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Atmospheric electrical discharges are now known to generate unexpectedly large amounts of the atmosphere’s primary oxidant, hydroxyl (OH), in thunderstorm anvils, where electrical discharges are caused by atmospheric charge separation. The question is “Do other electrical discharges also generate large amounts of oxidants?” In this paper, we demonstrate that corona formed on grounded metal objects under thunderstorms produce extreme amounts of OH, hydroperoxyl (HO 2 ), and ozone (O 3 ). Hundreds of parts per trillion to parts per billion of OH and HO 2 were measured during seven thunderstorms that passed over the rooftop site during an air quality study in Houston, TX in summer 2006. A combination of analysis of these field results and laboratory experiments shows that these extreme oxidant amounts were generated by corona on the inlet of the OH-measuring instrument and that corona are easier to generate on lightning rods than on the inlet. In the laboratory, increasing the electric field increased OH, HO 2 , and O 3 , with 14 times more O 3 generated than OH and HO 2 , which were equal. Calculations show that corona on lightning rods can annually generate OH that is 10–100 times ambient amounts within centimeters of the lightning rod and on high-voltage electrical power lines can generate OH that is 500 times ambient a meter away from the corona. Contrary to current thinking, previously unrecognized corona-generated OH, not corona-generated UV radiation, mostly likely initiates premature degradation of high-voltage polymer insulators. 

The role of hydroxyl radicals (OH) as a daytime oxidant is well established on a global scale. In specific source regions, such as the marine boundary layer and polluted coastal cities, other daytime oxidants, such as chlorine atoms (Cl) and even bromine atoms (Br), may compete with OH for the oxidation of volatile organic compounds (VOCs) and/or enhance the overall oxidation capacity of the atmosphere. However, the number of studies investigating halogen-initiated secondary organic aerosol (SOA) formation is extremely limited, resulting in large uncertainties in these oxidative aging processes. Here, we characterized the chemical composition and yield of laboratory SOA generated in an oxidation flow reactor (OFR) from the OH and Cl oxidation of n -dodecane ( n -C 12 ) and toluene, and the OH, Cl, and Br oxidation of isoprene and α-pinene. In the OFR, precursors were oxidized using integrated OH, Cl, and Br exposures ranging from 3.1 × 10 10 to 2.3 × 10 12 , 6.1 × 10 9 to 1.3× 10 12 and 3.2 × 10 10 to 9.7 × 10 12 molecules cm −3 s −1 , respectively. Like OH, Cl facilitated multistep SOA oxidative aging over the range of OFR conditions that were studied. In contrast, the extent of Br-initiated SOA oxidative aging was limited. SOA elemental ratios and mass yields obtained in the OFR studies were comparable to those obtained from OH and Cl oxidation of the same precursors in environmental chamber studies. Overall, our results suggest that alkane, aromatic, and terpenoid SOA precursors are characterized by distinct OH- and halogen-initiated SOA yields, and that while Cl may enhance the SOA formation potential in regions influenced by biogenic and anthropogenic emissions, Br may have the opposite effect. 

Reaction with the hydroxyl radical (OH) is often the first step in the removal of many atmospheric pollutants. The nitrogen oxides (NO_x) generated by lightning can increase the amount of HO_x(HO_x = OH + HO₂) present in the atmosphere, but direct HO_xproduction from lightning has never been quantitatively investigated in the laboratory. In this laboratory study, prodigious amounts of HO_xwere generated by both visible and subvisible electrical discharges over ranges of pressure and water vapor mixing ratios relevant to the troposphere. Also measured were NO, total nitrogen oxides (NO_x), ozone (O₃), and OH exposure, which is the integral of the hydroxyl radical concentration over time since the discharge. HO_xand OH exposure were approximately independent of pressure from 360 to 970 hPa and increased only slightly as water vapor increased from 1,000 to 8,000 parts per million volume (ppmv), while NO_xwas approximately independent of both pressure and water vapor over the same ranges. These laboratory measurements of excessive HO_xand OH exposure are similar to measurements of electrically generated HO_xdiscovered in electrified anvil clouds during a 2012 airborne study, thus demonstrating the relevance of these laboratory results to the atmosphere and the importance of understanding the electrically generated HO_xcontribution to atmospheric oxidation.

