Identification of the ns and nd Rydberg states of O2 for n=3–5

The 4s‐3d and 5s‐4dRydberg complexes of diatomic oxygen have been studied by (2+1) resonance‐enhanced multiphoton ionization of the X  3∑ g − ground state of O2. We have located and identified at least two vibrational levels of each of the following states: Three of four expected 4sσ Π states; all four expected 5sσ Π states; 18 of 22 expected 3d states (with only the states of the 3dσ orbital remaining unobserved); and 5 of the 10 predicted 4dπ states. State assignments were assisted by the following: the results of rotational cooling and laser polarization experiments which facilitated the rotational analysis, band positions, band intensities, and parameterized calculations. The experimentally determined state locations are compared with the state locations obtained from ab initio calculations. We have carried out isotope experiments and rotational linewidth analysis to study in some detail the mixing between the Rydberg states and the repulsive valence states as well as the mixing between the Rydberg states themselves. We conclude that direct predissociation dominates indirect predissociation as a dissociative mechanism, but there is evidence of Δv≠0 interactions which perturb the rotational structure of the 3dπ∑ and Δ states. The relative intensities of the states detected are found to span a range in excess of 104 with the nsσ Π states being the weakest and the ndπ ∑ states being the strongest. Photoionization of the ndπ ∑ states appears to be most affected by the shape resonance in the continuum. Our measurements confirm the expectation that many of the properties of the Rydberg states in the same series scale as (n*)−3

Identification of the nd Δ and Σ States and the 1,3Φ←←X 3Σ− g Transition of O2 by Resonant Multiphoton Ionization

Spectra of the 3dRydberg state region of O2 have been obtained by two‐photon resonant ionization of the ground electronic state. By varying the rotational distribution and radiation polarization, all observed bands were identified and attributed to excitation of Σ, Δ, and Φ states. Earlier assignments were corrected. The Δ and Φ assignments are complete while the Σ assignments are so far incomplete

Emission factors for open and domestic biomass burning for use in atmospheric models

Biomass burning (BB) is the second largest source of trace gases and the largest source of primary fine carbonaceous particles in the global troposphere. Many recent BB studies have provided new emission factor (EF) measurements. This is especially true for non-methane organic compounds (NMOC), which influence secondary organic aerosol (SOA) and ozone formation. New EF should improve regional to global BB emissions estimates and therefore, the input for atmospheric models. In this work we present an up-to-date, comprehensive tabulation of EF for known pyrogenic species based on measurements made in smoke that has cooled to ambient temperature, but not yet undergone significant photochemical processing. All EFs are converted to one standard form (g compound emitted per kg dry biomass burned) using the carbon mass balance method and they are categorized into 14 fuel or vegetation types. Biomass burning terminology is defined to promote consistency. We compile a large number of measurements of biomass consumption per unit area for important fire types and summarize several recent estimates of global biomass consumption by the major types of biomass burning. Post emission processes are discussed to provide a context for the emission factor concept within overall atmospheric chemistry and also highlight the potential for rapid changes relative to the scale of some models or remote sensing products. Recent work shows that individual biomass fires emit significantly more gas-phase NMOC than previously thought and that including additional NMOC can improve photochemical model performance. A detailed global estimate suggests that BB emits at least 400 Tg yr^(−1) of gas-phase NMOC, which is almost 3 times larger than most previous estimates. Selected recent results (e.g. measurements of HONO and the BB tracers HCN and CH_3CN) are highlighted and key areas requiring future research are briefly discussed

In situ measurements of trace gases, PM, and aerosol optical properties during the 2017 NW US wildfire smoke event

