Optical Properties of Wintertime Aerosols from Residential Wood Burning in Fresno, CA: Results from DISCOVER-AQ 2013.

The optical properties, composition and sources of the wintertime aerosols in the San Joaquin Valley (SJV) were characterized through measurements made in Fresno, CA during the 2013 DISCOVER-AQ campaign. PM2.5 extinction and absorption coefficients were measured at 405, 532, and 870 nm along with refractory black carbon (rBC) size distributions and concentrations. BC absorption enhancements (Eabs) were measured using two methods, a thermodenuder and mass absorption coefficient method, which agreed well. Relatively large diurnal variations in the Eabs at 405 nm were observed, likely reflecting substantial nighttime emissions of wood burning organic aerosols (OA) from local residential heating. Comparably small diurnal variations and absolute nighttime values of Eabs were observed at the other wavelengths, suggesting limited mixing-driven enhancement. Positive matrix factorization analysis of OA mass spectra from an aerosol mass spectrometer resolved two types of biomass burning OA, which appeared to have different chemical composition and absorptivity. Brown carbon (BrC) absorption was estimated to contribute up to 30% to the total absorption at 405 nm at night but was negligible (<10%) during the day. Quantitative understanding of retrieved BrC optical properties could be improved with more explicit knowledge of the BC mixing state and the distribution of coating thicknesses.

Regional Influence of Aerosol Emissions from Wildfires Driven by Combustion Efficiency: Insights from the BBOP Campaign.

Wildfires are important contributors to atmospheric aerosols and a large source of emissions that impact regional air quality and global climate. In this study, the regional and nearfield influences of wildfire emissions on ambient aerosol concentration and chemical properties in the Pacific Northwest region of the United States were studied using real-time measurements from a fixed ground site located in Central Oregon at the Mt. Bachelor Observatory (∼2700 m a.s.l.) as well as near their sources using an aircraft. The regional characteristics of biomass burning aerosols were found to depend strongly on the modified combustion efficiency (MCE), an index of the combustion processes of a fire. Organic aerosol emissions had negative correlations with MCE, whereas the oxidation state of organic aerosol increased with MCE and plume aging. The relationships between the aerosol properties and MCE were consistent between fresh emissions (∼1 h old) and emissions sampled after atmospheric transport (6-45 h), suggesting that biomass burning organic aerosol concentration and chemical properties were strongly influenced by combustion processes at the source and conserved to a significant extent during regional transport. These results suggest that MCE can be a useful metric for describing aerosol properties of wildfire emissions and their impacts on regional air quality and global climate.

Isomerisation of CF2ClCH2Cl and CFCl2CH2F by interchange of Cl and F atoms with analysis of the unimolecular reactions of both molecules.

The recombination of CF(2)Cl with CH(2)Cl and CFCl(2) with CH(2)F were employed to generate CF(2)ClCH(2)Cl* and CFCl(2)CH(2)F* molecules with 381 and 368 kJ mol(-1), respectively, of vibrational energy in a room-temperature bath gas. The unimolecular reactions of these molecules, which include HCl elimination, HF elimination, and isomerisation by interchange of chlorine and fluorine atoms, were characterized. The three rate constants for CFCl(2)CH(2)F were 2.9×10(7), 0.87×10(7) and 0.04×10(7) s(-1) for HCl elimination, isomerisation and HF elimination, respectively. The isomerisation reaction must be included to have a complete characterization of the unimolecular kinetics of CFCl(2)CH(2)F. The rate constants for HCl elimination and HF elimination from CF(2)ClCH(2)Cl were 14×10(7) and 0.37×10(7) s(-1), respectively. Isomerisation that has a rate constant less than 0.08×10(7) s(-1) is not important. These experimental rate constants were matched to calculated statistical rate constants to assign threshold energies, which are 264, 268, and 297 kJ mol(-1), respectively, for isomerisation, HCl elimination, and HF elimination for CFCl(2)CH(2)F and 314, 251, and 289 kJ mol(-1) in the same order for CF(2)ClCH(2)Cl. Density functional theory was used to evaluate the models that were needed for the statistical rate constants; the computational method was B3PW91/6-31G(d',p'). Threshold energies for the unimolecular reactions of CF(2)ClCH(2)Cl and CFCl(2)CH(2)F are compared to those for CF(2)ClCH(3) and CFCl(2)CH(3) to illustrate the elevation of threshold energies by F- or Cl-atom substitution at the beta carbon atom (identified by C(H)). The DFT calculations systematically underestimate the threshold energy for HCl elimination.

