HOx radical regeneration in isoprene oxidation via peroxy radical isomerisations. II: experimental evidence and global impact

2010 ◽  
Vol 12 (42) ◽  
pp. 14227 ◽  
Author(s):  
Jozef Peeters ◽  
Jean-François Müller
Keyword(s):  
Experimental Evidence ◽  
Peroxy Radical ◽  
Global Impact ◽  
Isoprene Oxidation

The Importance of Peroxy Radical Hydrogen-Shift Reactions in Atmospheric Isoprene Oxidation

2019 ◽  
Vol 123 (4) ◽  
pp. 920-932 ◽  
Author(s):  
Kristian H. Møller ◽  
Kelvin H. Bates ◽  
Henrik G. Kjaergaard
Keyword(s):  
Peroxy Radical ◽  
Hydrogen Shift ◽  
Isoprene Oxidation

scholarly journals Formaldehyde production from isoprene oxidation across NO<sub><i>x</i></sub> regimes

2016 ◽  
Vol 16 (4) ◽  
pp. 2597-2610 ◽  
Author(s):  
G. M. Wolfe ◽  
J. Kaiser ◽  
T. F. Hanisco ◽  
F. N. Keutsch ◽  
J. A. de Gouw ◽  
...  
Keyword(s):  
Transport Model ◽  
Model Simulation ◽  
Nonlinear Function ◽  
Peroxy Radical ◽  
Fold Increase ◽  
Oxidation Products ◽  
Box Model ◽  
Chemical Transport Model ◽  
Mixing Ratios ◽  
Isoprene Oxidation

Abstract. The chemical link between isoprene and formaldehyde (HCHO) is a strong, nonlinear function of NOx (i.e., NO + NO2). This relationship is a linchpin for top-down isoprene emission inventory verification from orbital HCHO column observations. It is also a benchmark for overall photochemical mechanism performance with regard to VOC oxidation. Using a comprehensive suite of airborne in situ observations over the southeast US, we quantify HCHO production across the urban–rural spectrum. Analysis of isoprene and its major first-generation oxidation products allows us to define both a "prompt" yield of HCHO (molecules of HCHO produced per molecule of freshly emitted isoprene) and the background HCHO mixing ratio (from oxidation of longer-lived hydrocarbons). Over the range of observed NOx values (roughly 0.1–2 ppbv), the prompt yield increases by a factor of 3 (from 0.3 to 0.9 ppbv ppbv−1), while background HCHO increases by a factor of 2 (from 1.6 to 3.3 ppbv). We apply the same method to evaluate the performance of both a global chemical transport model (AM3) and a measurement-constrained 0-D steady-state box model. Both models reproduce the NOx dependence of the prompt HCHO yield, illustrating that models with updated isoprene oxidation mechanisms can adequately capture the link between HCHO and recent isoprene emissions. On the other hand, both models underestimate background HCHO mixing ratios, suggesting missing HCHO precursors, inadequate representation of later-generation isoprene degradation and/or underestimated hydroxyl radical concentrations. Detailed process rates from the box model simulation demonstrate a 3-fold increase in HCHO production across the range of observed NOx values, driven by a 100 % increase in OH and a 40 % increase in branching of organic peroxy radical reactions to produce HCHO.

scholarly journals Glyoxal yield from isoprene oxidation and relation to formaldehyde: chemical mechanism, constraints from SENEX aircraft observations, and interpretation of OMI satellite data

2016 ◽  
Author(s):  
Christopher Chan Miller ◽  
Daniel J. Jacob ◽  
Eloise A. Marais ◽  
Karen Yu ◽  
Katherine R. Travis ◽  
...  
Keyword(s):  
Transport Model ◽  
Peroxy Radical ◽  
Satellite Observations ◽  
Chemical Mechanism ◽  
Chemical Transport Model ◽  
Formation Pathway ◽  
Isoprene Emission ◽  
Aircraft Observations ◽  
Isoprene Oxidation ◽  
Southeast Us

