Simultaneous Measurements of Atmospheric HONO and NO2 via Absorption Spectroscopy using Tunable Mid-Infrared Continuous-wave Quantum Cascade Lasers

Nitrous acid (HONO) is important as a significant source of hydroxyl radical (OH) in the troposphere and as a potent indoor air pollutant. It is thought to be generated in both environments via heterogeneous reactions involving nitrogen dioxide $(NO_2)$. In order to enable fast-response HONO detection suitable for eddy-covariance flux measurements and to provide a direct method that avoids interferences associated with derivatization, we have developed a 2-channel tunable infrared laser differential absorption spectrometer (TILDAS) capable of simultaneous high-frequency measurements of HONO and NO2. Beams from two mid-infrared continuous-wave mode quantum cascade lasers (cw-QCLs) traverse separate 210 m paths through a multi-pass astigmatic sampling cell at reduced pressure for the direct detection of HONO $(1660 cm^{−1})$ and $(NO_2)$ $(1604 cm^{−1})$. The resulting one-second detection limits (S/N=3) are 300 and 30 ppt (pmol/mol) for HONO and $(NO_2)$, respectively. Our HONO quantification is based on revised line-strengths and peak positions for cis-HONO in the 6-micron spectral region that were derived from laboratory measurements. An essential component of ambient HONO measurements is the inlet system and we demonstrate that heated surfaces and reduced pressure minimize sampling artifacts.Earth and Planetary SciencesEngineering and Applied Science

Uptake Coefficients of Some Volatile Organic Compounds by Soot and Their Application in Understanding Particulate Matter Evolution in Aircraft Engine Exhaust Plumes

To assist microphysical modeling on particulate matter (PM) evolution emitted from aircraft engines, uptake coefficients of some volatile organic compounds on soot were experimentally determined in this study. The determined values vary from (1.0±0.1)×10⁻⁶ for water-miscible propylene glycol to (2.5±0.1)×10⁻⁵ for 2,6-dimethylnaphthalene, a polycyclic aromatic hydrocarbon. An inverse power-law correlation between uptake coefficient on soot and solubility in water was observed. Using the correlation, microphysical simulations were performed for the exhaust plume evolution from an idling aircraft, and we found that the model-predicted volatile PM composition on soot is comparable with those results from past field measurements.United States. Department of Defense (Contract W912HQ-08-C-0052

Modelling carbonaceous aerosol from residential solid fuel burning with different assumptions for emissions

Evidence is accumulating that emissions of primary particulate matter (PM) from residential wood and coal combustion in the UK may be underestimated and/or spatially misclassified. In this study, different assumptions for the spatial distribution and total emission of PM from solid fuel (wood and coal) burning in the UK were tested using an atmospheric chemical transport model. Modelled concentrations of the PM components were compared with measurements from aerosol mass spectrometers at four sites in central and Greater London (ClearfLo campaign, 2012), as well as with measurements from the UK black carbon network. The two main alternative emission scenarios modelled were Base4x and combRedist. For Base4x, officially reported PM2.5 from the residential and other non-industrial combustion source sector were increased by a factor of four. For the combRedist experiment, half of the baseline emissions from this same source were redistributed by residential population density to simulate the effect of allocating some emissions to the smoke control areas (that are assumed in the national inventory to have no emissions from this source). The Base4x scenario yielded better daily and hourly correlations with measurements than the combRedist scenario for year-long comparisons of the solid fuel organic aerosol (SFOA) component at the two London sites. However, the latter scenario better captured mean measured concentrations across all four sites. A third experiment, Redist – all emissions redistributed linearly to population density, is also presented as an indicator of the maximum concentrations an assumption like this could yield. The modelled elemental carbon (EC) concentrations derived from the combRedist experiments also compared well with seasonal average concentrations of black carbon observed across the network of UK sites. Together, the two model scenario simulations of SFOA and EC suggest both that residential solid fuel emissions may be higher than inventory estimates and that the spatial distribution of residential solid fuel burning emissions, particularly in smoke control areas, needs re-evaluation. The model results also suggest the assumed temporal profiles for residential emissions may require review to place greater emphasis on evening (including “discretionary”) solid fuel burning

Oxygenated Aromatic Compounds are Important Precursors of Secondary Organic Aerosol in Biomass Burning Emissions

Biomass burning is the largest combustion-related source of volatile organic compounds (VOCs) to the atmosphere. We describe the development of a state-of-the-science model to simulate the photochemical formation of secondary organic aerosol (SOA) from biomass-burning emissions observed in dry (RH <20%) environmental chamber experiments. The modeling is supported by (i) new oxidation chamber measurements, (ii) detailed concurrent measurements of SOA precursors in biomass-burning emissions, and (iii) development of SOA parameters for heterocyclic and oxygenated aromatic compounds based on historical chamber experiments. We find that oxygenated aromatic compounds, including phenols and methoxyphenols, account for slightly less than 60% of the SOA formed and help our model explain the variability in the organic aerosol mass (R² = 0.68) and O/C (R² = 0.69) enhancement ratios observed across 11 chamber experiments. Despite abundant emissions, heterocyclic compounds that included furans contribute to ∼20% of the total SOA. The use of pyrolysis-temperature-based or averaged emission profiles to represent SOA precursors, rather than those specific to each fire, provide similar results to within 20%. Our findings demonstrate the necessity of accounting for oxygenated aromatics from biomass-burning emissions and their SOA formation in chemical mechanisms

Observation of a New J(PC)=1(+-) Isoscalar State in the Reaction Pi- Proton -> Omega Eta Neutron at 18 GeV/c

Results are presented on a partial wave analysis of the Omega Eta final state produced in Pi- Proton interactions at 18 GeVc where Omega -> Pi+ Pi- Pi0, Pi0 -> 2 Gammas, and Eta -> 2 Gammas. We observe the previously unreported decay mode Omega(1650) -> Omega Eta and a new 1(+-) meson state h1(1595) with a mass M=1594(15)(+10)(-60) MeV/c^2 and a width Gamma=384(60)(+70)(-100) MeV/c^2. The h1(1595) state exhibits resonant-like phase motion relative to the Omega(1650).Comment: Submitted to Physics Letters B Eight total pages including 11 figures and 1 tabl