Reactive Oxygen Species Production from Secondary Organic Aerosols: The Importance of Singlet Oxygen.

Organic aerosols are subjected to atmospheric processes driven by sunlight, including the production of reactive oxygen species (ROS) capable of transforming their physicochemical properties. In this study, secondary organic aerosols (SOA) generated from aromatic precursors were found to sensitize singlet oxygen (1O2), an arguably underappreciated atmospheric ROS. Specifically, we quantified 1O2, OH radical, and H2O2 quantum yields within photoirradiated solutions of laboratory-generated SOA from toluene, biphenyl, naphthalene, and 1,8-dimethylnaphthalene. At 5 mgC L-1 of SOA extracts, the average steady-state concentrations of 1O2 and of OH radicals in irradiated solutions were 3 ± 1 × 10-14 M and 3.6 ± 0.9 × 10-17 M, respectively. Furthermore, ROS quantum yields of irradiated ambient PM10 extracts were comparable to those from laboratory-generated SOA, suggesting a similarity in ROS production from both types of samples. Finally, by using our measured ROS concentrations, we predict that certain organic compounds found in aerosols, such as amino acids, organo-nitrogen compounds, and phenolic compounds have shortened lifetimes by more than a factor of 2 when 1O2 is considered as an additional sink. Overall, our findings highlight the importance of SOA as a source of 1O2 and its potential as a competitive ROS species in photooxidation processes.

Influence of humidity and iron(iii) on photodegradation of atmospheric secondary organic aerosol particles.

The absorption of solar actinic radiation by atmospheric secondary organic aerosol (SOA) particles drives condensed-phase photochemical processes, which lead to particle mass loss by the production of CO, CO2, hydrocarbons, and various oxygenated volatile organic compounds (OVOCs). We examined the influence of relative humidity (RH) and Fe(iii) content on the OVOC release and subsequent mass loss from secondary organic aerosol material (SOM) during UV irradiation. The samples were generated in a flow tube reactor from the oxidation of d-limonene by ozone. The SOM was collected with a Micro Orifice Uniform Deposit Impactor (MOUDI) on CaF2 windows. To selected samples, a variable amount of FeCl3 was added before irradiation. The resulting SOM samples, with or without added FeCl3, were irradiated with a 305 nm light-emitting diode and the release of several OVOCs, including acetic acid, acetone, formic acid and acetaldehyde, was measured with a Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-ToF-MS). The release of OVOCs from photodegradation of SOM at typical ambient mid-values of RH (30-70%) was 2-4 times higher than under dry conditions. The release of OVOCs was slightly enhanced in the presence of low concentrations of iron (0.04 Fe molar ratio) but it was suppressed at higher concentrations (0.50 Fe molar ratio) of iron indicating the existence of a complicated radical chemistry driving the photodegradation of SOM. Our findings suggest that the presence of iron in atmospheric aerosol particles will either increase or decrease release of OVOCs due to the photodegradation of SOM depending on whether the relative iron concentration is low or high, respectively. At atmospherically relevant RH conditions, the expected fractional mass loss induced by these photochemical processes from limonene SOA particles would be between 2 and 4% of particle mass per hour. Therefore, photodegradation is an important aging mechanism for this type of SOA.

Feasibility of Photosensitized Reactions with Secondary Organic Aerosol Particles in the Presence of Volatile Organic Compounds.

The ability of a complex mixture of organic compounds found in secondary organic aerosol (SOA) to act as a photosensitizer in the oxidation of volatile organic compounds (VOCs) was investigated. Different types of SOAs were produced in a smog chamber by oxidation of various biogenic and anthropogenic VOCs. The SOA particles were collected from the chamber onto an inert substrate, and the resulting material was exposed to 365 nm radiation in an air flow containing ∼200 ppbv of limonene vapor. The mixing ratio of limonene and other VOCs in the flow was observed with a proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS). The photosensitized uptake of limonene was observed for several SOA materials, with a lower limit for the reactive uptake coefficient on the scale of ∼10-5. The lower limit for the uptake coefficient under conditions of Los Angeles, California on the summer solstice at noon was estimated to be on the order of ∼10-6. Photoproduction of oxygenated VOCs (OVOCs) resulting from photodegradation of the SOA material also occurred in parallel with the photosensitized uptake of limonene. The estimated photosensitized limonene uptake rates by atmospheric SOA particles and vegetation surfaces appear to be too small to compete with the atmospheric oxidation of limonene by the hydroxyl radical or ozone. However, these processes could play a role in the leaf boundary layer where concentrations of oxidants are depleted and concentrations of VOCs are enhanced relative to the free atmosphere.