Abstract. Glyoxal (CHOCHO) is produced in the atmosphere by oxidation of volatile organic compounds (VOCs). It is measurable from space by solar backscatter along with formaldehyde (HCHO), another oxidation product of VOCs. Isoprene emitted by vegetation is the dominant source of CHOCHO and HCHO in most of the world. We use aircraft observations of CHOCHO and HCHO from the SENEX campaign over the Southeast US in summer 2013 to better understand the time-dependent yields from isoprene oxidation, their dependences on nitrogen oxides (NOx ≡ NO + NO2), the behaviour of the CHOCHO-HCHO relationship, the quality of OMI satellite observations, and the implications for using satellite CHOCHO observations as constraints on isoprene emission. We simulate the SENEX and OMI observations with the GEOS-Chem chemical transport model featuring a new chemical mechanism for CHOCHO formation from isoprene. The mechanism includes prompt CHOCHO formation under low-NOx conditions following the isomerization of the isoprene peroxy radical (ISOPO2). The SENEX observations provide support for this prompt CHOCHO formation pathway, and are generally consistent with the GEOS-Chem mechanism. Boundary layer CHOCHO and HCHO are strongly correlated in the observations and the model, with some departure under low-NOx conditions due to prompt CHOCHO formation. SENEX vertical profiles indicate a free tropospheric CHOCHO background that is absent from the model. The OMI CHOCHO data provide some support for this free tropospheric background and show Southeast US enhancements consistent with the isoprene source but a factor of 2 too low. Part of this OMI bias is due to excessive surface reflectivities assumed in the retrieval. The OMI CHOCHO and HCHO seasonal data over the Southeast US are tightly correlated and provide redundant proxies of isoprene emission. Higher temporal resolution in future geostationary satellite observations may enable detection of the prompt CHOCHO production under low-NOx conditions apparent in the SENEX data.

scholarly journals Formaldehyde production from isoprene oxidation across NO<sub><i>x</i></sub> regimes

2015 ◽  
Vol 15 (21) ◽  
pp. 31587-31620 ◽  
Author(s):  
G. M. Wolfe ◽  
J. Kaiser ◽  
T. F. Hanisco ◽  
F. N. Keutsch ◽  
J. A. de Gouw ◽  
...  
Keyword(s):  
First Generation ◽  
Transport Model ◽  
Peroxy Radical ◽  
Oxidation Products ◽  
Peroxy Radicals ◽  
Chemical Transport Model ◽  
Mixing Ratios ◽  
Urban Rural ◽  
Isoprene Oxidation ◽  
Southeast Us

Abstract. The chemical link between isoprene and formaldehyde (HCHO) is a strong, non-linear function of NOx (= NO + NO2). This relationship is a linchpin for top-down isoprene emission inventory verification from orbital HCHO column observations. It is also a benchmark for overall mechanism performance with regard to VOC oxidation. Using a comprehensive suite of airborne in situ observations over the Southeast US, we quantify HCHO production across the urban-rural spectrum. Analysis of isoprene and its major first-generation oxidation products allows us to define both a "prompt" yield of HCHO (molecules of HCHO produced per molecule of freshly-emitted isoprene) and the background HCHO mixing ratio (from oxidation of longer-lived hydrocarbons). Over the range of observed NOx values (roughly 0.1–2 ppbv), the prompt yield increases by a factor of 3 (from 0.3 to 0.9 ppbv ppbv−1), while background HCHO increases by more than a factor of 2 (from 1.5 to 3.3 ppbv). We apply the same method to evaluate the performance of both a global chemical transport model (AM3) and a measurement-constrained 0-D chemical box model. Both models reproduce the NOx dependence of the prompt HCHO yield, illustrating that models with updated isoprene oxidation mechanisms can adequately capture the link between HCHO and recent isoprene emissions. On the other hand, both models under-estimate background HCHO mixing ratios, suggesting missing HCHO precursors, inadequate representation of later-generation isoprene degradation and/or under-estimated hydroxyl radical concentrations. Moreover, we find that the total organic peroxy radical production rate is essentially independent of NOx, as the increase in oxidizing capacity with NOx is largely balanced by a decrease in VOC reactivity. Thus, the observed NOx dependence of HCHO mainly reflects the changing fate of organic peroxy radicals.