In mid-August through mid-September of 2017 a major wildfire smoke and haze episode strongly impacted most of the NW US and SW Canada. During this period our ground-based site in Missoula, Montana, experienced heavy smoke impacts for ∼ 500h (up to 471μ-3 hourly average PM2.5). We measured wildfire trace gases, PM2.5 (particulate matter ≤2.5μm in diameter), and black carbon and submicron aerosol scattering and absorption at 870 and 401nm. This may be the most extensive real-time data for these wildfire smoke properties to date. Our range of trace gas ratios for δNH3 δCO and δC2H4 δCO confirmed that the smoke from mixed, multiple sources varied in age from ∼ 2-3h to ∼ 1-2 days. Our study-average δCH4 δCO ratio (0.166±0.088) indicated a large contribution to the regional burden from inefficient smoldering combustion. Our δBC δCO ratio (0.0012±0.0005) for our ground site was moderately lower than observed in aircraft studies (∼ 0.0015) to date, also consistent with a relatively larger contribution from smoldering combustion. Our δBC δPM2.5 ratio (0.0095±0.0003) was consistent with the overwhelmingly non-BC (black carbon), mostly organic nature of the smoke observed in airborne studies of wildfire smoke to date. Smoldering combustion is usually associated with enhanced PM emissions, but our δPM2.5 δCO ratio (0.126±0.002) was about half the δPM1.0 δCO measured in fresh wildfire smoke from aircraft (∼ 0.266). Assuming PM2.5 is dominated by PM1, this suggests that aerosol evaporation, at least near the surface, can often reduce PM loading and its atmospheric/air-quality impacts on the timescale of several days. Much of the smoke was emitted late in the day, suggesting that nighttime processing would be important in the early evolution of smoke. The diurnal trends show brown carbon (BrC), PM2.5, and CO peaking in the early morning and BC peaking in the early evening. Over the course of 1 month, the average single scattering albedo for individual smoke peaks at 870nm increased from ∼ 0.9 to ∼ 0.96. B/scat401 B/scat870 was used as a proxy for the size and photochemical age of the smoke particles, with this interpretation being supported by the simultaneously observed ratios of reactive trace gases to CO. The size and age proxy implied that the Ångström absorption exponent decreased significantly after about 10h of daytime smoke aging, consistent with the only airborne measurement of the BrC lifetime in an isolated plume. However, our results clearly show that non-BC absorption can be important in typical regional haze and moderately aged smoke, with BrC ostensibly accounting for about half the absorption at 401nm on average for our entire data set

The tropical forest and fire emissions experiment: laboratory fire measurements and synthesis of campaign data

International audienceAs part of the Tropical Forest and Fire Emissions Experiment (TROFFEE), tropical forest fuels were burned in a large, biomass-fire simulation facility and the smoke was characterized with open-path Fourier transform infrared spectroscopy (FTIR), proton-transfer reaction mass spectrometry (PTR-MS), gas chromatography (GC), GC/PTR-MS, and filter sampling of the particles. In most cases, about one-third of the fuel chlorine ended up in the particles and about one-half remained in the ash. About 50% of the mass of non-methane organic compounds (NMOC) emitted by these fires could be identified with the available instrumentation. The lab fire emission factors (EF, g compound emitted per kg fuel burned) were coupled with EF obtained during the TROFFEE airborne and ground-based field campaigns. This revealed several types of EF dependence on parameters such as the ratio of flaming to smoldering combustion and fuel characteristics. The synthesis of data from the different TROFFEE platforms was also used to derive EF for all the measured species for both primary deforestation fires and pasture maintenance fires ? the two main types of biomass burning in the Amazon. Many of the EF are larger than those in widely-used earlier work. This is mostly due to the inclusion of newly-available, large EF for the initially-unlofted smoldering emissions and the assumption that these emissions make a significant contribution (~40%) to the total emissions from pasture fires. The TROFFEE EF for particles with aerodynamic diameter 2.5) is 14.8 g/kg for primary deforestation fires and 18.7 g/kg for pasture maintenance fires. These EFPM2.5 are significantly larger than a previous recommendation (9.1 g/kg) and lead to an estimated pyrogenic primary PM2.5 source for the Amazon that is 84% larger. Regional through global budgets for biogenic and pyrogenic emissions were roughly estimated. Coupled with previous measurements of secondary aerosol growth in the Amazon and source apportionment studies, the regional budgets suggest that ~5% of the total mass of the regionally generated NMOC end up as secondary organic aerosol within the Amazonian boundary layer within 1?3 days. The global budgets confirm that biogenic emissions and biomass burning are the two largest global sources of NMOC with an estimated production of approximately 1000 and 500 Tg/yr, respectively. It follows that plants and fires may also be the two main global sources of secondary organic aerosol. A limited set of emission ratios (ER) is given for sugar cane burning, which may help estimate the air quality impacts of burning this major crop, which is often grown in densely populated areas

Aerosol Mass and Optical Properties, Smoke Influence on O\u3csub\u3e3\u3c/sub\u3e, and High NO\u3csub\u3e3\u3c/sub\u3e Production Rates in a Western U.S. City Impacted by Wildfires

