scispace - formally typeset
Search or ask a question
Author

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.


Papers
More filters
Journal ArticleDOI
TL;DR: In this paper, the rate coefficient for the reaction OH + ClO → products (1) was measured under pseudo-first-order conditions in OH, and the value of k1 between 234 and 356 K was given by k1(T) = (8.9 ± 2.7) × 10-12 exp[(295 ± 95)/T] cm3 molecule-1 s-1, where uncertainties are 95% confidence limits and include estimated systematic uncertainties.
Abstract: The rate coefficient for the reaction OH + ClO → products (1) was measured under pseudo-first-order conditions in OH. A discharge flow system was used to produce ClO, and its concentration was measured by UV/visible absorption. OH was produced by pulsed laser photolysis of O3 (or ClO) at 248 nm in the presence of H2O and was monitored by laser-induced fluorescence. The value of k1 between 234 and 356 K is given by k1(T) = (8.9 ± 2.7) × 10-12 exp[(295 ± 95)/T] cm3 molecule-1 s-1, where uncertainties are 95% confidence limits and include estimated systematic uncertainties. Our value is compared with those from previous investigations.

25 citations

01 Jan 2014
TL;DR: In this article, the Montreal Protocol is used to measure changes in the global atmospheric abundance of ozone-depleting substances (ODSs) and the balance between its emission and removal.
Abstract: Changes in the global atmospheric abundance of a substance are determined by the balance between its emissionand removal. Declines observed for ozone-depleting substances (ODSs) controlled under the Montreal Protocol are due to global emission reductions that have made emissions smaller than removals. Mot ODSs are potent greenhouse gases. As the majority of ODSs have been phased out, demand for hydrochlorofluorocarbon (HCFC) and hydrofluorocarbon (HFC) substitutes for the substances controlled under the Montreal Protocol have increased; these are also greenhouse gases. HCFCs deplete much less ozone per kilogram emitted than chlorofluorocarbons (CFCs), while HFCs essentially deplete no ozone.

25 citations

Journal ArticleDOI
TL;DR: It is concluded that these compounds are acceptable substitutes for CFCs in terms of their impact on Earth's climate.
Abstract: Rate coefficients for reaction of the hydroxyl radical (OH) with three hydrofluorocarbons (HFCs) CF3CH2CH3, HFC-263fb, (k1); CF3CHFCH2F, HFC-245eb, (k2); and CHF2CHFCHF2, HFC-245ea, (k3); which are suggested as potential substitutes to chlorofluorocarbons (CFCs), were measured using pulsed laser photolysis−laser-induced fluorescence (PLP−LIF) between 235 and 375 K The Arrhenius expressions obtained are k1(T) = (436 ± 072) × 10-12 exp[−(1290 ± 40)/T] cm3 molecule-1 s-1; k2(T) = (123 ± 018) × 10-12 exp[−(1250 ± 40)/T] cm3 molecule-1 s-1; k3(T) = (191 ± 042) × 10-12 exp[−(1375 ± 100)/T] cm3 molecule-1 s-1 The quoted uncertainties are 95% confidence limits and include estimated systematic errors The present results are discussed and compared with rate coefficients available in the literature Our results are also compared with those calculated using structure activity relationships (SAR) for fluorinated compounds The IR absorption cross-sections at room temperature for these compounds were measured

24 citations

Journal ArticleDOI
TL;DR: In this paper, rate coefficient and product branching measurements for the reaction OH + bromopropane from 230 to 360 K were presented for a single-stage reaction with O(n 2 ).
Abstract: Article on rate coefficient and product branching measurements for the reaction OH + bromopropane from 230 to 360 K.

23 citations

Journal ArticleDOI
TL;DR: The peak cross section of the P(8) line was determined to be (1.98 ± 0.36) × 10−18 cm2, and the intensity of the entire band was normalized to this line as mentioned in this paper.
Abstract: Absorption cross sections for the A 2A″ (0,90,0) ← 2A′ (0,01,0) band of HCO were determined at 295 K using pulsed laser photolysis combined with cavity ring-down spectroscopy. Formyl radicals (HCO) were produced from the reaction of atomic chlorine, generated by photolysis of Cl2 at 335 nm, with formaldehyde. The concentration of HCO was calibrated using two independent photochemical methods. The peak cross section of the P(8) line was determined to be (1.98 ± 0.36) × 10−18 cm2, and the intensity of the entire band was normalized to this line. The quoted 2σ uncertainty includes estimated systematic errors. Comparisons to previously reported values of HCO cross sections in this band are discussed.

23 citations


Cited by
More filters
Journal ArticleDOI
TL;DR: The new HITRAN is greatly extended in terms of accuracy, spectral coverage, additional absorption phenomena, added line-shape formalisms, and validity, and molecules, isotopologues, and perturbing gases have been added that address the issues of atmospheres beyond the Earth.
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.

7,638 citations

Journal ArticleDOI
TL;DR: 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.
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.

5,370 citations

Journal ArticleDOI
TL;DR: In this paper, the authors provided an assessment 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.
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.

4,591 citations

Book ChapterDOI
01 Jan 2014
TL;DR: Myhre et al. as discussed by the authors presented the contribution of Working Group I to the Fifth Assessment Report of the Intergovernmental Panel on Climate Change (IPCC) 2013: 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)

3,684 citations

Journal ArticleDOI
TL;DR: The present status of knowledge of the gas phase reactions of inorganic Ox, Hox and NOx species and of selected classes of volatile organic compounds (VOCs) and their degradation products in the troposphere is discussed in this paper.

2,722 citations