Experimental evidence for efficient hydroxyl radical regeneration in isoprene oxidation

2013 ◽  
Vol 6 (12) ◽  
pp. 1023-1026 ◽  
Author(s):  
H. Fuchs ◽  
A. Hofzumahaus ◽  
F. Rohrer ◽  
B. Bohn ◽  
T. Brauers ◽  
...  
Keyword(s):  
Hydroxyl Radical ◽  
Experimental Evidence ◽  
Isoprene Oxidation

scholarly journals Glyoxal yield from isoprene oxidation and relation to formaldehyde: chemical mechanism, constraints from SENEX aircraft observations, and interpretation of OMI satellite data

2017 ◽  
Vol 17 (14) ◽  
pp. 8725-8738 ◽  
Author(s):  
Christopher Chan Miller ◽  
Daniel J. Jacob ◽  
Eloise A. Marais ◽  
Karen Yu ◽  
Katherine R. Travis ◽  
...  
Keyword(s):  
Transport Model ◽  
Peroxy Radical ◽  
Satellite Observations ◽  
Chemical Mechanism ◽  
Chemical Transport Model ◽  
Formation Pathway ◽  
Earth Observing System ◽  
Aircraft Observations ◽  
Isoprene Oxidation ◽  
Southeast Us

Abstract. Glyoxal (CHOCHO) is produced in the atmosphere by the oxidation of volatile organic compounds (VOCs). Like formaldehyde (HCHO), another VOC oxidation product, it is measurable from space by solar backscatter. Isoprene emitted by vegetation is the dominant source of CHOCHO and HCHO in most of the world. We use aircraft observations of CHOCHO and HCHO from the SENEX campaign over the southeast US in summer 2013 to better understand the CHOCHO time-dependent yield from isoprene oxidation, its dependence on nitrogen oxides (NOx  ≡  NO + NO2), the behavior of the CHOCHO–HCHO relationship, the quality of OMI CHOCHO satellite observations, and the implications for using CHOCHO observations from space as constraints on isoprene emissions. We simulate the SENEX and OMI observations with the Goddard Earth Observing System chemical transport model (GEOS-Chem) featuring a new chemical mechanism for CHOCHO formation from isoprene. The mechanism includes prompt CHOCHO formation under low-NOx conditions following the isomerization of the isoprene peroxy radical (ISOPO2). The SENEX observations provide support for this prompt CHOCHO formation pathway, and are generally consistent with the GEOS-Chem mechanism. Boundary layer CHOCHO and HCHO are strongly correlated in the observations and the model, with some departure under low-NOx conditions due to prompt CHOCHO formation. SENEX vertical profiles indicate a free-tropospheric CHOCHO background that is absent from the model. The OMI CHOCHO data provide some support for this free-tropospheric background and show southeast US enhancements consistent with the isoprene source but a factor of 2 too low. Part of this OMI bias is due to excessive surface reflectivities assumed in the retrieval. The OMI CHOCHO and HCHO seasonal data over the southeast US are tightly correlated and provide redundant proxies of isoprene emissions. Higher temporal resolution in future geostationary satellite observations may enable detection of the prompt CHOCHO production under low-NOx conditions apparent in the SENEX data.

How do memory modules differentially contribute to familiarity and recollection?

2019 ◽  
Vol 42 ◽  
Author(s):  
Olya Hakobyan ◽  
Sen Cheng
Keyword(s):  
Recognition Memory ◽  
Experimental Evidence ◽  
Subjective Experience ◽  
Target Article ◽  
Memory Modules ◽  
Familiarity And Recollection ◽  
Memory Contents

Abstract We fully support dissociating the subjective experience from the memory contents in recognition memory, as Bastin et al. posit in the target article. However, having two generic memory modules with qualitatively different functions is not mandatory and is in fact inconsistent with experimental evidence. We propose that quantitative differences in the properties of the memory modules can account for the apparent dissociation of recollection and familiarity along anatomical lines.

