Large aperture [O I] photometry of comets Hyakutake, Halley, and Austin: implications for the photochemistry of OH

NASA Astrophysics Data System (ADS)

Morgenthaler, J. P.; Harris, W. M.; Scherb, F.; Combi, M. R.

2004-11-01

The 6300 Å component of the oxygen (1D) doublet is a bright, easily observed line in cometary comae that results primarily from the photodissociation of water and its daughter, OH. If the cometary emission can be separated from foreground airglow, either by foreground subtraction or spectral resolution comparable to the geocentric velocity of the comet, [O I] photometry should, in principle make an excellent proxy for Q(H2O). With cometary geocentric velocities frequently less than 60 km/s, spectral separation requires instruments with resolving powers of >10000, which for conventional grating spectrographs, implies a slit width of order one arcsecond. Maximum slit length, limited by practical considerations is therefore of order a few arcminutes. For a typical geocentric distance of 1 AU, [O I] emission in this FOV is dominated by water photodissociation, so with only knowledge of water photochemistry and an estimate of the aperture correction from the distribution along the slit, water production rates can be derived (e.g. Fink et al. 1990). Interferometric techniques, such as Fabry-Perot, Michelson, and Spatial Heterodyne Spectroscopy (SHS) achieve very high spectral resolution over FOVs of arcminutes to degrees. Using the 1 degree FOV Wisconsin H-alpha Mapper (WHAM), we recorded images and spectra of comet Hale-Bopp that encompassed the entire [O I] coma. In this case, the emission was dominated by OH photodissociation. Using conventional OH photochemistry, our derived Q(H2O) values were a factor of 3-4 higher than the accepted values, suggesting a revision to the OH photochemistry is needed (Morgenthaler et al. 2001). In this work, we will revisit our large aperture [O I] measurements of comets 1P/Halley, C/1989X1 Austin, and C/1996 B2 Hyakutake and show that revision of the OH photochemistry is necessary to bring these results into agreement with accepted Q(H2O) values. This work is funded by the NASA Planetary Atmospheres program.

Excited-state hydrogen atom abstraction initiates the photochemistry of β-2′-deoxycytidine† †Electronic supplementary information (ESI) available: Including relevant preliminary results as well as illustrations and geometrical parameters of selected structures. See DOI: 10.1039/c4sc03761h Click here for additional data file.

PubMed Central

Campos, Jesús; Šponer, Judit E.; Šponer, Jiří

2015-01-01

Understanding the effects of ultraviolet radiation on nucleotides in solution is an important step towards a comprehensive description of the photochemistry of nucleic acids and their constituents. Apart from having implications for mutagenesis and DNA photoprotection mechanisms, the photochemistry of cytidines is a central element in UV-assisted syntheses of pyrimidine nucleotides under prebiotically plausible conditions. In this contribution, we present UV-irradiation experiments of β-2′-deoxycytidine in aqueous solution involving H–D exchange followed by NMR spectroscopic analysis of the photoproducts. We further elucidate the outcome of these experiments by means of high-level quantum chemical calculations. In particular, we show that prolonged UV-irradiation of cytidine may lead to H–C1′ hydrogen atom abstraction by the carbonyl oxygen atom of cytosine. This process may enable photoanomerisation and nucleobase loss, two previously unexplained photoreactions observed in pyrimidine nucleotides. PMID:27182431

Photochemistry in terrestrial exoplanet atmospheres. III. Photochemistry and thermochemistry in thick atmospheres on super Earths and mini Neptunes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Renyu; Seager, Sara, E-mail: hury@caltech.edu

Some super Earths and mini Neptunes will likely have thick atmospheres that are not H{sub 2}-dominated. We have developed a photochemistry-thermochemistry kinetic-transport model for exploring the compositions of thick atmospheres on super Earths and mini Neptunes, applicable for both H{sub 2}-dominated atmospheres and non-H{sub 2}-dominated atmospheres. Using this model to study thick atmospheres for wide ranges of temperatures and elemental abundances, we classify them into hydrogen-rich atmospheres, water-rich atmospheres, oxygen-rich atmospheres, and hydrocarbon-rich atmospheres. We find that carbon has to be in the form of CO{sub 2} rather than CH{sub 4} or CO in a H{sub 2}-depleted water-dominated thick atmospheremore » and that the preferred loss of light elements from an oxygen-poor carbon-rich atmosphere leads to the formation of unsaturated hydrocarbons (C{sub 2}H{sub 2} and C{sub 2}H{sub 4}). We apply our self-consistent atmosphere models to compute spectra and diagnostic features for known transiting low-mass exoplanets GJ 1214 b, HD 97658 b, and 55 Cnc e. For GJ 1214 b, we find that (1) C{sub 2}H{sub 2} features at 1.0 and 1.5 μm in transmission and C{sub 2}H{sub 2} and C{sub 2}H{sub 4} features at 9-14 μm in thermal emission are diagnostic for hydrocarbon-rich atmospheres; (2) a detection of water-vapor features and a confirmation of the nonexistence of methane features would provide sufficient evidence for a water-dominated atmosphere. In general, our simulations show that chemical stability has to be taken into account when interpreting the spectrum of a super Earth/mini Neptune. Water-dominated atmospheres only exist for carbon to oxygen ratios much lower than the solar ratio, suggesting that this kind of atmospheres could be rare.« less

Constraining the Volatile Composition and Coma Photochemistry in Jupiter Family Comet 41P/Tuttle-Giacobini-Kresak with High Resolution IR and Optical Spectroscopy

NASA Astrophysics Data System (ADS)