Evaluating our understanding of smoke from wild and prescribed fires can benefit from downwind measurements that include inert tracers to test production and transport and reactive species to test chemical mechanisms. We characterized smoke from fires in coniferous forest fuels for \u3e1,000 hr over two summers (2017 and 2018) at our Missoula, Montana, surface station and found a narrow range for key properties. ΔPM2.5/ΔCO was 0.1070 ± 0.0278 (g/g) or about half the age-independent ratios obtained at free troposphere elevations (0.2348 ± 0.0326). The average absorption Ångström exponent across both years was 1.84 ± 0.18, or about half the values available for very fresh smoke. Brown carbon (BrC) was persistent (~50% of absorption at 401 nm) in both years, despite differences in smoke age. ΔBC/ΔCO doubled from 2017 to 2018, but the average across 2 years was within 33% of recent airborne measurements, suggesting low sampling bias among platforms. Switching from a 1.0 to a 2.5 micron cutoff increased the mass scattering and mass absorption coefficients, suggesting often overlooked supermicron particles impact the optical properties of moderately aged smoke. O3 was elevated ~6 ppb on average over a full diurnal period when wildfire smoke was present, and smoke-associated O3 increases were highest (~9 pbb) at night, suggesting substantial upwind production. NOx was mostly local in origin. NOx spurred high rates of NO3 production, including in the presence of wildfire smoke (up to 2.44 ppb hr−1) and at least one nighttime BrC secondary formation event that could have impacted next-day photochemistry

Evolution of trace gases and particles emitted by a chaparral fire in California

Biomass burning (BB) is a major global source of trace gases and particles. Accurately representing the production and evolution of these emissions is an important goal for atmospheric chemical transport models. We measured a suite of gases and aerosols emitted from an 81 hectare prescribed fire in chaparral fuels on the central coast of California, US on 17 November 2009. We also measured physical and chemical changes that occurred in the isolated downwind plume in the first ~4 h after emission. The measurements were carried out onboard a Twin Otter aircraft outfitted with an airborne Fourier transform infrared spectrometer (AFTIR), aerosol mass spectrometer (AMS), single particle soot photometer (SP2), nephelometer, LiCor CO_2 analyzer, a chemiluminescence ozone instrument, and a wing-mounted meteorological probe. Our measurements included: CO_2; CO; NO_x; NH_3; non-methane organic compounds; organic aerosol (OA); inorganic aerosol (nitrate, ammonium, sulfate, and chloride); aerosol light scattering; refractory black carbon (rBC); and ambient temperature, relative humidity, barometric pressure, and three-dimensional wind velocity. The molar ratio of excess O_3 to excess CO in the plume (ΔO_3/ΔCO) increased from −5.13 (±1.13) × 10^(−3) to 10.2 (±2.16) × 10^(−2) in ~4.5 h following smoke emission. Excess acetic and formic acid (normalized to excess CO) increased by factors of 1.73 ± 0.43 and 7.34 ± 3.03 (respectively) over the same time since emission. Based on the rapid decay of C_2H_4 we infer an in-plume average OH concentration of 5.27 (±0.97) × 10^6 molec cm^(−3), consistent with previous studies showing elevated OH concentrations in biomass burning plumes. Ammonium, nitrate, and sulfate all increased over the course of 4 h. The observed ammonium increase was a factor of 3.90 ± 2.93 in about 4 h, but accounted for just ~36% of the gaseous ammonia lost on a molar basis. Some of the gas phase NH_3 loss may have been due to condensation on, or formation of, particles below the AMS detection range. NO_x was converted to PAN and particle nitrate with PAN production being about two times greater than production of observable nitrate in the first ~4 h following emission. The excess aerosol light scattering in the plume (normalized to excess CO_2) increased by a factor of 2.50 ± 0.74 over 4 h. The increase in light scattering was similar to that observed in an earlier study of a biomass burning plume in Mexico where significant secondary formation of OA closely tracked the increase in scattering. In the California plume, however, ΔOA/ΔCO_2 decreased sharply for the first hour and then increased slowly with a net decrease of ~20% over 4 h. The fraction of thickly coated rBC particles increased up to ~85% over the 4 h aging period. Decreasing OA accompanied by increased scattering/particle coating in initial aging may be due to a combination of particle coagulation and evaporation processes. Recondensation of species initially evaporated from the particles may have contributed to the subsequent slow rise in OA. We compare our results to observations from other plume aging studies and suggest that differences in environmental factors such as smoke concentration, oxidant concentration, actinic flux, and RH contribute significantly to the variation in plume evolution observations

Biomass burning and urban air pollution over the Central Mexican Plateau

Observations during the 2006 dry season of highly elevated concentrations of cyanides in the atmosphere above Mexico City (MC) and the surrounding plains demonstrate that biomass burning (BB) significantly impacted air quality in the region. We find that during the period of our measurements, fires contribute more than half of the organic aerosol mass and submicron aerosol scattering, and one third of the enhancement in benzene, reactive nitrogen, and carbon monoxide in the outflow from the plateau. The combination of biomass burning and anthropogenic emissions will affect ozone chemistry in the MC outflow

Trace gas and particle emissions from domestic and industrial biofuel use and garbage burning in central Mexico

