Quantifying the Nitrogen Sources and Secondary Formation of Ambient HONO with a Stable Isotopic Method.

Nitrous acid (HONO) is a reactive gas that plays an important role in atmospheric chemistry. However, accurately quantifying its direct emissions and secondary formation in the atmosphere as well as attributing it to specific nitrogen sources remains a significant challenge. In this study, we developed a novel method using stable nitrogen and oxygen isotopes (δ15N; δ18O) for apportioning ambient HONO in an urban area in North China. The results show that secondary formation was the dominant HONO formation processes during both day and night, with the NO2 heterogeneous reaction contributing 59.0 ± 14.6% in daytime and 64.4 ± 10.8% at nighttime. A Bayesian simulation demonstrated that the average contributions of coal combustion, biomass burning, vehicle exhaust, and soil emissions to HONO were 22.2 ± 13.1, 26.0 ± 5.7, 28.6 ± 6.7, and 23.2 ± 8.1%, respectively. We propose that the isotopic method presents a promising approach for identifying nitrogen sources and the secondary formation of HONO, which could contribute to mitigating HONO and its adverse effects on air quality.

Beyond the Ångström Exponent: Probing Additional Information in Spectral Curvature and Variability of In Situ Aerosol Hyperspectral (0.3-0.7 µm) Optical Properties.

Ångström exponents (α) allow reconstruction of aerosol optical spectra over a broad range of wavelengths from measurements at two or more wavelengths. Hyperspectral measurements of atmospheric aerosols provide opportunities to probe measured spectra for information inaccessible from only a few wavelengths. Four sets of hyperspectral in situ aerosol optical coefficients (aerosol-phase total extinction, σ ext, and absorption, σ abs; liquid-phase soluble absorption from methanol, σ MeOH-abs, and water, σ DI-abs, extracts) were measured from biomass burning aerosols (BBAs). Hyperspectral single scattering albedo (ω), calculated from σ ext and σ abs, provide spectral resolution over a wide spectral range rare for this optical parameter. Observed spectral shifts between σ abs and σ MeOH-abs/σ DI-abs argue in favor of measuring σ abs rather than reconstructing it from liquid extracts. Logarithmically transformed spectra exhibited curvature better fit by second-order polynomials than linear α. Mapping second order fit coefficients (a 1, a 2) revealed samples from a given fire tended to cluster together, that is, aerosol spectra from a given fire were similar to each other and somewhat distinct from others. Separation in (a 1, a 2) space for spectra with the same α suggest additional information in second-order parameterization absent from the linear fit. Spectral features found in the fit residuals indicate more information in the measured spectra than captured by the fits. Above-detection σ MeOH-abs at 0.7 µm suggests assuming all absorption at long visible wavelengths is BC to partition absorption between BC and brown carbon (BrC) overestimates BC and underestimates BrC across the spectral range. Hyperspectral measurements may eventually discriminate BBA among fires in different ecosystems under variable conditions.

Formation of Substituted Alkyls as Precursors of Peroxy Radicals with a Rapid H-Shift in the Atmosphere.

Long straight-chain alkyl peroxy (ROO) radicals substituted with C═C and oxo functional groups are expected to undergo a rapid hydrogen shift (H-shift), which is a critical step in the atmospheric autoxidation mechanism. The existence of a weak tertiary C-H bond plays a key role in the rapid H-shift. Here, the reaction kinetics between OH and two typical long straight-chain functionalized volatile organic compounds, 3-methyl-1-hexene (3-MH) and 2-methylpentanal (2-MP), was theoretically investigated to reveal the fate of the weak C-H bond. The results indicate that the most favored reaction pathways are direct consumption (H-abstraction of 2-MP) and indirect destruction (addition of OH to 3-MH) of the "weak" tertiary C-H bond. The yields of abstraction pathways producing precursors of ROO radicals that undergo rapid H-shifts are computed to be less than 10% for both 3-MH + OH and 2-MP + OH reactions.

Exploring the OH-initiated reactions of styrene in the atmosphere and the role of van der Waals complex.

Reacting with OH provides a major sink for styrene in the atmosphere, with three possible pathways including OH-addition, H-abstraction and addition-dissociation reactions. However, the total rate coefficients of styrene + OH were measured as 1.2-6.2 × 10-11 cm3 molecule-1 s-1 under atmospheric conditions, varying by a maximum factor of 5. On the other hand, only one theoretical work reported this rate coefficient as 19.1 × 10-11 cm3 molecule-1 s-1, which exhibits up to 16 times that measured in laboratory studies. In the present study, the reaction kinetics of styrene + OH was extensively studied with high-level quantum chemical methods combined with RRKM/master equation simulations. In particular, we carried out theoretical treatments for the formation of pre-reaction Van der Waals complexes of styrene + OH, and examined their influence on the reaction kinetics. The total rate coefficient for styrene + OH is calculated to be 1.7 × 10-11 cm3 molecule-1 s-1 at 300 K, 1 atm. The main products are addß (88.2%), add5 (6.9%), addα (1.9%) and add3 (1.7%). Using our computed rate coefficient and the global atmospheric hydroxyl radical concentration (2 × 106 radicals per cm3), the lifetime of styrene in the atmosphere is estimated at 8.0 h. The degradation of styrene might be negligible for the formation of ozone in the atmosphere based upon the photochemical ozone creation potentials calculation. The computed product yields indicate that addß via subsequent reactions could significantly produce formaldehyde and benzaldehyde that were observed in previous experimental studies on styrene oxidation, and contribute to the formation of secondary organic aerosols.