McKay, Adam; DiSanti, Michael A.; Cochran, Anita L.; Dello Russo, Neil; Bonev, Boncho P.; Vervack, Ronald J.; Gibb, Erika L.; Roth, Nathan X.; Kawakita, Hideyo

2017-10-01

Over the past 20 years optical and IR spectroscopy of cometary comae has expanded our understanding both of cometary volatile composition and coma photochemistry. However, these observations tend to be biased towards Nearly Isotropic Comets (NIC's) from the Oort Cloud, rather than the generally fainter and less active Jupiter Family Comets (JFC's) that are thought to originate from the Scattered Disk. However, early 2017 provided a rare opportunity to study several JFC's. We present preliminary results from IR and optical spectroscopy of JFC 41P/Tuttle-Giacobini-Kresak obtained during its 2017 apparition. IR spectra were obtained with the NIRSPEC instrument on Keck II and the new iSHELL spectrograph on NASA IRTF. High spectral resolution optical spectra were obtained with the Tull Coude spectrograph on the 2.7-meter Harlan J. Smith Telescope at McDonald Observatory. We will discuss mixing ratios of HCN, NH3, C2H6, C2H2, H2CO, and CH3OH compared to H2O and compare these to previous observations of comets. Preliminary results from the NIRSPEC observations indicate that 41P has typical C2H2 and HCN abundances compared to other JFC's, while the C2H6 abundance is similar to that of NIC's, but is enriched compared to other JFC's. H2CO appears to be heavily depleted in 41P. Analysis of the iSHELL spectra is underway and we will include results from these observations, which complement those from NIRSPEC and extend the scope or our compositional study by measuring additional molecules. We will also present abundances for CN, C2, NH2, C3, and CH obtained from the optical spectra and discuss the implications for the coma photochemistry.This work is supported by the NASA Postdoctoral Program, administered by the Universities Space Research Association, with additional funding from the NSF and NASA PAST.

Constraining the Volatile Composition and Coma Photochemistry in Jupiter Family Comet 41P/Tuttle-Giacobini-Kresak with High Resolution IR and Optical Spectroscopy

NASA Astrophysics Data System (ADS)

McKay, Adam; DiSanti, Michael; Cochran, Anita; Dello Russo, Neil; Bonev, Boncho; Vervack, Ronald; Gibb, Erika; Roth, Nathan; Kawakita, Hideyo

2018-01-01

Over the past 20 years optical and IR spectroscopy of cometary comae has expanded our understanding both of cometary volatile composition and coma photochemistry. However, these observations tend to be biased towards Nearly Isotropic Comets (NIC'S) from the Oort Cloud, rather than the generally fainter and less active Jupiter Family Comets (JFC's) that are thought to originate from the Scattered Disk. However, early 2017 provided a rare opportunity to study several JFC's. We present preliminary results from IR and optical spectroscopy of JFC 41P/Tuttle-Giacobini-Kresak obtained during its 2017 apparition. IR spectra were obtained with the NIRSPEC instrument on Keck II and the new iSHELL spectrograph on NASA IRTF. High spectral resolution optical spectra were obtained with the Tull Coude spectrograph on the 2.7-meter Harlan J. Smith Telescope at McDonald Observatory. We will discuss mixing ratios of HCN, NH3, C2H6, C2H2, H2CO, and CH3OH compared to H2O and compare these to previous observations of comets. Preliminary results from the NIRSPEC observations indicate that 41P has typical C2H2 and HCN abundances compared to other JFC's, while the C2H6 abundance is similar to that of NIC's, but is enriched compared to other JFC's. H2CO appears to be heavily depleted in 41P. Analysis of the iSHELL spectra is underway and we will include results from these observations, which complement those from NIRSPEC and extend the scope or our compositional study by measuring additional molecules. We will also present abundances for CN, C2, NH2, C3, and CH obtained from the optical spectra and discuss the implications for the coma photochemistry.This work is supported by the NASA Postdoctoral Program, administered by the Universities Space Research Association, with additional funding from the NSF and NASA PAST.

Nuclear thermal propulsion test facility requirements and development strategy

NASA Technical Reports Server (NTRS)

Allen, George C.; Warren, John; Clark, J. S.

1991-01-01

The Nuclear Thermal Propulsion (NTP) subpanel of the Space Nuclear Propulsion Test Facilities Panel evaluated facility requirements and strategies for nuclear thermal propulsion systems development. High pressure, solid core concepts were considered as the baseline for the evaluation, with low pressure concepts an alternative. The work of the NTP subpanel revealed that a wealth of facilities already exists to support NTP development, and that only a few new facilities must be constructed. Some modifications to existing facilities will be required. Present funding emphasis should be on long-lead-time items for the major new ground test facility complex and on facilities supporting nuclear fuel development, hot hydrogen flow test facilities, and low power critical facilities.

78 FR 32626 - Pacific Fishery Management Council (Pacific Council); Public Meeting

Federal Register 2010, 2011, 2012, 2013, 2014

2013-05-31

... Species Advisory 8 a.m Terrace A-D Room. Subpanel. Highly Migratory Species Management 8 a.m Terrace E-F... Royal E Room. Budget Committee 2 p.m Granada Room. Enforcement Consultants 5 p.m Royal D-F Room. Thursday, June 20, 2013: California State Delegation......... 7 a.m Royal E Room. Oregon State Delegation 7...

Mental Health in Deafness. Experimental Issue 2. Fall 1978.

ERIC Educational Resources Information Center

Robinson, Luther D., Ed.

