility particle sizer (SMPS) was used to study this system. Hydroxyl radicals were produced by 254 nm photolysis of O3 in the presence of water vapour. The kinetics of the heterogeneous oxidation of the BES particles was studied by monitoring the loss of a mass fragment of BES with the ToF-AMS as a function of OH exposure. We measured an initial OH uptake coefficient of ?0 = 1.26 (±0.04), confirming that this reaction is highly efficient. The density of BES particles increased by up to 20% of the original BES particle density at the highest OH exposure studied, consistent with the particle becoming more oxidized. Electrospray ionization mass spectrometry analysis showed that the major particle-phase reaction products are multifunctional carbonyls and alcohols with higher molecular weights than the starting material. Volatilization of oxidation products accounted for a maximum of 17% decrease of the particle volume at the highest OH exposure studied. Tropospheric organic aerosols will become more oxidized from heterogeneous photochemical oxidation, which may affect not only their physical and chemical properties, but also their hygroscopicity and cloud nucleation activity

Heterogeneous oxidation of saturated organic aerosols by hydroxyl radicals: uptake kinetics, condensed-phase products, and particle size change

International audienceThe kinetics and reaction mechanism for the heterogeneous oxidation of saturated organic aerosols by gas-phase OH radicals were investigated under NOx-free conditions. The reaction of 150 nm diameter Bis(2-ethylhexyl) sebacate (BES) particles with OH was studied as a proxy for chemical aging of atmospheric aerosols containing saturated organic matter. An aerosol reactor flow tube combined with an Aerodyne time-of-flight aerosol mass spectrometer (ToF-AMS) and scanning mobility particle sizer (SMPS) was used to study this system. Hydroxyl radicals were produced by 254 nm photolysis of O3 in the presence of water vapour. The kinetics of the heterogeneous oxidation of the BES particles was studied by monitoring the loss of a mass fragment of BES with the ToF-AMS as a function of OH exposure. We measured an initial OH uptake coefficient of ?0=1.3 (±0.4), confirming that this reaction is highly efficient. The density of BES particles increased by up to 20% of the original BES particle density at the highest OH exposure studied, consistent with the particle becoming more oxidized. Electrospray ionization mass spectrometry analysis showed that the major particle-phase reaction products are multifunctional carbonyls and alcohols with higher molecular weights than the starting material. Volatilization of oxidation products accounted for a maximum of 17% decrease of the particle volume at the highest OH exposure studied. Tropospheric organic aerosols will become more oxidized from heterogeneous photochemical oxidation, which may affect not only their physical and chemical properties, but also their hygroscopicity and cloud nucleation activity

Formaldehyde measurements by Proton transfer reaction – Mass Spectrometry (PTR-MS): correction for humidity effects

Formaldehyde measurements can provide useful information about photochemical activity in ambient air, given that HCHO is formed via numerous oxidation processes. Proton transfer reaction mass spectrometry (PTR-MS) is an online technique that allows measurement of VOCs at the sub-ppbv level with good time resolution. PTR-MS quantification of HCHO is hampered by the humidity dependence of the instrument sensitivity, with higher humidity leading to loss of PTR-MS signal. In this study we present an analytical, first principles approach to correct the PTR-MS HCHO signal according to the concentration of water vapor in sampled air. The results of the correction are validated by comparison of the PTR-MS results to those from a Hantzsch fluorescence monitor which does not have the same humidity dependence. Results are presented for an intercomparison made during a field campaign in rural Ontario at Environment Canada's Centre for Atmospheric Research Experiments