Collection Method for Isotopic Analysis of Gaseous Nitrous Acid.

The sources and chemistry of gaseous nitrous acid (HONO) in the environment are of great interest. HONO is a major source of atmospheric hydroxyl radical (OH), which impacts air quality and climate. HONO is also a major indoor pollutant that threatens human health. However, the large uncertainty of HONO sources and chemistry hinders an accurate prediction of the OH budget. Isotopic analysis of HONO may provide a tool for tracking the sources and chemistry of HONO. In this study, a modified annular denuder system (ADS) was developed to quantitatively capture HONO for offline nitrogen and oxygen isotopic analysis (δ15N and δ18O) using the denitrifier method. The ADS method was tested using laboratory generated HONO (400 ppbv to 1 ppmv) and validated by parallel HONO collection with a standard, basic impinger (BI) method. The ADS system shows complete capture of HONO without isotopic fractionation. The uncertainty (1σ) based on repeated measurements across the entire analytical procedure is 0.6‰ for δ15N and 0.5‰ for δ18O. The ADS method was also tested in roadside collections of ambient HONO (0.4-1.3 ppbv) for isotopic analysis and was found to be robust for low concentration collections over 3 and 12 h collection times. In order to ensure ability to use this method in the laboratory and in the field, storage conditions for the collected HONO samples were tested and samples can be stored with consistent δ15N and δ18O for 60 days. This method enables future work to utilize the isotopic composition of HONO for studying HONO chemical formation pathways, as well as atmospheric sources and chemistry.

Cascade upgrading of γ-valerolactone to biofuels.

Cascade upgrading of γ-valerolactone (GVL), produced from renewable cellulosic biomass, with selective conversion to biofuels pentyl valerate (PV) and pentane in one pot using a bifunctional Pd/HY catalyst is described. Excellent catalytic performance (over 99% conversion of GVL, 60.6% yield of PV and 22.9% yield of pentane) was achieved in one step. These biofuels can be targeted for gasoline and jet fuel applications.

Rate constants and kinetic isotope effects for methoxy radical reacting with NO2 and O2.

Relative rate studies were carried out to determine the temperature dependent rate constant ratio k1/k2a: CH3O· + O2 → HCHO + HO2· and CH3O· + NO2 (+M) → CH3ONO2 (+M) over the temperature range 250­333 K in an environmental chamber at 700 Torr using Fourier transform infrared detection. Absolute rate constants k2 were determined using laser flash photolysis/laser-induced fluorescence under the same conditions. The analogous experiments were carried out for the reactions of the perdeuterated methoxy radical (CD3O·). Absolute rate constants k2 were in excellent agreement with the recommendations of the JPL Data Evaluation panel. The combined data (i.e., k1/k2 and k2) allow the determination of k1 as 1.3(­0.5)(+0.9) × 10(­14) exp[−(663 ± 144)/T] cm(3) s(­1), corresponding to 1.4 × 10(­15) cm(3) s(­1) at 298 K. The rate constant at 298 K is in excellent agreement with previous work, but the observed temperature dependence is less than was previously reported. The deuterium isotope effect, kH/kD, can be expressed in the Arrhenius form as k1/k3 = (1.7(­0.4)(+0.5)) exp((306 ± 70)/T). The deuterium isotope effect does not appear to be greatly influenced by tunneling, which is consistent with a previous theoretical work by Hu and Dibble. (Hu, H.; Dibble, T. S., J. Phys. Chem. A 2013, 117, 14230­14242.)

The model of nano-scale copper particle removal from silicon surface in high pressure CO2 + H2O and CO2 + H2O + IPA cleaning solutions.

This study focuses on the description of the static forces in CO2-H2O and CO2-H2O-IPA cleaning solutions with a separate fluid phase entrapped between nano-scale copper particles and a silicon surface. Calculations demonstrate that increasing the pressure of the cleaning system decreases net adhesion force (NAF) between the particle and silicon. The NAF of a particle for in CO2-H2O-IPA system is less than that in CO2-H2O system, suggesting that the particles enter into bulk layer more easily as the CO2-H2O cleaning system is added IPA.