The publication contains four articles on the subject of mental health as it relates to deaf persons. "Deaf Americans and the President's Commission on Mental Health" discusses the Commission Report as a whole (by L. Robinson), the Report of the Task Subpanel on Special Populations (by B. Sachs), and the section on mental health needs of…

The importance of Titan's current mass loss processes to understanding the evolution of Titan's atmosphere

NASA Astrophysics Data System (ADS)

Mandt, Kathleen; Waite, J. Hunter, Jr.; Bell, Jared; Mousis, Olivier

2010-04-01

Current isotopic ratios in planetary atmospheres have played an important role in determining how that atmosphere has evolved over geologic time scales (e.g. Donahue et al. 1997, Lunine et al. 1999). The current 12C/13C ratio in methane is a particularly useful indicator of Titan's atmospheric evolutionary history (Mandt et al. 2009). Primordial 12C/13C ratios throughout the solar system are limited to 89.01+4.45-2.67. (Alexander et al. 2007, Martins et al. 2008), while the methane 12C/13C ratio measured by GCMS and CIRS are 82.3+/-1.0 and 76.6+/-2.7 respectively (Niemann et al. 2005, Nixon et al. 2008). This is well below the primordial range, suggesting fractionation of the isotopes by atmospheric processes. A number of atmospheric mass loss processes can fractionate the isotopes over geologic time scales. Photochemistry and escape are of particular importance (Donahue et al 1997, Mandt et al. 2009). Measurements of the 12C/13C ratios in C2 hydrocarbons show evidence of fractionation due to photochemistry (Nixon et al. 2008) that is most likely due to a kinetic isotope effect (KIE). A KIE is a mildly efficient fractionating process in which reactions involving 12C occur 1.04 times faster than reactions involving 13C. A moderate time scale, on the order of 50 to 400 million years, is required to change the 12C/13C ratio of the atmospheric methane inventory. The exact length of this time scale depends directly on the methane photochemical loss rate. Titan's photochemistry is extremely complex, and although the total photochemical loss rate is photon-limited (Lorenz et al. 1997), the literature provides a range of loss rates between 4.9 x 10^9 cm-2s-1 (Wilson and Atreya 2004) and 3.4 x 10^10 cm-2s-1 (Lebonnois et al. 2003). This range can alter the time scale for fractionation in the carbon isotopes by as much as a factor of 8. INMS measurements of the methane 12C/13C ratio in the upper atmosphere show that atmospheric escape is a more efficient fractionating process than photochemistry (Mandt et al. 2009). The literature provides a range of possible values for the methane escape rates that depend on the input parameters to upper atmospheric models (Bell et al. 2010). The escape rate of methane could be as little as 2.75 x 10^7 cm-2s-1 (de la Haye et al. 2007) or as great as 3.0 x 10^9 cm-2s-1 (Yelle et al. 2008). This range of loss rates can alter the time scale for fractionation by as much as a factor of 5. Although the photochemical fractionation is less efficient than the escape rate, variance in its value has a greater impact on the time required to fractionate the isotopes because the magnitude of the photochemical loss is much greater than that of the escape rate. Thus, a better quantification of both mass loss rates is key to understanding the evolutionary history of Titan's atmosphere.

Growth in elevated CO(2) can both increase and decrease photochemistry and photoinhibition of photosynthesis in a predictable manner. Dactylis glomerata grown in two levels of nitrogen nutrition.

PubMed

Hymus, G J; Baker, N R; Long, S P

2001-11-01

Biochemically based models of C(3) photosynthesis can be used to predict that when photosynthesis is limited by the amount of Rubisco, increasing atmospheric CO(2) partial pressure (pCO(2)) will increase light-saturated linear electron flow through photosystem II (J(t)). This is because the stimulation of electron flow to the photosynthetic carbon reduction cycle (J(c)) will be greater than the competitive suppression of electron flow to the photorespiratory carbon oxidation cycle (J(o)). Where elevated pCO(2) increases J(t), then the ratio of absorbed energy dissipated photochemically to that dissipated non-photochemically will rise. These predictions were tested on Dactylis glomerata grown in fully controlled environments, at either ambient (35 Pa) or elevated (65 Pa) pCO(2), and at two levels of nitrogen nutrition. As was predicted, for D. glomerata grown in high nitrogen, J(t) was significantly higher in plants grown and measured at elevated pCO(2) than for plants grown and measured at ambient pCO(2). This was due to a significant increase in J(c) exceeding any suppression of J(o). This increase in photochemistry at elevated pCO(2) protected against photoinhibition at high light. For plants grown at low nitrogen, J(t) was significantly lower in plants grown and measured at elevated pCO(2) than for plants grown and measured at ambient pCO(2). Elevated pCO(2) again suppressed J(o); however growth in elevated pCO(2) resulted in an acclimatory decrease in leaf Rubisco content that removed any stimulation of J(c). Consistent with decreased photochemistry, for leaves grown at low nitrogen, the recovery from a 3-h photoinhibitory treatment was slower at elevated pCO(2).

