Isoprene Peroxy Radical Dynamics

Approximately 500 Tg of 2-methyl-1,3-butadiene (isoprene) is emitted by deciduous trees each year. Isoprene oxidation in the atmosphere is initiated primarily by addition of hydroxyl radicals (OH) to C_4 or C_1 in a ratio 0.57 ± 0.03 (1σ) to produce two sets of distinct allylic radicals. Oxygen (O_2) adds to these allylic radicals either δ (Z or E depending on whether the allylic radical is cis or trans) or β to the OH group forming six distinct peroxy radical isomers. Due to the enhanced stability of the allylic radical, however, these peroxy radicals lose O_2 in competition with bimolecular reactions. In addition, the Z-δ hydroxy peroxy radical isomers undergo unimolecular 1,6 H-shift isomerization. Here, we use isomer-resolved measurements of the reaction products of the peroxy radicals to diagnose this complex chemistry. We find that the ratio of δ to β hydroxy peroxy radicals depends on their bimolecular lifetime (τ_(bimolecular)). At τ_(bimolecular) ≈ 0.1 s, a transition occurs from a kinetically to a largely thermodynamically controlled distribution at 297 K. Thus, in nature, where τ_(bimolecular) > 10 s, the distribution of isoprene hydroxy peroxy radicals will be controlled primarily by the difference in the relative stability of the peroxy radical isomers. In this regime, β hydroxy peroxy radical isomers comprise ∼95% of the radical pool, a much higher fraction than in the nascent (kinetic) distribution. Intramolecular 1,6 H-shift isomerization of the Z-δ hydroxy peroxy radical isomers produced from OH addition to C_4 is estimated to be ∼4 s^(–1) at 297 K. While the Z-δ isomer is initially produced in low yield, it is continually reformed via decomposition of the β hydroxy peroxy radicals. As a result, unimolecular chemistry from this isomer contributes about half of the atmospheric fate of the entire pool of peroxy radicals formed via addition of OH at C_4 for typical atmospheric conditions (τ_(bimolecular) = 100 s and T = 25 C). In contrast, unimolecular chemistry following OH addition at C_1 is slower and less important

Airborne measurements of western U.S. wildfire emissions: Comparison with prescribed burning and air quality implications

Wildfires emit significant amounts of pollutants that degrade air quality. Plumes from three wildfires in the western U.S. were measured from aircraft during the Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC^4RS) and the Biomass Burning Observation Project (BBOP), both in summer 2013. This study reports an extensive set of emission factors (EFs) for over 80 gases and 5 components of submicron particulate matter (PM_1) from these temperate wildfires. These include rarely, or never before, measured oxygenated volatile organic compounds and multifunctional organic nitrates. The observed EFs are compared with previous measurements of temperate wildfires, boreal forest fires, and temperate prescribed fires. The wildfires emitted high amounts of PM_1 (with organic aerosol (OA) dominating the mass) with an average EF that is more than 2 times the EFs for prescribed fires. The measured EFs were used to estimate the annual wildfire emissions of carbon monoxide, nitrogen oxides, total nonmethane organic compounds, and PM_1 from 11 western U.S. states. The estimated gas emissions are generally comparable with the 2011 National Emissions Inventory (NEI). However, our PM_1 emission estimate (1530 ± 570 Gg yr^(−1)) is over 3 times that of the NEI PM_(2.5) estimate and is also higher than the PM_(2.5) emitted from all other sources in these states in the NEI. This study indicates that the source of OA from biomass burning in the western states is significantly underestimated. In addition, our results indicate that prescribed burning may be an effective method to reduce fine particle emissions

A Spitzer Spectroscopic Survey of Low Ionization Nuclear Emission-line Regions: Characterization of the Central Source

We have conducted a comprehensive mid-IR spectroscopic investigation of 67 Low Ionization Nuclear Emission Line Regions (LINERs) using archival observations from the high resolution modules of the Infrared Spectrograph on board the Spitzer Space Telescope. Using the [NeV] 14 and 24um lines as active galactic nuclei (AGN) diagnostics, we detect active black holes in 39% of the galaxies in our sample, many of which show no signs of activity in either the optical or X-ray bands. In particular, a detailed comparison of multi-wavelength diagnostics shows that optical studies fail to detect AGN in galaxies with large far-IR luminosities. These observations emphasize that the nuclear power source in a large percentage of LINERs is obscured in the optical. Indeed, the majority of LINERs show mid-IR [NeV]14/[NeV]24um flux ratios well below the theoretical low-density limit, suggesting that there is substantial extinction toward even the [NeV]-emitting region . Combining optical, X-ray, and mid-IR diagnostics, we find an AGN detection rate in LINERs of 74%, higher than previously reported statistics of the fraction of LINERs hosting AGN. The [NeV]24um /[OIV]26um mid-IR line flux ratio in "AGN-LINERs" is similar to that of standard AGN, suggesting that the spectral energy distribution (SED) of the intrinsic optical/UV continuum is similar in the two. This result is in contrast to previous suggestions of a UV deficit in the intrinsic broadband continuum emission in AGN-LINERs. Consistent with our finding of extinction to the [NeV]-emitting region, we propose that extinction may also be responsible for the observed optical/UV deficit seen in at least some AGN-LINERs.Comment: Accepted for publication in Ap

Rapid hydrolysis of tertiary isoprene nitrate efficiently removes NO_x from the atmosphere