Photodegradation of Secondary Organic Aerosol Particles as a Source of Small, Oxygenated Volatile Organic Compounds.

We investigated the photodegradation of secondary organic aerosol (SOA) particles by near-UV radiation and photoproduction of oxygenated volatile organic compounds (OVOCs) from various types of SOA. We used a smog chamber to generate SOA from α-pinene, guaiacol, isoprene, tetradecane, and 1,3,5-trimethylbenzene under high-NOx, low-NOx, or ozone oxidation conditions. The SOA particles were collected on a substrate, and the resulting material was exposed to several mW of near-UV radiation (λ ∼ 300 nm) from a light-emitting diode. Various OVOCs, including acetic acid, formic acid, acetaldehyde, and acetone were observed during photodegradation, and their SOA-mass-normalized fluxes were estimated with a Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-ToF-MS). All the SOA, with the exception of guaiacol SOA, emitted OVOCs upon irradiation. Based on the measured OVOC emission rates, we estimate that SOA particles would lose at least ∼1% of their mass over a 24 h period during summertime conditions in Los Angeles, California. This condensed-phase photochemical process may produce a few Tg/year of gaseous formic acid, the amount comparable to its primary sources. The condensed-phase SOA photodegradation processes could therefore measurably affect the budgets of both particulate and gaseous atmospheric organic compounds on a global scale.

Chemical Characterization of Nanoparticles and Volatiles Present in Mainstream Hookah Smoke.

Waterpipe smoking is becoming more popular worldwide and there is a pressing need to better characterize the exposure of smokers to chemical compounds present in the mainstream smoke. We report real-time measurements of mainstream smoke for carbon monoxide, volatile organic compounds and nanoparticle size distribution and chemical composition using a custom dilution flow tube. A conventional tobacco mixture, a dark leaf unwashed tobacco and a nicotine-free herbal tobacco were studied. Results show that carbon monoxide is present in the mainstream smoke and originates primarily from the charcoal used to heat the tobacco. Online measurements of volatile organic compounds in mainstream smoke showed an overwhelming contribution from glycerol. Gas phase analysis also showed that very little filtration of the gas phase products is provided by the percolation of mainstream smoke through water. Waterpipe smoking generated high concentrations of 4-100 nm nanoparticles, which were mainly composed of sugar derivatives and especially abundant in the first 10 min of the smoking session. These measured emissions of volatiles and particles are compared with those from a reference cigarette (3R4F) and represent the equivalent of the emission of one or more entire cigarettes for a single puff of hookah smoke. Considerations related to the health impacts of waterpipe smoking are discussed.

Multiple Aggregation Pathways in Human γS-Crystallin and Its Aggregation-Prone G18V Variant.

Purpose: Cataract results from the formation of light-scattering precipitates due to point mutations or accumulated damage in the structural crystallins of the eye lens. Although excised cataracts are predominantly amorphous, in vitro studies show that crystallins are capable of adopting a variety of morphologies depending on the preparation method. Here we characterize thermal, pH-dependent, and UV-irradiated aggregates from wild-type human γS-crystallin (γS-WT) and its aggregation-prone variant, γS-G18V. Methods: Aggregates of γS-WT and γS-G18V were prepared under acidic, neutral, and basic pH conditions and held at 25°C or 37°C for 48 hours. UV-induced aggregates were produced by irradiation with a 355-nm laser. Aggregation and fibril formation were monitored via turbidity and thioflavin T (ThT) assays. Aggregates were characterized using intrinsic aromatic fluorescence, powder x-ray diffraction, and mass spectrometry. Results: γS-crystallin aggregates displayed different characteristics depending on the preparation method. γS-G18V produced a larger amount of detectable aggregates than did γS-WT and at less-extreme conditions. Aggregates formed under basic and acidic conditions yielded elevated ThT fluorescence; however, aggregates formed at low pH did not produce strongly turbid solutions. UV-induced aggregates produced highly turbid solutions but displayed only moderate ThT fluorescence. X-ray diffraction confirms amyloid character in low-pH samples and UV-irradiated samples, although the relative amounts vary. Conclusions: γS-G18V demonstrates increased aggregation propensity compared to γS-WT when treated with heat, acid, or UV light. The resulting aggregates differ in their ThT fluorescence and turbidity, suggesting that at least two different aggregation pathways are accessible to both proteins under the conditions tested.