Photochemistry of iron citrates initiated by UV-VIS light

NASA Astrophysics Data System (ADS)

Corral Arroyo, Pablo; Dou, Jing; Alpert, Peter; Krieger, Ulrich; Ammann, Markus

2017-04-01

Aerosol aging refers to the multitude of physical and chemical transformation atmospheric particles undergo, which play an important role in the impact of aerosols on climate, air quality and health. Aging processes may be started by chromophores, which act as photocatalysts that induce the oxidation of non-absorbing molecules [1]. Iron (Fe(III)) carboxylate complexes absorb light below about 500 nm, which is followed by ligand to metal charge transfer (LMCT) resulting in the reduction of iron to Fe(II) and oxidation of the carboxylate ligands, a process that represents an important sink of organic acids in the troposphere [2]. Our goal is to investigate how these photochemical processes contribute to the change of chemical and physical properties of the aerosol particles. To achieve this scope, we carry out coated wall flow tube experiments, exposing films with iron citrate to UV light, which will give information about the radical and LVOC production (connecting the CWFT to a Chemiluminescent Detector or PTR-TOF-MS respectively). From extracting and analyzing the films after irradiation with UV light, we obtain a profile of low-volatility products evolving from the photochemistry of iron citrates. By Scanning Transmission X-Ray Microspectroscopy (STXM) we analyze changes in the C K-edge and Fe L-edge in particles loaded with iron citrate upon exposure to light and follow their chemical and structural evolution upon photochemical oxidation in situ to investigate the degradation kinetics under varying environmental conditions. [1] George G., Ammann M., D'Anna B., Donaldson D. J., Nizkorodov S. A., Heterogeneous photochemistry in the Atmosphere, Chem. Rev., 2015, 115 (10), pp 4218-4258 [2] Weller, C., Horn, S., and Herrmann, H.: Photolysis of Fe(III) carboxylate complexes: Fe(II) quantum yields and reaction mechanisms, Photochemistry and Photobiology A: Chemistry, 268, 24-36, 2013.

Matrix Isolation Spectroscopy and Photochemistry of Triplet 1,3-DIMETHYLPROPYNYLIDENE (MeC3Me)

NASA Astrophysics Data System (ADS)

Knezz, Stephanie N.; Waltz, Terese A.; Haenni, Benjamin C.; Burrmann, Nicola J.; McMahon, Robert J.

2015-06-01

Acetylenic carbenes and conjugated carbon chain molecules of the HCnH family are relevant to the study of combustion and chemistry in the interstellar medium (ISM). Propynylidene (HC3H) has been thoroughly studied and its structure and photochemistry determined. Here, we produce triplet diradical 1,3-dimethylpropynylidene (MeC3Me) photochemically from a precursor diazo compound in a cryogenic matrix (N2 or Ar) at 10 K, and spectroscopic analysis is carried out. The infrared, electronic absorption, and electron paramagnetic resonance spectra were examined in light of the parent (HC3H) system to ascertain the effect of alkyl substituents on delocalized carbon chains of this type. Computational analysis, EPR, and infrared analysis indicate a triplet ground state with a quasilinear structure. Infrared experiments reveal photochemical reaction to penten-3-yne upon UV irradiation. Further experimental and computational results pertaining to the structure and photochemistry will be presented. Seburg, R. A.; Patterson, E. V.; McMahon, R. J., Structure of Triplet Propynylidene (HCCCH) as Probed by IR, UV/vis, and EPR Spectroscopy of Isotopomers. Journal of the American Chemical Society 2009, 131 (26), 9442-9455.

Atmospheric chemistry of carboxylic acids: microbial implication versus photochemistry

NASA Astrophysics Data System (ADS)

Vaïtilingom, M.; Charbouillot, T.; Deguillaume, L.; Maisonobe, R.; Parazols, M.; Amato, P.; Sancelme, M.; Delort, A.-M.

2011-08-01

The objective of this work was to compare experimentally the contribution of photochemistry vs. microbial activity to the degradation of carboxylic acids present in cloud water. For this, we selected 17 strains representative of the microflora existing in real clouds and worked on two distinct artificial cloud media that reproduce marine and continental cloud chemical composition. Photodegradation experiments with hydrogen peroxide (H2O2) as a source of hydroxyl radicals were performed under the same microcosm conditions using two irradiation systems. Biodegradation and photodegradation rates of acetate, formate, oxalate and succinate were measured on both media at 5 °C and 17 °C and were shown to be on the same order of magnitude (around 10-10-10-11 M s-1). The chemical composition (marine or continental origin) had little influence on photodegradation and biodegradation rates while the temperature shift from 17 °C to 5 °C decreased biodegradation rates of a factor 2 to 5. In order to test other photochemical scenarios, theoretical photodegradation rates were calculated considering hydroxyl (OH) radical concentration values in cloud water estimated by cloud chemistry modelling studies and available reaction rate constants of carboxylic compounds with both hydroxyl and nitrate radicals. Considering high OH concentration ([OH] = 1 × 10-12 M) led to no significant contribution of microbial activity in the destruction of carboxylic acids. On the contrary, for lower OH concentration (at noon, [OH] = 1 × 10-14 M), microorganisms could efficiently compete with photochemistry and in similar contributions than the ones estimated by our experimental approach. Combining these two approaches (experimental and theoretical), our results led to the following conclusions: oxalate was only photodegraded; the photodegradation of formate was usually more efficient than its biodegradation; the biodegradation of acetate and succinate seemed to exceed their photodegradation.

Photochemistry of Mo(CO) sub 6 in the gas phase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ganske, J.A.; Rosenfeld, R.N.

