James B. Burkholder

Bio: James B. Burkholder is an academic researcher from Earth System Research Laboratory. The author has contributed to research in topics: Absorption spectroscopy & Absorption (electromagnetic radiation). The author has an hindex of 36, co-authored 84 publications receiving 4185 citations. Previous affiliations of James B. Burkholder include Cooperative Institute for Research in Environmental Sciences.

Rate coefficients for the reaction of OH with (E)-2-pentenal, (E)-2-hexenal, and (E)-2-heptenal

Abstract: Rate coefficients for the gas-phase reaction of the OH radical with (E)-2-pentenal (CH3CH2CHCHCHO), (E)-2-hexenal (CH3(CH2)2CHCHCHO), and (E)-2-heptenal (CH3(CH2)3CHCHCHO), a series of unsaturated aldehydes, over the temperature range 244–374 K at pressures between 23 and 150 Torr (He, N2) are reported. Rate coefficients were measured under pseudo-first-order conditions in OH with OH radicals produced via pulsed laser photolysis of HNO3 or H2O2 at 248 nm and detected by pulsed laser-induced fluorescence. The rate coefficients were independent of pressure and the room temperature rate coefficients and Arrhenius expressions obtained are (cm3 molecule−1 s−1 units): k1(297 K) = (4.3 ± 0.6) × 10−11, k1(T) = (7.9 ± 1.2) × 10−12 exp[(510 ± 20)/T]; k2(297 K) = (4.4 ± 0.5) × 10−11, k2(T) = (7.5 ± 1.1) × 10−12 exp[(520 ± 30)/T]; and k3(297 K) = (4.4 ± 0.7) × 10−11, k3(T) = (9.7 ± 1.5) × 10−12 exp[(450 ± 20)/T] for (E)-2-pentenal, (E)-2-hexenal and (E)-2-heptenal, respectively. The quoted uncertainties are 2σ (95% confidence level) and include estimated systematic errors. Rate coefficients are compared with previously published room temperature values and the discrepancies are discussed. The atmospheric degradation of unsaturated aldehydes is also discussed.

Oxalyl chloride, ClC(O)C(O)Cl: UV/vis spectrum and Cl atom photolysis quantum yields at 193, 248, and 351 nm.

Abstract: Oxalyl chloride, (ClCO)2, has been used as a Cl atom photolytic precursor in numerous laboratory kinetic and photochemical studies. In this study, the UV/vis absorption spectrum of (ClCO)2 and the Cl atom quantum yields in its photolysis at 193, 248, and 351 nm are reported. The UV/vis spectrum was measured between 200 and 450 nm at 296 K using diode array spectroscopy in conjunction with an absolute cross section obtained at 213.9 nm. Our results are in agreement with the spectrum reported by Baklanov and Krasnoperov [J. Phys. Chem. A 105, 97–103 (2001)10.1021/jp0019456], which was obtained at 11 discrete wavelengths between 193.3 and 390 nm. Cl atom quantum yields, Φ(λ), were measured using pulsed laser photolysis coupled with time resolved atomic resonance fluorescence detection of Cl. The UV photolysis of (ClCO)2 has been shown in previous studies to occur via an impulsive three-body dissociation mechanism, (COCl)2 + hv → ClCO* + Cl + CO (2), where the excited ClCO radical, ClCO*, either dissociates o...

Vibrational relaxation in ozone recombination

Abstract: The time dependence of different components of the population of vibrationally excited ozone is measured during its formation by recombination, using changes in the shape of the vibronic absorption continuum as a probe. The time dependence of the population of every component of the total population is distinguished as either the ground state P000, states excited only in the bending mode P0x0, or states excited in the stretching mode Pxxx. In addition, two levels of states excited in the stretching mode are distinguished. The results give values for the V→T relaxation of the bending mode k2 that are consistent with the values obtained in other laboratories. For relaxation by O2 in the absence of O3†–O3† mode equilibration, the value obtained for the ratio of the rate constant k12, for V→V transfer from the stretching modes to bend, to k2 is α = 0.4±0.1. Assuming that the newly recombined ozone initially relaxes through a quasicontinuum of levels, for which the rules for energy exchange are not known, it i...

Infrared line intensity measurements in the v = 0–1 band of the ClO radical

Abstract: Integrated line intensity measurements in the ClO-radical fundamental vibrational v = 0-1 band were carried out using a high-resolution Fourier transform spectrometer coupled to a long-path-length absorption cell. The results of a series of measurements designed to minimize systematic errors, yielded a value of the fundamental IR band intensity of the ClO-radical equal to 9.68 + or - 1.45/sq cm per atm at 296 K. This result is consistent with all the earlier published results, with the exception of measurements reported by Kostiuk et al. (1986) and Lang et al. (1988).

Deriving global OH abundance and atmospheric lifetimes for long-lived gases: a search for CH3CCl3 alternatives

Abstract: An accurate estimate of global hydroxyl radical (OH) abundance is important for projections of air quality, climate, and stratospheric ozone recovery. As the atmospheric mixing ratios of methyl chloroform (CH3CCl3) (MCF), the commonly used OH reference gas, approaches zero, it is important to find alternative approaches to infer atmospheric OH abundance and variability. The lack of global bottom-up emission inventories is the primary obstacle in choosing a MCF alternative. We illustrate that global emissions of long-lived trace gases can be inferred from their observed mixing ratio differences between the Northern Hemisphere (NH) and Southern Hemisphere (SH), given realistic estimates of their NH-SH exchange time, the emission partitioning between the two hemispheres, and the NH versus SH OH abundance ratio. Using the observed long-term trend and emissions derived from the measured hemispheric gradient, the combination of HFC-32 (CH2F2), HFC-134a (CH2FCF3, HFC-152a (CH3CHF2), and HCFC-22 (CHClF2), instead of a single gas, will be useful as a MCF alternative to infer global and hemispheric OH abundance and trace gas lifetimes. The primary assumption on which this multispecies approach relies is that the OH lifetimes can be estimated by scaling the thermal reaction rates of a reference gas at 272 K on global and hemispheric scales. Thus, the derived hemispheric and global OH estimates are forced to reconcile the observed trends and gradient for all four compounds simultaneously. However, currently, observations of these gases from the surface networks do not provide more accurate OH abundance estimate than that from MCF.

The HITRAN 2008 molecular spectroscopic database

Abstract: 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.

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

Abstract: 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.

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

Abstract: 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.

Anthropogenic and Natural Radiative Forcing

Abstract: 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)