In central Mexico during the spring of 2007 we measured the initial emissions of 12 gases and the aerosol speciation for elemental and organic carbon (EC, OC), anhydrosugars, Cl−, NO[subscript 3]−, and 20 metals from 10 cooking fires, four garbage fires, three brick making kilns, three charcoal making kilns, and two crop residue fires. Global biofuel use has been estimated at over 2600 Tg/y. With several simple case studies we show that cooking fires can be a major, or the major, source of several gases and fine particles in developing countries. Insulated cook stoves with chimneys were earlier shown to reduce indoor air pollution and the fuel use per cooking task. We confirm that they also reduce the emissions of VOC pollutants per mass of fuel burned by about half. We did not detect HCN emissions from cooking fires in Mexico or Africa. Thus, if regional source attribution is based on HCN emissions typical for other types of biomass burning (BB), then biofuel use and total BB will be underestimated in much of the developing world. This is also significant because cooking fires are not detected from space. We estimate that ~2000 Tg/y of garbage are generated globally and about half may be burned, making this a commonly overlooked major global source of emissions. We estimate a fine particle emission factor (EFPM2.5) for garbage burning of ~10.5±8.8 g/kg, which is in reasonable agreement with very limited previous work. We observe large HCl emission factors in the range 2–10 g/kg. Consideration of the Cl content of the global waste stream suggests that garbage burning may generate as much as 6–9 Tg/yr of HCl, which would make it a major source of this compound. HCl generated by garbage burning in dry environments may have a relatively greater atmospheric impact than HCl generated in humid areas. Garbage burning PM[subscript 2.5] was found to contain levoglucosan and K in concentrations similar to those for biomass burning, so it could be a source of interference in some areas when using these tracers to estimate BB. Galactosan was the anhydrosugar most closely correlated with BB in this study. Fine particle antimony (Sb) shows initial promise as a garbage burning tracer and suggests that this source could contribute a significant amount of the PM2.5 in the Mexico City metropolitan area. The fuel consumption and emissions due to industrial biofuel use are difficult to characterize regionally. This is partly because of the diverse range of fuels used and the very small profit margins of typical micro-enterprises. Brick making kilns produced low total EFPM[subscript 2.5] (~1.6 g/kg), but very high EC/OC ratios (6.72). Previous literature on brick kilns is scarce but does document some severe local impacts. Coupling data from Mexico, Brazil, and Zambia, we find that charcoal making kilns can exhibit an 8-fold increase in VOC/CO over their approximately one-week lifetime. Acetic acid emission factors for charcoal kilns were much higher in Mexico than elsewhere. Our dirt charcoal kiln EFPM2.5 emission factor was ~1.1 g/kg, which is lower than previous recommendations intended for all types of kilns. We speculate that some PM[subscript 2.5] is scavenged in the walls of dirt kilns.National Science Foundation (U.S.) (Grant ATM-0513055)United States. Dept. of Defense (Strategic Environmental Research and Development Program (SERDP))United States. Dept. of Agriculture (Agreement 07-JV-11221649-060)United States. Dept. of Agriculture (Agreement 08-JV-11272166-039)United States. Forest ServiceRocky Mountain Research Station (Fort Collins, Colo.)Pacific Southwest Research Statio

The Tropical Forest and Fire Emissions Experiment: method evaluation of volatile organic compound emissions measured by PTR-MS, FTIR, and GC from tropical biomass burning

Volatile Organic Compound (VOC) emissions from fires in tropical forest fuels were quantified using Proton-Transfer-Reaction Mass Spectrometry (PTRMS), Fourier Transform Infrared Spectroscopy (FTIR) and gas chromatography (GC) coupled to PTRMS (GC-PTR-MS). We investigated VOC emissions from 19 controlled laboratory fires at the USFS (United States Forest Service) Fire Sciences Laboratory and 16 fires during an intensive airborne field campaign during the peak of the burning season in Brazil in 2004. The VOC emissions were dominated by oxygenated VOCs (OVOC) (OVOC/NMHC ~4:1, NMHC: non-methane hydrocarbons) The specificity of the PTR-MS instrument, which measures the mass to charge ratio of VOCs ionized by H<sub>3</sub>O<sup>+</sup> ions, was validated by gas chromatography and by intercomparing in-situ measurements with those obtained from an open path FTIR instrument. Emission ratios for methyl vinyl ketone, methacrolein, crotonaldehyde, acrylonitrile and pyrrole were measured in the field for the first time. Our measurements show a higher contribution of OVOCs than previously assumed for modeling purposes. Comparison of fresh (<15 min) and aged (>1 h–1 d) smoke suggests altered emission ratios due to gas phase chemistry for acetone but not for acetaldehyde and methanol. Emission ratios for numerous, important, reactive VOCs with respect to acetonitrile (a biomass burning tracer) are presented