1989-03-09

We report a study of the photochemistry of Mo(CO){sub 6} in the gas phase. Time-resolved infrared laser absorption spectroscopy is used to monitor the vibrational spectroscopy and lifetimes of the coordinatively unsaturated species formed upon photolyses at 351, 248, and 193 nm. The infrared spectra observed indicate that Mo(CO){sub 5} has C{sub 4v} symmetry, Mo(CO){sub 4} has C{sub 2v} symmetry, and Mo(CO){sub 3} has C{sub 3v} symmetry. All three unsaturated species undergo rapid association reactions with Mo(CO){sub 6} and with CO. Mo(CO){sub 5} recombines with CO with a high-pressure limiting rate constant of 2.0 ({plus minus}0.2) {times} 10{sup 6} Torr{supmore » {minus}1}s{sup {minus}1}. The corresponding rate constants for Mo(CO){sub 4} and Mo(CO){sub 3} are 7.5 ({plus minus}1.5) {times} 10{sup 6} and 1.8 ({plus minus}1.0) {times} 10{sup 7} Torr{sup {minus}1}s{sup {minus}1}, respectively.« less

On the Involvement of Single-Bond Rotation in the Primary Photochemistry of Photoactive Yellow Protein

PubMed Central

Stahl, Andreas D.; Hospes, Marijke; Singhal, Kushagra; van Stokkum, Ivo; van Grondelle, Rienk; Groot, Marie Louise; Hellingwerf, Klaas J.

2011-01-01

Prior experimental observations, as well as theoretical considerations, have led to the proposal that C4-C7 single-bond rotation may play an important role in the primary photochemistry of photoactive yellow protein (PYP). We therefore synthesized an analog of this protein's 4-hydroxy-cinnamic acid chromophore, (5-hydroxy indan-(1E)-ylidene)acetic acid, in which rotation across the C4-C7 single bond has been locked with an ethane bridge, and we reconstituted the apo form of the wild-type protein and its R52A derivative with this chromophore analog. In PYP reconstituted with the rotation-locked chromophore, 1), absorption spectra of ground and intermediate states are slightly blue-shifted; 2), the quantum yield of photochemistry is ∼60% reduced; 3), the excited-state dynamics of the chromophore are accelerated; and 4), dynamics of the thermal recovery reaction of the protein are accelerated. A significant finding was that the yield of the transient ground-state intermediate in the early phase of the photocycle was considerably higher in the rotation-locked samples than in the corresponding samples reconstituted with p-coumaric acid. In contrast to theoretical predictions, the initial photocycle dynamics of PYP were observed to be not affected by the charge of the amino acid residue at position 52, which was varied by 1), varying the pH of the sample between 5 and 10; and 2), site-directed mutagenesis to construct R52A. These results imply that C4-C7 single-bond rotation in PYP is not an alternative to C7=C8 double-bond rotation, in case the nearby positive charge of R52 is absent, but rather facilitates, presumably with a compensatory movement, the physiological Z/E isomerization of the blue-light-absorbing chromophore. PMID:21889456

75 FR 19940 - Pacific Fishery Management Council; Public Meeting

Federal Register 2010, 2011, 2012, 2013, 2014

2010-04-16

... Pacific Fishery Management Council (Council) will convene a meeting of the Ecosystem Advisory Subpanel... Ecosystem Fishery Management Plan (EFMP). The Council's Ecosystem Plan Development Team (EPDT) has taken the...

A higher order panel method for linearized supersonic flow

NASA Technical Reports Server (NTRS)

Ehlers, F. E.; Epton, M. A.; Johnson, F. T.; Magnus, A. E.; Rubbert, P. E.

1979-01-01

The basic integral equations of linearized supersonic theory for an advanced supersonic panel method are derived. Methods using only linear varying source strength over each panel or only quadratic doublet strength over each panel gave good agreement with analytic solutions over cones and zero thickness cambered wings. For three dimensional bodies and wings of general shape, combined source and doublet panels with interior boundary conditions to eliminate the internal perturbations lead to a stable method providing good agreement experiment. A panel system with all edges contiguous resulted from dividing the basic four point non-planar panel into eight triangular subpanels, and the doublet strength was made continuous at all edges by a quadratic distribution over each subpanel. Superinclined panels were developed and tested on s simple nacelle and on an airplane model having engine inlets, with excellent results.

Matrix isolation infrared spectra and photochemistry of hydantoin.

PubMed

Ildiz, Gulce Ogruc; Nunes, Cláudio M; Fausto, Rui

2013-01-31

Hydantoin (C(3)H(4)N(2)O(2), 2,4-imidazolidinedione) was isolated in argon matrix at 10 K and its infrared spectrum and unimolecular photochemistry were investigated. The molecular structure of the compound was studied both at the DFT(B3LYP) and MP2 levels of approximation with valence triple- and quadruple-ζ basis sets (6-311++G(d,p); cc-pVQZ). It was concluded that the minima in the potential energy surfaces of the molecule correspond to C(1) symmetry structures. However, the energy barrier separating the two-equivalent-by-symmetry minima stays below their zero-point energy, which makes the C(s) symmetry structure, which separates the two minima, the experimentally relevant one. The electronic structure of the molecule was studied in detail by performing the Natural Bond Orbital analysis of its electronic configuration within the DFT(B3LYP)/cc-pVQZ space. The infrared spectrum of the matrix isolated compound was fully assigned also with help of the theoretically predicted spectrum. Upon irradiation at λ = 230 nm, matrix-isolated hydantoin was found to photofragment into isocyanic acid, CO, and methylenimine.

The relative abundance of ethane to acetylene in the Jovian stratosphere

NASA Technical Reports Server (NTRS)

Allen, Mark; Yung, Yuk L.; Gladstone, G. R.

1992-01-01

The inclusion of the results of laboratory kinetics studies on the reaction of C2H3 and H2 to yield C2H4, which is suggestive of an efficient chemical mechanism for the hydrogenation of C2H2 to C2H6, can be included in a comprehensive model of the Jupiter atmosphere hydrocarbon photochemistry to explain the observed altitude variation of the C2H6/C2H2 ratio. The sensitivity of these results to uncertainties in key low-temperature rate constants is demonstrated. These key reaction-rate constants decrease with falling temperature.