Redox Reactions in Lipid Membranes as a Model for Primordial Energy-Conserving Systems

1997 ◽  
Vol 161 ◽  
pp. 437-442
Author(s):  
Salvatore Di Bernardo ◽  
Romana Fato ◽  
Giorgio Lenaz
Keyword(s):  
Experimental Evidence ◽  
Lipid Membranes ◽  
Energy Supply ◽  
Redox Reactions ◽  
Living Systems ◽  
Asymmetric Distribution ◽  
Conservation Of Energy ◽  
Asymmetrical Distribution ◽  
Energy Conserving ◽  
Living Organisms

AbstractOne of the peculiar aspects of living systems is the production and conservation of energy. This aspect is provided by specialized organelles, such as the mitochondria and chloroplasts, in developed living organisms. In primordial systems lacking specialized enzymatic complexes the energy supply was probably bound to the generation and maintenance of an asymmetric distribution of charged molecules in compartmentalized systems. On the basis of experimental evidence, we suggest that lipophilic quinones were involved in the generation of this asymmetrical distribution of charges through vectorial redox reactions across lipid membranes.

A Method for Setting the Clearance Angle

1972 ◽  
Vol 30 ◽  
pp. 388-389
Author(s):  
Michael T. Bucek ◽  
Howard J. Arnott
Keyword(s):  
Experimental Evidence ◽  
Light Source ◽  
Black Spot ◽  
Critical Factor ◽  
Clearance Angle ◽  
Crude Approximation ◽  
Ultrathin Sections

It is believed by the authors, with supporting experimental evidence, that as little as 0.5°, or less, knife clearance angle may be a critical factor in obtaining optimum quality ultrathin sections. The degree increments located on the knife holder provides the investigator with only a crude approximation of the angle at which the holder is set. With the increments displayed on the holder one cannot set the clearance angle precisely and reproducibly. The ability to routinely set this angle precisely and without difficulty would obviously be of great assistance to the operator. A device has been contrived to aid the investigator in precisely setting the clearance angle. This device is relatively simple and is easily constructed. It consists of a light source and an optically flat, front surfaced mirror with a minute black spot in the center. The mirror is affixed to the knife by placing it permanently on top of the knife holder.

Introductory Remarks

1980 ◽  
Vol 38 ◽  
pp. 598-599
Author(s):  
H. Mohri
Keyword(s):  
Muscle Contraction ◽  
Experimental Evidence ◽  
Sea Urchin ◽  
Constant Length ◽  
Thin Filaments ◽  
Bridge Formation ◽  
Thick Filaments ◽  
Sliding Mechanism ◽  
Radial Spokes ◽  
Cilia And Flagella

In 1959, Afzelius observed the presence of two rows of arms projecting from each outer doublet microtubule of the so-called 9 + 2 pattern of cilia and flagella, and suggested a possibility that the outer doublet microtubules slide with respect to each other with the aid of these arms during ciliary and flagellar movement. The identification of the arms as an ATPase, dynein, by Gibbons (1963)strengthened this hypothesis, since the ATPase-bearing heads of myosin molecules projecting from the thick filaments pull the thin filaments by cross-bridge formation during muscle contraction. The first experimental evidence for the sliding mechanism in cilia and flagella was obtained by examining the tip patterns of molluscan gill cilia by Satir (1965) who observed constant length of the microtubules during ciliary bending. Further evidence for the sliding-tubule mechanism was given by Summers and Gibbons (1971), using trypsin-treated axonemal fragments of sea urchin spermatozoa. Upon the addition of ATP, the outer doublets telescoped out from these fragments and the total length reached up to seven or more times that of the original fragment. Thus, the arms on a certain doublet microtubule can walk along the adjacent doublet when the doublet microtubules are disconnected by digestion of the interdoublet links which connect them with each other, or the radial spokes which connect them with the central pair-central sheath complex as illustrated in Fig. 1. On the basis of these pioneer works, the sliding-tubule mechanism has been established as one of the basic mechanisms for ciliary and flagellar movement.

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