This paper describes the contents of the 2016 edition of the HITRAN molecular spectroscopic compilation. The new edition replaces the previous HITRAN edition of 2012 and its updates during the intervening years. The HITRAN molecular absorption compilation is composed of five major components: the traditional line-by-line spectroscopic parameters required for high-resolution radiative-transfer codes, infrared absorption cross-sections for molecules not yet amenable to representation in a line-by-line form, collision-induced absorption data, aerosol indices of refraction, and general tables such as partition sums that apply globally to the data. The new HITRAN is greatly extended in terms of accuracy, spectral coverage, additional absorption phenomena, added line-shape formalisms, and validity. Moreover, molecules, isotopologues, and perturbing gases have been added that address the issues of atmospheres beyond the Earth. Of considerable note, experimental IR cross-sections for almost 300 additional molecules important in different areas of atmospheric science have been added to the database. The compilation can be accessed through www.hitran.org. Most of the HITRAN data have now been cast into an underlying relational database structure that offers many advantages over the long-standing sequential text-based structure. The new structure empowers the user in many ways. It enables the incorporation of an extended set of fundamental parameters per transition, sophisticated line-shape formalisms, easy user-defined output formats, and very convenient searching, filtering, and plotting of data. A powerful application programming interface making use of structured query language (SQL) features for higher-level applications of HITRAN is also provided.

/pdf/the-hitran-2008-molecular-spectroscopic-database-1ud8clpej3.pdf

The HITRAN 2008 molecular spectroscopic database

Nitric oxide contrasts with most intercellular messengers because it diffuses rapidly and isotropically through most tissues with little reaction but cannot be transported through the vasculature due to rapid destruction by oxyhemoglobin. The rapid diffusion of nitric oxide between cells allows it to locally integrate the responses of blood vessels to turbulence, modulate synaptic plasticity in neurons, and control the oscillatory behavior of neuronal networks. Nitric oxide is not necessarily short lived and is intrinsically no more reactive than oxygen. The reactivity of nitric oxide per se has been greatly overestimated in vitro because no drain is provided to remove nitric oxide. Nitric oxide persists in solution for several minutes in micromolar concentrations before it reacts with oxygen to form much stronger oxidants like nitrogen dioxide. Nitric oxide is removed within seconds in vivo by diffusion over 100 microns through tissues to enter red blood cells and react with oxyhemoglobin. The direct toxicity of nitric oxide is modest but is greatly enhanced by reacting with superoxide to form peroxynitrite (ONOO-). Nitric oxide is the only biological molecule produced in high enough concentrations to out-compete superoxide dismutase for superoxide. Peroxynitrite reacts relatively slowly with most biological molecules, making peroxynitrite a selective oxidant. Peroxynitrite modifies tyrosine in proteins to create nitrotyrosines, leaving a footprint detectable in vivo. Nitration of structural proteins, including neurofilaments and actin, can disrupt filament assembly with major pathological consequences. Antibodies to nitrotyrosine have revealed nitration in human atherosclerosis, myocardial ischemia, septic and distressed lung, inflammatory bowel disease, and amyotrophic lateral sclerosis.

Nitric oxide, superoxide, and peroxynitrite: the good, the bad, and ugly.

Black carbon aerosol plays a unique and important role in Earth's climate system. Black carbon is a type of carbonaceous material with a unique combination of physical properties. This assessment provides an evaluation of black-carbon climate forcing that is comprehensive in its inclusion of all known and relevant processes and that is quantitative in providing best estimates and uncertainties of the main forcing terms: direct solar absorption; influence on liquid, mixed phase, and ice clouds; and deposition on snow and ice. These effects are calculated with climate models, but when possible, they are evaluated with both microphysical measurements and field observations. Predominant sources are combustion related, namely, fossil fuels for transportation, solid fuels for industrial and residential uses, and open burning of biomass. Total global emissions of black carbon using bottom-up inventory methods are 7500 Gg yr−1 in the year 2000 with an uncertainty range of 2000 to 29000. However, global atmospheric absorption attributable to black carbon is too low in many models and should be increased by a factor of almost 3. After this scaling, the best estimate for the industrial-era (1750 to 2005) direct radiative forcing of atmospheric black carbon is +0.71 W m−2 with 90% uncertainty bounds of (+0.08, +1.27) W m−2. Total direct forcing by all black carbon sources, without subtracting the preindustrial background, is estimated as +0.88 (+0.17, +1.48) W m−2. Direct radiative forcing alone does not capture important rapid adjustment mechanisms. A framework is described and used for quantifying climate forcings, including rapid adjustments. The best estimate of industrial-era climate forcing of black carbon through all forcing mechanisms, including clouds and cryosphere forcing, is +1.1 W m−2 with 90% uncertainty bounds of +0.17 to +2.1 W m−2. Thus, there is a very high probability that black carbon emissions, independent of co-emitted species, have a positive forcing and warm the climate. We estimate that black carbon, with a total climate forcing of +1.1 W m−2, is the second most important human emission in terms of its climate forcing in the present-day atmosphere; only carbon dioxide is estimated to have a greater forcing. Sources that emit black carbon also emit other short-lived species that may either cool or warm climate. Climate forcings from co-emitted species are estimated and used in the framework described herein. When the principal effects of short-lived co-emissions, including cooling agents such as sulfur dioxide, are included in net forcing, energy-related sources (fossil fuel and biofuel) have an industrial-era climate forcing of +0.22 (−0.50 to +1.08) W m−2 during the first year after emission. For a few of these sources, such as diesel engines and possibly residential biofuels, warming is strong enough that eliminating all short-lived emissions from these sources would reduce net climate forcing (i.e., produce cooling). When open burning emissions, which emit high levels of organic matter, are included in the total, the best estimate of net industrial-era climate forcing by all short-lived species from black-carbon-rich sources becomes slightly negative (−0.06 W m−2 with 90% uncertainty bounds of −1.45 to +1.29 W m−2). The uncertainties in net climate forcing from black-carbon-rich sources are substantial, largely due to lack of knowledge about cloud interactions with both black carbon and co-emitted organic carbon. In prioritizing potential black-carbon mitigation actions, non-science factors, such as technical feasibility, costs, policy design, and implementation feasibility play important roles. The major sources of black carbon are presently in different stages with regard to the feasibility for near-term mitigation. This assessment, by evaluating the large number and complexity of the associated physical and radiative processes in black-carbon climate forcing, sets a baseline from which to improve future climate forcing estimates.

