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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
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Journal ArticleDOI
TL;DR: In this article, the temperature dependent UV absorption cross sections of the haloalkanes CF3Br, CF2ClBr and CF2Br2 were measured over the temperature range 210 to 296 K and the wavelength range 190 to 320 run.
Abstract: The temperature dependent UV absorption cross sections of the haloalkanes CF3Br, CF2ClBr, CF2Br2, and CF2BrCF2Br are reported. The UV absorption cross sections were measured over the temperature range 210 to 296 K and the wavelength range 190 to 320 run. Upper limits of the rate coefficients for the reactions of OH with CF3Br, CF2Br2, CF2ClBr, and CF2BrCF2Br were also determined using both pulsed photolysis and flow tube techniques. The rate coefficients at 296 K were found to be <1.2×10−16, <1.5×10−16, <5.0×10−16, and <1.5×10−16 cm3 molec−1 s−1 for CF3Br, CF2ClBr, CF2Br2, and CF2BrCF2Br, respectively. The UV absorption cross-section data and OH reaction rate coefficients of these species were combined with a one-dimensional model to yield atmospheric lifetimes of 65, 16, 3.2, and <20 years for CF3Br, CF2ClBr, CF2Br2, and CF2BrCF2Br, respectively.

54 citations

Journal ArticleDOI
TL;DR: In this article, the relative absorption cross sections for the ClOO radical were measured in the region 220-280 nm and the absolute UV absorption cross section at 246.0 nm, the peak of the absorption, was determined to be (2.98±0.23)×10 -17 cm 2 molecule -1.
Abstract: The relative absorption cross sections for the ClOO radical were measured in the region 220-280 nm. The absolute UV absorption cross section at 246.0 nm, the peak of the absorption, was determined to be (2.98±0.23)×10 -17 cm 2 molecule -1 . Using this value, the cross sections in the 220-280-nm range were calculated. The equilibrium constant for the Cl+O 2 ⇄ClOO reaction was measured at six temperatures between 191 and 250 K

52 citations

Journal ArticleDOI
TL;DR: In this paper, the room temperature UV absorption spectrum of HOCl was measured over the wavelength range 200 to 380 nm with a diode array spectrometer and the measured absorption cross section at 242 nm was (2.1 +/- 0.3) x 10 exp -19/sq cm (2 sigma error limits).
Abstract: The room temperature UV absorption spectrum of HOCl was measured over the wavelength range 200 to 380 nm with a diode array spectrometer. The absorption spectrum was identified from UV absorption spectra recorded following UV photolysis of equilibrium mixtures of Cl2O/H2O/HOCl. The HOCl spectrum is continuous with a maximum at 242 nm and a secondary peak at 304 nm. The measured absorption cross section at 242 nm was (2.1 +/- 0.3) x 10 exp -19/sq cm (2 sigma error limits). These results are in excellent agreement with the work of Knauth et al. (1979) but in poor agreement with the more recent measurements of Mishalanie et al. (1986) and Permien et al. (1988). An HOCl nu2 infrared band intensity of 230 +/- 35/sq cm atm was determined based on this UV absorption cross section. The present results are compared with these previous measurements and the discrepancies are discussed.

51 citations

Journal ArticleDOI
TL;DR: In this paper, the absorption cross sections of BrONO2 between 200 and 500 nm were measured over the temperature range 298 to 220 K using a diode array spectrometer.
Abstract: The absorption cross sections of BrONO2 between 200 and 500 nm were measured over the temperature range 298 to 220 K using a diode array spectrometer. The BrONO2 absorption cross sections are weakly dependent on temperature at wavelengths 450 nm; at 480 nm the cross section decreased by ∼35% in going from 298 K to 220 K. Our room temperature absorption cross sections are in good agreement with the measurements of Spencer and Rowland (1978) over the common wavelength range of the measurements, 200 to 390 nm. We show that wavelengths longer than 390 nm must be included in the calculation of the BrONO2 atmospheric photolysis rate. We also show that photolysis of BrONO2 could be a significant atmospheric loss process for odd oxygen (due to halogen chemistry) below about 25 km. The infrared absorption cross sections for the BrONO2 band centered at 803.3 cm−1 were also measured. The integrated band strength was (2.7±0.5) × 10−17 cm2 molecule−1 cm−1.

50 citations

Journal ArticleDOI
TL;DR: Harder et al. as mentioned in this paper used pulsed laser photolysis of NO{sub 2} to produce oxygen atoms and time-resolved vacuum UV resonance fluorescence detection of O atoms.
Abstract: Nitrogen oxides, NO and NO{sub 2} (collectively called No{sub x}), play a crucial role in atmospheric ozone chemistry: they lead to photochemical ozone production in the troposphere and catalytic ozone destruction in the stratosphere. The rate coefficient (k{sub 1}) for the reaction O({sup 3}P) + NO{sub 2} {r_arrow} O{sub 2} + NO was measured under pseudo-first-order conditions in O({sup 3}P) atom concentration over the temperature range 220--412 K. Measurements were made using pulsed laser photolysis of NO{sub 2} to produce oxygen atoms and time-resolved vacuum UV resonance fluorescence detection of O atoms. The NO{sub 2} concentration was measured using three techniques: flow rate, UV absorption, and chemical titration (NO + O{sub 3} {r_arrow} NO{sub 2} + O{sub 2}). The NO{sub 2} UV absorption cross section at 413.4 nm was determined as a function of temperature using the chemical titration and flow methods. Including the low-temperature data of Harder et al., the temperature-dependent No{sub 2} cross section is given by {sigma}{sub 413.4}(T) = (9.49 {minus} 0.00549 T) {times} 10{sup {minus}19} cm{sup 2} molecule{sup {minus}1}. The measured rate coefficients for reaction 1 can be expressed as k{sub 1}(T) = (5.26 {+-} 0.60) {times} 10{sup {minus}12} exp[(209 {+-} 35)/T] cm{sup 3} molecule{sup {minus}1}more » s{sup {minus}1}, where the quoted uncertainties are 2{sigma} and include estimated systematic errors. This result is compared with previously reported measurements of k{sub 1}.« less

49 citations


Cited by
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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