Isotopic characterization of nitrogen oxides (NO\u3ci\u3ex\u3c/i\u3e), nitrous acid (HONO), and nitrate (\u3ci\u3ep\u3c/i\u3eNO3-) from laboratory biomass burning during FIREX

New techniques have recently been developed and applied to capture reactive nitrogen species, including nitrogen oxides (NOx D NOCNO2), nitrous acid (HONO), nitric acid (HNO3), and particulate nitrate (pNO3 ), for accurate measurement of their isotopic composition. Here, we report – for the first time – the isotopic composition of HONO from biomass burning (BB) emissions collected during the Fire Influence on Regional to Global Environments Experiment (FIREX, later evolved into FIREX-AQ) at the Missoula Fire Science Laboratory in the fall of 2016. We used our newly developed annular denuder system (ADS), which was verified to completely capture HONO associated with BB in comparison with four other high-timeresolution concentration measurement techniques, including mist chamber–ion chromatography (MC–IC), open-path Fourier transform infrared spectroscopy (OP-FTIR), cavityenhanced spectroscopy (CES), and proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF)

Isotopic characterization of nitrogen oxides (NOx), nitrous acid (HONO), and nitrate (pNO3−) from laboratory biomass burning during FIREX

New techniques have recently been developed and applied to capture reactive nitrogen species, including nitrogen oxides (NOx=NO+NO2), nitrous acid (HONO), nitric acid (HNO3), and particulate nitrate (pNO−3), for accurate measurement of their isotopic composition. Here, we report – for the first time – the isotopic composition of HONO from biomass burning (BB) emissions collected during the Fire Influence on Regional to Global Environments Experiment (FIREX, later evolved into FIREX-AQ) at the Missoula Fire Science Laboratory in the fall of 2016. We used our newly developed annular denuder system (ADS), which was verified to completely capture HONO associated with BB in comparison with four other high-time-resolution concentration measurement techniques, including mist chamber–ion chromatography (MC–IC), open-path Fourier transform infrared spectroscopy (OP-FTIR), cavity-enhanced spectroscopy (CES), and proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF). In 20 “stack” fires (direct emission within ∼5 s of production by the fire) that burned various biomass materials from the western US, δ15N–NOx ranges from −4.3 ‰ to +7.0 ‰, falling near the middle of the range reported in previous work. The first measurements of δ15N–HONO and δ18O–HONO in biomass burning smoke reveal a range of −5.3 ‰ to +5.8 ‰ and +5.2 ‰ to +15.2 ‰, respectively. Both HONO and NOx are sourced from N in the biomass fuel, and δ15N–HONO and δ15N–NOx are strongly correlated (R2=0.89, p\u3c0.001), suggesting HONO is directly formed via subsequent chain reactions of NOx emitted from biomass combustion. Only 5 of 20 pNO−3 samples had a sufficient amount for isotopic analysis and showed δ15N and δ18O of pNO−3 ranging from −10.6 ‰ to −7.4 ‰ and +11.5 ‰ to +14.8 ‰, respectively. Our δ15N of NOx, HONO, and pNO−3 ranges can serve as important biomass burning source signatures, useful for constraining emissions of these species in environmental applications. The δ18O of HONO and NO−3 obtained here verify that our method is capable of determining the oxygen isotopic composition in BB plumes. The δ18O values for both of these species reflect laboratory conditions (i.e., a lack of photochemistry) and would be expected to track with the influence of different oxidation pathways in real environments. The methods used in this study will be further applied in future field studies to quantitatively track reactive nitrogen cycling in fresh and aged western US wildfire plumes

Isotopic evidence for dominant secondary production of HONO in near-ground wildfire plumes