QTAIM analysis of the HF, HCl, HBr, and HOH elimination reactions of halohydrocarbons and halohydroalcohols.

The 1,2-HX elimination reaction (where X = F, Cl, Br, OH) has been established as an important reaction in the degradation of compounds introduced into the upper atmosphere, including common CFC replacement compounds. By analyzing the electron densities of the transition state geometries of these reactions using QTAIM, we see that we can divide these reactions into two types. For HF and HOH elimination, the transition state is a complete ring of bonds, and neither the C-H nor the C-X bonds have been broken at the maximum of energy. There is very little accumulation of electron density on the X atom, with the majority of charge being lost by the hydrogen atom undergoing elimination, being transferred on to the two carbon atoms. In HCl and HBr elimination, a similar loss of electron density of the hydrogen atom is accompanied by significant accumulation of electron density on the X atom and a smaller change in electron density on the carbon atoms. The C-X bond is broken in the transition state geometry, with no ring critical point being present. This may explain the relative stabilities of halohydrocarbons and haloalcohols with respect to loss of H-X.

Characterization of the unimolecular water elimination reaction from 1-propanol, 3,3,3-propan-1-ol-d3, 3,3,3-trifluoropropan-1-ol, and 3-chloropropan-1-ol.

The unimolecular reactions of 1-propanol, 3,3,3-propan-1-ol-d3, 3,3,3-trifluoropropan-1-ol, and 3-chloropropan-1-ol have been studied by the chemical activation technique. The recombination of CH3, CD3, CF3, and CH2Cl radicals with CH2CH2OH radicals at room temperature was used to generate vibrationally excited CH3CH2CH2OH, CD3CH2CH2OH, CF3CH2CH2OH, and CH2ClCH2CH2OH molecules. The principal unimolecular reaction for propanol and propanol-d3 with 90 kcal mol(-1) of vibrational energy is 1,2-H2O elimination with rate constants of 3.4 x 10(5) and 1.4 x 10(5) s(-1), respectively. For CH2ClCH2CH2OH also with 90 kcal mol(-1) of energy, 2,3-HCl elimination with a rate constant of 3.0 x 10(7) s(-1) is more important than 1,2-H2O elimination; the branching fractions are 0.95 and 0.05. For CF3CH2CH2OH with an energy of 102 kcal mol(-1), 1,2-H2O elimination has a rate constant of 7.9 x 10(5) and 2,3-HF elimination has a rate constant of 2.6 x 10(5) s(-1). Density functional theory was used to obtain models for the molecules and their transition states. The frequencies and moments of inertia from these models were used to calculate RRKM rate constants, which were used to assign threshold energies by comparing calculated and experimental rate constants. This comparison gives the threshold energy for H2O elimination from 1-propanol as 64 kcal mol(-1). The threshold energies for 1,2-H2O and 2,3-HCl elimination from CH2ClCH2CH2OH were 59 and 54 kcal mol(-1), respectively. The threshold energies for H2O and HF elimination from CF3CH2CH2OH are 62 and 70 kcal mol(-1), respectively. The structures of the transition states for elimination of HF, HCl, and H2O are compared.

Modeling NH4NO3 Over the San Joaquin Valley During the 2013 DISCOVER-AQ Campaign.