Photochemistry of the α-Al 2O 3-PETN interface

DOE PAGES

Tsyshevsky, Roman V.; Zverev, Anton; Mitrofanov, Anatoly; ...

2016-02-29

Optical absorption measurements are combined with electronic structure calculations to explore photochemistry of an α-Al 2O 3-PETN interface formed by a nitroester (pentaerythritol tetranitrate, PETN, C 5H 8N 4O 12) and a wide band gap aluminum oxide (α-Al 2O 3) substrate. The first principles modeling is used to deconstruct and interpret the α-Al 2O 3-PETN absorption spectrum that has distinct peaks attributed to surface F 0-centers and surfacePETN transitions. We predict the low energy α-Al 2O 3 F 0-centerPETN transition, producing the excited triplet state, and α-Al 2O 3 F- 0-centerPETN charge transfer, generating the PETN anion radical. This impliesmore » that irradiation by commonly used lasers can easily initiate photodecomposition of both excited and charged PETN at the interface. As a result, the feasible mechanism of the photodecomposition is proposed.« less

Photochemistry, mixing and transport in Jupiter’s stratosphere constrained by Cassini

NASA Astrophysics Data System (ADS)

Hue, Vincent; Hersant, Franck; Cavalié, Thibault; Dobrijevic, Michel

2015-11-01

Jupiter’s obliquity and eccentricity drive the seasonal forcing on its atmosphere. The seasonal variations on its stratospheric temperature through radiative heating and composition through photochemistry are smaller than for Saturn, due to a lower obliquity and eccentricity. Although the physical conditions in these two planets are different, the stratospheric photochemistry is initiated and controlled by the methane photolysis [1]. We adapted a 2D (altitude-latitude) seasonal photochemical model of Saturn [2] to Jupiter. We compare the seasonal effects on the atmospheric composition between these two planets. We use previous 1D photochemical models for the vertical mixing efficiency [1,3] and recent Cassini observations to constrain the meridional mixing efficiency and transport processes [4,5,6].Cassini’s flyby of Jupiter has allowed mapping its stratospheric temperature as a function of latitude [7]. It has also revealed the meridional distribution of hydrocarbons [8,9], which were suggested by earlier studies [10,4]. Previous models suggest that vertical mixing alone is not sufficient to reproduce the observations of C2H2 and C2H6 [5,6], and that meridional mixing is needed. We show that, in addition to meridional mixing, advective circulation is required to reproduce Cassini observations of C2H6. Preliminary results from our model suggest an equator-to-pole circulation cell in Jupiter’s stratosphere, around 30-0.01 mbar.References[1] Moses et al., 2005. JGR 110, 8001.[2] Hue et al., 2015. Icarus 257, 163-184.[3] Gladstone et al., 1996. Icarus 119, 1-52.[4] Kunde et al., 2004. Science 305, 1582-1587.[5] Liang et al., 2005. ApJ Lett. 635, L177-L180.[6] Lellouch et al., 2006. Icarus 184 (2), 478-497.[7] Simon-Miller et al., 2006. Icarus 180 (1), 98-112.[8] Nixon et al., 2007. Icarus 188, 47-71.[9] Nixon et al., 2010. PSS 58, 1667-1680.[10] Maguire et al., 1984. Bulletin of the AAS 16, 647-647.

Photochemistry of coronene in cosmic water ice analogs at different concentrations.

PubMed

de Barros, A L F; Mattioda, A L; Ricca, A; Cruz, G; Allamandola, L J

2017-10-20

This work presents the photochemistry of ultraviolet (UV) irradiated coronene in water ices at 15 K, studied using mid-infrared Fourier transform (FTIR) spectroscopy for C 24 H 12 :H 2 O at concentrations of (1:50), (1:150), (1:200), (1:300) and (1:400). Previous UV irradiation studies of anthracene:H 2 O, pyrene:H 2 O and benzo[ghi]perylene:H 2 O ices at 15 K have shown that aromatic alcohols and ketones, as well as CO 2 and H 2 CO are formed at very low temperatures. Like-wise, here, in addition to the coronene cation, hydroxy-, keto-, and protonated coronene (coronene-H + ) are formed. The rate constants for the decay of neutral coronene and for the formation of photoproducts have been derived. It is shown that PAHs and their UV-induced PAH:H 2 O photoproducts have mid-infrared spectroscopic signatures in the 5-8 μ m region that can contribute to the interstellar ice components described by Boogert et al. (2008) as C1-C5. Our results suggest that oxygenated and hydrogenated PAHs could be in UV-irradiated regions of the ISM where water-rich ices are important.

Photochemistry of Coronene in Cosmic Water Ice Analogs at Different Concentrations

NASA Astrophysics Data System (ADS)

de Barros, A. L. F.; Mattioda, A. L.; Ricca, A.; Cruz-Diaz, G. A.; Allamandola, L. J.

2017-10-01

This work presents the photochemistry of ultraviolet (UV) irradiated coronene in water ices at 15 K studied using mid-infrared Fourier transform (FTIR) spectroscopy for C24H12:H2O at concentrations of (1:50), (1:150), (1:200), (1:300), and (1:400). Previous UV irradiation studies of anthracene:H2O, pyrene:H2O, and benzo[ghi]perylene:H2O ices at 15 K have shown that aromatic alcohols and ketones, as well as CO2 and H2CO, are formed at very low temperatures. Likewise, here, in addition to the coronene cation, hydroxy-, keto-, and protonated coronene (coronene H+) are formed. The rate constants for the decay of neutral coronene and for the formation of photoproducts have been derived. It is shown that Polycyclic Aromatic Hydrocarbons (PAHs) and their UV induced PAH:H2O photoproducts have mid-infrared spectroscopic signatures in the 5-8 μm region that can contribute to the interstellar ice components described by Boogert et al. as C1-C5. Our results suggest that oxygenated and hydrogenated PAHs could be in UV-irradiated regions of the interstellar medium where water-rich ices are important.

