Nitrogen oxides and PAN in plumes from boreal fires during ARCTAS-B and their impact on ozone: an integrated analysis of aircraft and satellite observations

We determine enhancement ratios for NO_x, PAN, and other NO_y species from boreal biomass burning using aircraft data obtained during the ARCTAS-B campaign and examine the impact of these emissions on tropospheric ozone in the Arctic. We find an initial emission factor for NO_x of 1.06 g NO per kg dry matter (DM) burned, much lower than previous observations of boreal plumes, and also one third the value recommended for extratropical fires. Our analysis provides the first observational confirmation of rapid PAN formation in a boreal smoke plume, with 40% of the initial NO_x emissions being converted to PAN in the first few hours after emission. We find little clear evidence for ozone formation in the boreal smoke plumes during ARCTAS-B in either aircraft or satellite observations, or in model simulations. Only a third of the smoke plumes observed by the NASA DC8 showed a correlation between ozone and CO, and ozone was depleted in the plumes as often as it was enhanced. Special observations from the Tropospheric Emission Spectrometer (TES) also show little evidence for enhanced ozone in boreal smoke plumes between 15 June and 15 July 2008. Of the 22 plumes observed by TES, only 4 showed ozone increasing within the smoke plumes, and even in those cases it was unclear that the increase was caused by fire emissions. Using the GEOS-Chem atmospheric chemistry model, we show that boreal fires during ARCTAS-B had little impact on the median ozone profile measured over Canada, and had little impact on ozone within the smoke plumes observed by TES

Near-UV photolysis cross sections of CH_3OOH and HOCH_2OOH determined via action spectroscopy

Knowledge of molecular photolysis cross sections is important for determining atmospheric lifetimes and fates of many species. A method and laser apparatus for measurement of these cross sections in the near-ultraviolet (UV) region is described. The technique is based on action spectroscopy, where the yield of a photodissociation product (in this case OH) is measured as a function of excitation energy. For compounds yielding OH, this method can be used to measure near-UV photodissociation cross section as low as 10−23 cm2 molecule−1. The method is applied to determine the photodissociation cross sections for methyl hydroperoxide (CH3OOH; MHP) and hydroxymethyl hydroperoxide (HOCH2OOH; HMHP) in the 305–365 nm wavelength range. The measured cross sections are in good agreement with previous measurements of absorption cross sections

GFIT2: an experimental algorithm for vertical profile retrieval from near-IR spectra

An algorithm for retrieval of vertical profiles from ground-based spectra in the near IR is described and tested. Known as GFIT2, the algorithm is primarily intended for CO₂, and is used exclusively for CO₂ in this paper. Retrieval of CO₂ vertical profiles from ground-based spectra is theoretically possible, would be very beneficial for carbon cycle studies and the validation of satellite measurements, and has been the focus of much research in recent years. GFIT2 is tested by application both to synthetic spectra and to measurements at two Total Carbon Column Observing Network (TCCON) sites. We demonstrate that there are approximately 3° of freedom for the CO2 profile, and the algorithm performs as expected on synthetic spectra. We show that the accuracy of retrievals of CO₂ from measurements in the 1.61μ (6220 cm⁻¹) spectral band is limited by small uncertainties in calculation of the atmospheric spectrum. We investigate several techniques to minimize the effect of these uncertainties in calculation of the spectrum. These techniques are somewhat effective but to date have not been demonstrated to produce CO₂ profile retrievals with sufficient precision for applications to carbon dynamics. We finish by discussing ongoing research which may allow CO₂ profile retrievals with sufficient accuracy to significantly improve the scientific value of the measurements from that achieved with column retrievals