/pdf/bounding-the-role-of-black-carbon-in-the-climate-system-a-1fc3novd9r.pdf

Bounding the role of black carbon in the climate system: A scientific assessment

This chapter should be cited as: Myhre, G., D. Shindell, F.-M. Bréon, W. Collins, J. Fuglestvedt, J. Huang, D. Koch, J.-F. Lamarque, D. Lee, B. Mendoza, T. Nakajima, A. Robock, G. Stephens, T. Takemura and H. Zhang, 2013: Anthropogenic and Natural Radiative Forcing. In: Climate Change 2013: The Physical Science Basis. Contribution of Working Group I to the Fifth Assessment Report of the Intergovernmental Panel on Climate Change [Stocker, T.F., D. Qin, G.-K. Plattner, M. Tignor, S.K. Allen, J. Boschung, A. Nauels, Y. Xia, V. Bex and P.M. Midgley (eds.)]. Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA. Coordinating Lead Authors: Gunnar Myhre (Norway), Drew Shindell (USA)

Anthropogenic and Natural Radiative Forcing

http://joenschem.com/yahoo_site_admin/assets/docs/atkinson2000r.93190106.pdf

Atmospheric chemistry of VOCs and NOx

The ultraviolet absorption spectra of a number of alkyl iodides which have been found in the troposphere, CH3I, C2H5I, CH3CH2CH2I, CH3CHICH3, CH2I2, and CH2ClI, have been measured over the wavelength range 200–380 nm and at temperatures between 298 and 210 K. The absorption spectra of the monoiodides CH3I, C2H5I, CH3CH2CH2I, and CH3CHICH3 are nearly identical in shape and magnitude and consist of single broad bands centered near 260 nm. The addition of a chlorine atom in CH2ClI shifts its spectrum to longer wavelengths (σmax at 270 nm). The spectrum of CH2I2 is further red-shifted, reaching a maximum of 3.85×10−18 cm2 molecule−1 at 288 nm and exhibiting strong absorption in the solar actinic region, λ>290 nm. Atmospheric photolysis rate constants, J values, have been calculated assuming quantum efficiencies of unity for different solar zenith angles as a function of altitude using the newly measured cross sections. Surface photolysis rate constants, calculated from the absorption cross sections measured at 298 K, range from 3×10−6 s−1 for CH3I to 5×10−3 s−1 for CH2I2 at a solar zenith angle of 40°.

https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/97JD00530

Temperature dependence of UV absorption cross sections and atmospheric implications of several alkyl iodides

Lifetimes of Stratospheric Ozone-Depleting Substances, Their Replacements, and Related Species

The UV absorption cross-sections of methyl, ethyl and
isopropyl nitrate between 233 and 340 nm have been measured
using a diode array spectrometer in the temperature range
240–360 K. The absorption cross-sections of these
alkyl nitrates decrease with increasing wavelength and
decrease with decreasing temperature for λ>280 nm.
The photodissociation quantum yield for
CH
 3
ONO
 2
 to produce NO
 2
 and
CH
 3
O was found to be essentially unity at 248 nm
using transient UV absorption methods. Production of O and H
atoms in the photodissociation of methyl nitrate at 248 and
308 nm were found to be negligible using resonance
fluorescence detection of the atoms. High quantum yields for
O atoms were measured following 193 nm photolysis of methyl
nitrate. The OH radical was measured to be a photoproduct
with a very small quantum yield. Using the OH rate
coefficients reported in the accompanying paper and the UV
absorption cross-sections and the photodissociation quantum
yields measured here, the first-order rate constants for
atmospheric loss of methyl, ethyl and isopropyl nitrate were
calculated. Photolysis was found to be the dominant
atmospheric loss process for the three alkyl nitrates.

Atmospheric fate of several alkyl nitrates Part2UV absorption cross-sectionsand photodissociation quantum yields

Gas-Phase UV/Visible Absorption Spectra of HOBr and Br2O

The ozone, O3, absorption cross sections between 410 and 760 nm, the Chappuis band, were measured at 220, 240, 260, and 280 K relative to that at room temperature using a diode array spectrometer. The measured cross sections varied very slightly, less than 1%, with decreasing temperature between 550 and 660 nm, near the peak of the Chappuis band. At wavelengths away from the peak, the absorption cross sections decreased with decreasing temperature; e.g., about 40% at 420 nm between 298 and 220 K. These results are compared with previous measurements and the impact on atmospheric measurements are discussed.

James B. Burkholder

Papers

Temperature dependence of UV absorption cross sections and atmospheric implications of several alkyl iodides

Lifetimes of Stratospheric Ozone-Depleting Substances, Their Replacements, and Related Species

Atmospheric fate of several alkyl nitrates Part2UV absorption cross-sectionsand photodissociation quantum yields

Gas-Phase UV/Visible Absorption Spectra of HOBr and Br2O

Temperature dependence of the ozone absorption spectrum over the wavelength range 410 to 760 nm