The formation of a suite of isoprene-derived hydroxy nitrate (IHN) isomers during the OH-initiated oxidation of isoprene affects both the concentration and distribution of nitrogen oxide free radicals (NO_x). Experiments performed in an atmospheric simulation chamber suggest that the lifetime of the most abundant isomer, 1,2-IHN, is shortened significantly by a water-mediated process (leading to nitric acid formation), while the lifetime of a similar isomer, 4,3-IHN, is not. Consistent with these chamber studies, NMR kinetic experiments constrain the 1,2-IHN hydrolysis lifetime to less than 10 s in deuterium oxide (D₂O) at 298 K, whereas the 4,3-IHN isomer has been observed to hydrolyze much less efficiently. These laboratory findings are used to interpret observations of the IHN isomer distribution in ambient air. The IHN isomer ratio (1,2-IHN to 4,3-IHN) in a high NO_x environment decreases rapidly in the afternoon, which is not explained using known gas-phase chemistry. When simulated with an observationally constrained model, we find that an additional loss process for the 1,2-IHN isomer with a time constant of about 6 h best explains our atmospheric measurements. Using estimates for 1,2-IHN Henry’s law constant and atmospheric liquid water volume, we show that condensed-phase hydrolysis of 1,2-IHN can account for this loss process. Simulations from a global chemistry transport model show that the hydrolysis of 1,2-IHN accounts for a substantial fraction of NO_x lost (and HNO₃ produced), resulting in large impacts on oxidant formation, especially over forested regions

Isoprene NO_3 Oxidation Products from the RO_2 + HO_2 Pathway

We describe the products of the reaction of the hydroperoxy radical (HO_2) with the alkylperoxy radical formed following addition of the nitrate radical (NO_3) and O_2 to isoprene. NO_3 adds preferentially to the C_1 position of isoprene (>6 times more favorably than addition to C_4), followed by the addition of O_2 to produce a suite of nitrooxy alkylperoxy radicals (RO_2). At an RO_2 lifetime of ∼30 s, δ-nitrooxy and β-nitrooxy alkylperoxy radicals are present in similar amounts. Gas-phase product yields from the RO_2 + HO_2 pathway are identified as 0.75–0.78 isoprene nitrooxy hydroperoxide (INP), 0.22 methyl vinyl ketone (MVK) + formaldehyde (CH_2O) + hydroxyl radical (OH) + nitrogen dioxide (NO_2), and 0–0.03 methacrolein (MACR) + CH_2O + OH + NO_2. We further examined the photochemistry of INP and identified propanone nitrate (PROPNN) and isoprene nitrooxy hydroxyepoxide (INHE) as the main products. INHE undergoes similar heterogeneous chemistry as isoprene dihydroxy epoxide (IEPOX), likely contributing to atmospheric secondary organic aerosol formation

A NuSTAR Survey of Nearby Ultraluminous Infrared Galaxies

We present a Nuclear Spectroscopic Telescope Array (NuSTAR), Chandra, and XMM-Newton survey of nine of the nearest ultraluminous infrared galaxies (ULIRGs). The unprecedented sensitivity of NuSTAR at energies above 10 keV enables spectral modeling with far better precision than was previously possible. Six of the nine sources observed were detected sufficiently well by NuSTAR to model in detail their broadband X-ray spectra, and recover the levels of obscuration and intrinsic X-ray luminosities. Only one source (IRAS 13120–5453) has a spectrum consistent with a Compton-thick active galactic nucleus (AGN), but we cannot rule out that a second source (Arp 220) harbors an extremely highly obscured AGN as well. Variability in column density (reduction by a factor of a few compared to older observations) is seen in IRAS 05189–2524 and Mrk 273, altering the classification of these borderline sources from Compton-thick to Compton-thin. The ULIRGs in our sample have surprisingly low observed fluxes in high-energy (>10 keV) X-rays, especially compared to their bolometric luminosities. They have lower ratios of unabsorbed 2–10 keV to bolometric luminosity, and unabsorbed 2–10 keV to mid-IR [O iv] line luminosity than do Seyfert 1 galaxies. We identify IRAS 08572+3915 as another candidate intrinsically X-ray weak source, similar to Mrk 231. We speculate that the X-ray weakness of IRAS 08572+3915 is related to its powerful outflow observed at other wavelengths

NuSTAR unveils a Compton-thick type 2 quasar in MrK 34

We present Nuclear Spectroscopic Telescope Array (NuSTAR) 3-40 keV observations of the optically selected Type 2 quasar (QSO2) SDSS J1034+6001 or Mrk 34. The high-quality hard X-ray spectrum and archival XMM-Newton data can be fitted self-consistently with a reflection-dominated continuum and a strong Fe K? fluorescence line with equivalent width >1 keV. Prior X-ray spectral fitting below 10 keV showed the source to be consistent with being obscured by Compton-thin column densities of gas along the line of sight, despite evidence for much higher columns from multiwavelength data. NuSTAR now enables a direct measurement of this column and shows that N H lies in the Compton-thick (CT) regime. The new data also show a high intrinsic 2-10 keV luminosity of L 2-10 ~ 1044 erg s–1, in contrast to previous low-energy X-ray measurements where L 2-10 lesssim 1043 erg s–1 (i.e., X-ray selection below 10 keV does not pick up this source as an intrinsically luminous obscured quasar). Both the obscuring column and the intrinsic power are about an order of magnitude (or more) larger than inferred from pre-NuSTAR X-ray spectral fitting. Mrk 34 is thus a "gold standard" CT QSO2 and is the nearest non-merging system in this class, in contrast to the other local CT quasar NGC 6240, which is currently undergoing a major merger coupled with strong star formation. For typical X-ray bolometric correction factors, the accretion luminosity of Mrk 34 is high enough to potentially power the total infrared luminosity. X-ray spectral fitting also shows that thermal emission related to star formation is unlikely to drive the observed bright soft component below ~3 keV, favoring photoionization instead