Near-IR photodissociation of peroxy acetyl nitrate

Measurements of the C-H overtone transition strengths combined with estimates of the photodissociation cross sections for these transitions suggest that near-IR photodissociation of peroxy acetyl nitrate (PAN) is less significant (Jnear−IR ~3×10^−8 s^−1 at noon) in the lower atmosphere than competing sinks resulting from unimolecular decomposition and ultraviolet photolysis. This is in contrast to the photochemical behavior of a related peroxy nitrate, pernitric acid (PNA), that undergoes rapid near-IR photolysis in the atmosphere with Jnear−IR ~10^−5 s^−1 at noon (Roehl et al., 2002). This difference is attributed to the larger binding energy and larger number of vibrational degrees of 10 freedom in PAN, which make 4[Greek nu]CH the lowest overtone excitation with a high photodissociation yield (as opposed to 2[Greek nu]OH in PNA)

Isoprene photooxidation : new insights into the production of acids and organic nitrates

We describe a nearly explicit chemical mechanism for isoprene photooxidation guided by chamber studies that include time-resolved observation of an extensive suite of volatile compounds. We provide new constraints on the chemistry of the poorly-understood isoprene δ-hydroxy channels, which account for more than one third of the total isoprene carbon flux and a larger fraction of the nitrate yields. We show that the cis branch dominates the chemistry of the δ-hydroxy channel with less than 5% of the carbon following the trans branch. The modelled yield of isoprene nitrates is 12±3% with a large difference between the δ and β branches. The oxidation of these nitrates releases about 50% of the NOx. Methacrolein nitrates (modelled yield ≃15±3% from methacrolein) and methylvinylketone nitrates (modelled yield ≃11±3% yield from methylvinylketone) are also observed. Propanone nitrate, produced with a yield of 1% from isoprene, appears to be the longest-lived nitrate formed in the total oxidation of isoprene. We find a large molar yield of formic acid and suggest a novel mechanism leading to its formation from the organic nitrates. Finally, the most important features of this mechanism are summarized in a condensed scheme appropriate for use in global chemical transport models

Exploring Oxidation in the Remote Free Troposphere: Insights from Atmospheric Tomography (ATom)

Earth's atmosphere oxidizes the greenhouse gas methane and other gases, thus determining their lifetimes and oxidation products. Much of this oxidation occurs in the remote, relatively clean free troposphere above the planetary boundary layer, where the oxidation chemistry is thought to be much simpler and better understood than it is in urban regions or forests. The NASA airborne Atmospheric Tomography study (ATom) was designed to produce cross sections of the detailed atmospheric composition in the remote atmosphere over the Pacific and Atlantic Oceans during four seasons. As part of the extensive ATom data set, measurements of the atmosphere's primary oxidant, hydroxyl (OH), and hydroperoxyl (HO₂) are compared to a photochemical box model to test the oxidation chemistry. Generally, observed and modeled median OH and HO₂ agree to with combined uncertainties at the 2σ confidence level, which is ~±40%. For some seasons, this agreement is within ~±20% below 6 km altitude. While this test finds no significant differences, OH observations increasingly exceeded modeled values at altitudes above 8 km, becoming ~35% greater, which is near the combined uncertainties. Measurement uncertainty and possible unknown measurement errors complicate tests for unknown chemistry or incorrect reaction rate coefficients that would substantially affect the OH and HO₂ abundances. Future analysis of detailed comparisons may yield additional discrepancies that are masked in the median values

A Model of Sympatric Speciation Through Reinforcement

Sympatric speciation, i.e. the evolutionary split of one species into two in the same environment, has been a highly troublesome concept. It has been a questioned if it is actually possible. Even though there have been a number of reported results both in the wild and from controlled experiments in laboratories, those findings are both hard to get and hard to analyze, or even repeat. In the current study we propose a mathematical model which addresses the question of sympatric speciation and the evolution of reinforcement. Our aim has been to capture some of the essential features such as: phenotype, resources, competition, heritage, mutation, and reinforcement, in as simple a way as possible. Still, the resulting model is not too easy to grasp with purely analytical tools, so we have also complemented those studies with stochastic simulations. We present a few results that both illustrates the usefulness of such a model, but also rises new biological questions about sympatric speciation and reinforcement in particular

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