Photochemistry of Saturn's Atmosphere. 1; Hydrocarbon Chemistry and Comparisons with ISO Observations

NASA Technical Reports Server (NTRS)

Moses, Julianne I.; Bezard, Bruno; Lellouch, Emmanuel; Gladstone, G. Randall; Feuchtgruber, Helmut; Allen, Mark

2000-01-01

To investigate the details of hydrocarbon photochemistry on Saturn, we have developed a one-dimensional diurnally averaged model that couples hydrocarbon and oxygen photochemistry, molecular and eddy diffusion, radiative transfer, and condensation. The model results are compared with observations from the Infrared Space Observatory (ISO) to place tighter constraints on molecular abundances, to better define Saturn's eddy diffusion coefficient profile, and to identify important chemical schemes that control the abundances of the observable hydrocarbons in Saturn's upper atmosphere. From the ISO observations, we determine that the column 12 densities of CH3, CH3C2H, and C4H2 above 10 mbar are 4 (sup +2) (sub -1.5) x 10 (exp 13) cm (sup -2), (1.1 plus or minus 0.3) x 10 (exp 15) cm (exp -2), and (1.2 plus or minus 0.3) x 10 (exp 14) cm (sup -2), respectively. The observed ISO emission features also indicate C2H2 mixing ratios of 1.2 (sup +0.9) (sub -0.6) x 10 (exp -6) at 0.3 mbar and (2.7 plus or minus 0.8) x 10 (exp -7) at 1.4 mbar, and a C2H6 mixing ratio of (9 plus or minus 2.5) x 10 (exp -6) at 0.5 mbar. Upper limits are provided for C2H4, CH2CCH2, C3H8, and C6H2 sensitivity of the model results to variations in the eddy diffusion coefficient profile, the solar flux, the CH4 photolysis branching ratios, the atomic hydrogen influx, and key reaction rates are discussed in detail. We find that C4H2 and CH3C2H are particularly good tracers of important chemical processes and physical conditions in Saturn's upper atmosphere, and C2H6 is a good tracer of the eddy diffusion coefficient in Saturn's lower stratosphere. The eddy diffusion coefficient must be smaller than approximately 3 x 10 (exp 4) sq cm s (sup -1) at pressures greater than 1 mbar in order to reproduce the C2H6 abundance inferred from ISO observations. The eddy diffusion coefficients in the upper stratosphere could be constrained by observations of CH3 radicals if the low-temperature chemistry of CH3 were better understood. We also discuss the implications of our modeling for aerosol formation in Saturn's lower stratosphere-diacetylene, butane, and water condense between approximately 1 and 300 mbar in our model and will dominate stratospheric haze formation at nonauroral latitudes. Our photochemical models will be useful for planning observational sequences and for analyzing data from the upcoming Cassini mission.

Mechanism of cyanoacetylene photochemistry at 185 and 254 nm

NASA Technical Reports Server (NTRS)

Clarke, D. W.; Ferris, J. P.

1996-01-01

The role of cyanoacetylene (HC3N) in the atmospheric photochemistry of Titan and its relevance to polymer formation are discussed. Investigation of the relative light absorption of HC3N, acetylene (C2H2), and diacetylene (C4H2) revealed that HC3N is an important absorber of UV light in the 205- to 225-nanometer wavelength region in Titan's polar regions. Laboratory studies established that photolysis of C2H2 initiates the polymerization of HC3N even though the HC3N is not absorbing the UV light. Quantum yield measurements establish that HC3N is 2-5 times as reactive as C2H2 for polymer formation. Photolysis of HC3N with 185-nanometer light in the presence of N2, H2, Ar, or CF4 results in a decrease in the yield of 1,3,5-tricyanobenzene (1,3,5-tcb), while photolysis in the presence of CH4, C2H6, or n-C4H10 results in an increase in 1,3,5-tcb. The rate of loss of HC3N is increased by all gases except H2, where it is unchanged. It was not possible to detect 1,3,5-tcb as a photoproduct when the partial pressure of HC3N was decreased to 1 torr. Photolysis of HC3N with 254-nanometer light in the presence of H2 or N2 results in the formation of 1,2,4-tcb, while photolysis in the presence of CH4, C2H6, or n-C4H10 results in the formation of increasing amounts of 1,3,5-tcb. Mechanisms for the formation of polymers are presented.

Spectra and Photochemistry of Relevance to Icy Outer Solar System Objects

NASA Technical Reports Server (NTRS)

Bernstein, M. P.; Sandford, S. A.; Allamandola, L. J.; Fonda, Mark (Technical Monitor)

2003-01-01

The Astrochemistry Lab at NASA Ames (www.astrochem.org) has an interest in the organic photochemistry of extraterrestrial ices, having traditionally performed experiments under interstellar conditions. We have recently embarked on projects for PG\\&G to measure spectra and elucidate the photochemistry of ices relevant to outer Solar System objects. 1) We will report on the determination of real and imaginary indicies of refraction of H2O and N2 dominated ices containing simple, common, extraterrestrial molecules such as NH3, HCN, formaldehyde, \\& methanol. 2) We will compare and contrast the photochemistry of H2O ices containing organic molecules at 100 K with previously reported work at 15 K.