The San Joaquin Valley (SJV) of California experiences high concentrations of particulate matter NH4NO3 during episodes of meteorological stagnation in winter. A rich data set of observations related to NH4NO3 formation was acquired during multiple periods of elevated NH4NO3 during the Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) field campaign in SJV in January and February 2013. Here NH4NO3 is simulated during the SJV DISCOVER-AQ study period with the Community Multiscale Air Quality (CMAQ) model, diagnostic model evaluation is performed using the DISCOVER-AQ data set, and integrated reaction rate analysis is used to quantify HNO3 production rates. Simulated NO3- generally agrees well with routine monitoring of 24-hr average NO3-, but comparisons with hourly average NO3- measurements in Fresno revealed differences at higher time resolution. Predictions of gas-particle partitioning of total nitrate (HNO3 + NO3-) and NHx (NH3 + NH4+) generally agree well with measurements in Fresno, although partitioning of total nitrate to HNO3 is sometimes overestimated at low relative humidity in afternoon. Gas-particle partitioning results indicate that NH4NO3 formation is limited by HNO3 availability in both the model and ambient. NH3 mixing ratios are underestimated, particularly in areas with large agricultural activity, and additional work on the spatial allocation of NH3 emissions is warranted. During a period of elevated NH4NO3, the model predicted that the OH + NO2 pathway contributed 46% to total HNO3production in SJV and the N2O5 heterogeneous hydrolysis pathway contributed 54%. The relative importance of the OH + NO2 pathway for HNO3 production is predicted to increase as NOx emissions decrease.

Observational assessment of the role of nocturnal residual-layer chemistry in determining daytime surface particulate nitrate concentrations.

This study discusses an analysis of combined airborne and ground observations of particulate nitrate (NO3 - (p)) concentrations made during the wintertime DISCOVER-AQ study at one of the most polluted cities in the United States, Fresno, CA in the San Joaquin Valley (SJV) and focuses on development of understanding of the various processes that impact surface nitrate concentrations during pollution events. The results provide an explicit case-study illustration of how nighttime chemistry can influence daytime surface-level NO3 - (p) concentrations, complementing previous studies in the SJV. The observations exemplify the critical role that nocturnal chemical production of NO3 - (p) aloft in the residual layer (RL) can play in determining daytime surface-level NO3 - (p) concentrations. Further, they indicate that nocturnal production of NO3 - (p) in the RL, along with daytime photochemical production, can contribute substantially to the build-up and sustaining of severe pollution episodes. The exceptionally shallow nocturnal boundary layer heights characteristic of wintertime pollution events in the SJV intensifies the importance of nocturnal production aloft in the residual layer to daytime surface concentrations. The observations also demonstrate that dynamics within the RL can influence the early-morning vertical distribution of NO3 - (p), despite low wintertime wind speeds. This overnight reshaping of the vertical distribution above the city plays an important role in determining the net impact of nocturnal chemical production on local and regional surface-level NO3 - (p) concentrations. Entrainment of clean free tropospheric air into the boundary layer in the afternoon is identified as an important process that reduces surface-level NO3 - (p) and limits build-up during pollution episodes. The influence of dry deposition of HNO3 gas to the surface on daytime particulate nitrate concentrations is important but limited by an excess of ammonia in the region, which leads to only a small fraction of nitrate existing in the gas-phase even during the warmer daytime. However, in late afternoon, when diminishing solar heating leads to a rapid fall in the mixed boundary layer height, the impact of surface deposition is temporarily enhanced and can lead to a substantial decline in surface-level particulate nitrate concentrations; this enhanced deposition is quickly arrested by a decrease in surface temperature, which drops the gas-phase fraction to near zero. The overall importance of enhanced late afternoon gas-phase loss to the multiday build-up of pollution events is limited by the very shallow nocturnal boundary layer. The case study here demonstrates that mixing down of NO3 - (p) from the RL can contribute a majority of the surface-level NO3 - (p) in the morning (here, ~80%), and a strong influence can persist into the afternoon even when photochemical production is maximum. The particular day-to-day contribution of aloft nocturnal NO3 - (p) production to surface concentrations will depend on prevailing chemical and meteorological conditions. Although specific to the SJV, the observations and conceptual framework further developed here provide general insights into the evolution of pollution episodes in wintertime environments.