 

Abstract. In the aqueous phase, fine particulate matter can form reactive species (RS)that influence the aging, properties, and health effects of atmosphericaerosols. In this study, we explore the RS yields of aerosol samples froma remote forest (Hyytiälä, Finland) and polluted urban locations(Mainz, Germany; Beijing, China), and we relate the RS yields to differentchemical constituents and reaction mechanisms. Ultra-high-resolution massspectrometry was used to characterize organic aerosol composition, electronparamagnetic resonance (EPR) spectroscopy with a spin-trapping technique wasapplied to determine the concentrations of ⚫OH,O2⚫-, and carbon- or oxygen-centered organic radicals, anda fluorometric assay was used to quantify H2O2. The aqueousH2O2-forming potential per mass unit of ambient PM2.5(particle diameter < 2.5 µm) was roughly the same for allinvestigated samples, whereas the mass-specific yields of radicals werelower for sampling sites with higher concentrations of PM2.5. Theabundances of water-soluble transition metals and aromatics in ambientPM2.5 were positively correlated with the relative fraction of⚫OH and negatively correlated with the relative fraction ofcarbon-centered radicals. In contrast, highly oxygenated organic molecules(HOM) were positively correlated with the relative fraction ofcarbon-centered radicals and negatively correlated with the relativefraction of ⚫OH. Moreover, we found that the relative fractionsof different types of radicals formed by ambient PM2.5 were comparableto surrogate mixtures comprising transition metal ions, organichydroperoxide, H2O2, and humic or fulvic acids. The interplay oftransition metal ions (e.g., iron and copper ions), highly oxidized organicmolecules (e.g., hydroperoxides), and complexing or scavenging agents (e.g.,humic or fulvic acids) leads to nonlinear concentration dependencies inaqueous-phase RS production. A strong dependence on chemical compositionwas also observed for the aqueous-phase radical yields oflaboratory-generated secondary organic aerosols (SOA) from precursormixtures of naphthalene and β-pinene. Our findings show how thecomposition of PM2.5 can influence the amount and nature ofaqueous-phase RS, which may explain differences in the chemical reactivityand health effects of particulate matter in clean and polluted air. 

Abstract. The chemical complexity of biomass burning organic aerosol (BBOA) greatlyincreases with photochemical aging in the atmosphere, necessitatingcontrolled laboratory studies to inform field observations. In theseexperiments, BBOA from American white oak (Quercus alba) leaf andheartwood samples was generated in a custom-built emissions and combustionchamber and photochemically aged in a potential aerosol mass (PAM) flowreactor. A thermal desorption aerosol gas chromatograph (TAG) was used inparallel with a high-resolution time-of-flight aerosol mass spectrometer(AMS) to analyze BBOA chemical composition at different levels ofphotochemical aging. Individual compounds were identified and integrated toobtain relative decay rates for key molecules. A recently developedchromatogram binning positive matrix factorization (PMF) technique was usedto obtain mass spectral profiles for factors in TAG BBOA chromatograms,improving analysis efficiency and providing a more complete determination ofunresolved complex mixture (UCM) components. Additionally, the recentlycharacterized TAG decomposition window was used to track molecular fragmentscreated by the decomposition of thermally labile BBOA during sampledesorption. We demonstrate that although most primary (freshly emitted) BBOAcompounds deplete with photochemical aging, certain components eluting withinthe TAG thermal decomposition window are instead enhanced. Specifically, theincreasing trend in the decomposition m∕z 44 signal (CO2+)indicates formation of secondary organic aerosol (SOA) in the PAM reactor.Sources of m∕z 60 (C2H4O2+), typically attributed tofreshly emitted BBOA in AMS field measurements, were also investigated. Fromthe TAG chemical speciation and decomposition window data, we observed adecrease in m∕z 60 with photochemical aging due to the decay ofanhydrosugars (including levoglucosan) and other compounds, as well as anincrease in m∕z 60 due to the formation of thermally labile organic acidswithin the PAM reactor, which decompose during TAG sample desorption. Whenaging both types of BBOA (leaf and heartwood), the AMS data exhibit acombination of these two contributing effects, causing limited change to theoverall m∕z 60 signal. Our observations demonstrate the importance ofchemically speciated data in fully understanding bulk aerosol measurementsprovided by the AMS in both laboratory and field studies. 

Dimethyl sulfide (DMS), emitted from the oceans, is the most abundant biological source of sulfur to the marine atmosphere. Atmospheric DMS is oxidized to condensable products that form secondary aerosols that affect Earth’s radiative balance by scattering solar radiation and serving as cloud condensation nuclei. We report the atmospheric discovery of a previously unquantified DMS oxidation product, hydroperoxymethyl thioformate (HPMTF, HOOCH 2 SCHO), identified through global-scale airborne observations that demonstrate it to be a major reservoir of marine sulfur. Observationally constrained model results show that more than 30% of oceanic DMS emitted to the atmosphere forms HPMTF. Coincident particle measurements suggest a strong link between HPMTF concentration and new particle formation and growth. Analyses of these observations show that HPMTF chemistry must be included in atmospheric models to improve representation of key linkages between the biogeochemistry of the ocean, marine aerosol formation and growth, and their combined effects on climate.