Nitrous acid (HONO) is an important precursor to hydroxyl radical (OH) that determines atmospheric oxidative capacity and thus impacts climate and air quality. Wildfire is not only a major direct source of HONO, it also results in highly polluted conditions that favor the heterogeneous formation of HONO from nitrogen oxides (NOx= NO + NO2) and nitrate on both ground and particle surfaces. However, these processes remain poorly constrained. To quantitatively constrain the HONO budget under various fire and/or smoke conditions, we combine a unique dataset of field concentrations and isotopic ratios (15N / 14N and 18O / 16O) of NOx and HONO with an isotopic box model. Here we report the first isotopic evidence of secondary HONO production in near-ground wildfire plumes (over a sample integration time of hours) and the subsequent quantification of the relative importance of each pathway to total HONO production. Most importantly, our results reveal that nitrate photolysis plays a minor role (\u3c5 %) in HONO formation in daytime aged smoke, while NO2-to-HONO heterogeneous conversion contributes 85 %–95 % to total HONO production, followed by OH + NO (5 %–15 %). At nighttime, heterogeneous reduction of NO2 catalyzed by redox active species (e.g., iron oxide and/or quinone) is essential (≥ 75 %) for HONO production in addition to surface NO2 hydrolysis. Additionally, the 18O / 16O of HONO is used for the first time to constrain the NO-to-NO2 oxidation branching ratio between ozone and peroxy radicals. Our approach provides a new and critical way to mechanistically constrain atmospheric chemistry and/or air quality models on a diurnal timescale

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

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 (delta N-15; delta O-18) 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

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 <i>k</i>₁/<i>k</i>_2a: CH₃O· + O₂ → HCHO + HO₂· and CH₃O· + NO₂ (+M) → CH₃ONO₂ (+M) over the temperature range 250–333 K in an environmental chamber at 700 Torr using Fourier transform infrared detection. Absolute rate constants <i>k</i>₂ 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 <i>k</i>₂ were in excellent agreement with the recommendations of the JPL Data Evaluation panel. The combined data (i.e., <i>k</i>₁/<i>k</i>₂ and <i>k</i>₂) allow the determination of <i>k</i>₁ as 1.3_–0.5^+0.9 × 10^–14 exp[−(663 ± 144)/<i>T</i>] cm³ s^–1, corresponding to 1.4 × 10^–15 cm³ 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, <i>k</i>_H/<i>k</i>_D, can be expressed in the Arrhenius form as <i>k</i>₁/<i>k</i>₃ = (1.7_–0.4^+0.5) exp((306 ± 70)/<i>T</i>). 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., <i>J. Phys. Chem. A</i> <b>2013</b>, <i>117</i>, 14230–14242.

Fire Influence on Regional to Global Environments and Air Quality (FIREX‐AQ)

The NOAA/NASA Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) experiment was a multi-agency, inter-disciplinary research effort to: (a) obtain detailed measurements of trace gas and aerosol emissions from wildfires and prescribed fires using aircraft, satellites and ground-based instruments, (b) make extensive suborbital remote sensing measurements of fire dynamics, (c) assess local, regional, and global modeling of fires, and (d) strengthen connections to observables on the ground such as fuels and fuel consumption and satellite products such as burned area and fire radiative power. From Boise, ID western wildfires were studied with the NASA DC-8 and two NOAA Twin Otter aircraft. The high-altitude NASA ER-2 was deployed from Palmdale, CA to observe some of these fires in conjunction with satellite overpasses and the other aircraft. Further research was conducted on three mobile laboratories and ground sites, and 17 different modeling forecast and analyses products for fire, fuels and air quality and climate implications. From Salina, KS the DC-8 investigated 87 smaller fires in the Southeast with remote and in-situ data collection. Sampling by all platforms was designed to measure emissions of trace gases and aerosols with multiple transects to capture the chemical transformation of these emissions and perform remote sensing observations of fire and smoke plumes under day and night conditions. The emissions were linked to fuels consumed and fire radiative power using orbital and suborbital remote sensing observations collected during overflights of the fires and smoke plumes and ground sampling of fuels