Ice Loads and Ship Response to Ice. Summer 1982/Winter 1983 Test Program

DTIC Science & Technology

1984-12-01

approximately 100 ft2 (9.2 M 2) was instrumented to measure ice pressures by measuring compressive strains in the webs of transverse frames. The panel...compressive strains in the webs of transverse frames. The panel was divided into 60 sub-panel areas, six rows of,-ten frames, over which uniform pressures...the Web and the Selection of Gage Spacing . . .............. 18 4.3 Across the Frame Influence on Strain .......... 20 4.4 Construction of the Data

Modeling of synchrotron-based laboratory simulations of Titan's ionospheric photochemistry

NASA Astrophysics Data System (ADS)

Carrasco, Nathalie; Peng, Zhe; Pernot, Pascal

2014-11-01

The APSIS reactor has been designed to simulate in the laboratory with a VUV synchrotron irradiation the photochemistry occurring in planetary upper atmospheres. A N2-CH4 Titan-like gas mixture has been studied, whose photochemistry in Titan's ionospheric irradiation conditions leads to a coupled chemical network involving both radicals and ions. In the present work, an ion-neutral coupled model is developed to interpret the experimental data, taking into account the uncertainties on the kinetic parameters by Monte Carlo sampling. The model predicts species concentrations in agreement with mass spectrometry measurements of the methane consumption and product blocks intensities. Ion chemistry and in particular dissociative recombination are found to be very important through sensitivity analysis. The model is also applied to complementary environmental conditions, corresponding to Titan's ionospheric average conditions and to another existing synchrotron setup. An innovative study of the correlations between species concentrations identifies two main competitive families, leading respectively to saturated and unsaturated species. We find that the unsaturated growth family, driven by C2H2 , is dominant in Titan's upper atmosphere, as observed by the Cassini INMS. But the saturated species are substantially more intense in the measurements of the two synchrotron experimental setups, and likely originate from catalysis by metallic walls of the reactors.

Photochemistry of the Martian atmosphere (mean conditions)

NASA Astrophysics Data System (ADS)

Krasnopolsky, V. A.

1993-02-01

An attempt is made to develop the simplest model of the photochemistry to the Martian atmosphere which fits experimental data without adjustment of the reaction rate coefficients. Based on gas phase models of CO2-H2O chemistry, it is concluded that odd hydrogen reactions are effective enough to provide smaller amounts of CO and O3 than measured. Nitrogen chemistry may be important and should be taken into account. Even the very low sulfur amount of 10 exp -8 can contribute substantially to the Martian photochemistry. Ozone turns out to be the best tracer of the photochemistry.

Non-Methane Hydrocarbon Measurements Aboard the NOAA Research Vessel Ronald H. Brown during the 2002 New England Air Quality Study (NEAQS 2002)

NASA Astrophysics Data System (ADS)

Goldan, P. D.; Kuster, W. C.; Williams, E.; Fehsenfeld, F. C.

2003-12-01

During the NEAQS 2002 study, in-situ NMHC measurements were made aboard the NOAA research vessel Ronald H. Brown by a two channel automated gas chromatograph using both flame ionization and mass-spectrometric detection techniques. Five minute average samples were cryogenically trapped each 1/2 hour and analyzed immediately for C2 through C10 alkanes, C2 through C5 alkenes, C6 through C9 aromatics, C2 through C8 aldehydes and ketones, C1 through C5 alcohols and a variety of compounds of biogenic origin including 6 monoterpenes, isoprene and its primary oxidation products methacrolein and methylvinyl ketone. The relative contributions of these classes of compounds to OH photochemistry has been determined for air masses ranging from those showing significant anthropogenic influence to clean marine air. For the most anthropogenically influenced air masses, alkenes were observed to play a dominant role whereas oxy-hydrocarbons, principally acetaldehyde, were observed to dominate under clean marine conditions. Both the NMHC measurements and back trajectory analyses indicated periods of significant influx into the New England coastal region of urban air masses showing elevated ozone levels from the Boston/Providence urban corridor. About as frequently, less photochemically mature air masses, depleted in ozone but laden with light reactive alkenes, were observed coming from the Portsmouth NH/Kittery ME coastal urban complex. Even in the presence of these anthropogenic plumes, biogenic hydrocarbons appear to dominate OH photochemistry in the New England region much of the time. Data demonstrating all of these conclusions will be shown.

Ultraviolet and Visible Photochemistry of Methanol at 3D Mesoporous Networks: TiO2 and Au-TiO2

DTIC Science & Technology

2013-05-23

methanol photochemistry at three-dimensionally (3D) networked aerogels of TiO2 or Au–TiO2 reveals that incorporated Au nanoparticles strongly sensitize...the oxide nanoarchitecture to visible light. Methanol dissociatively adsorbs at the surfaces of TiO2 and Au–TiO2 aerogels under dark, high-vacuum...photochemistry at three-dimensionally (3D) networked aerogels of TiO2 or Au–TiO2 reveals that incorporated Au nanoparticles strongly sensitize the oxide

Photochemistry of 1- and 2-Naphthols and Their Water Clusters: The Role of 1 ππ*(La ) Mediated Hydrogen Transfer to Carbon Atoms.

PubMed

Novak, Jurica; Prlj, Antonio; Basarić, Nikola; Corminboeuf, Clémence; Došlić, Nađa

2017-06-16

The computational analysis of the isomer- and conformer-dependent photochemistry of 1- and 2-naphthols and their microsolvated water clusters is motivated by their very different excited state reactivities. We present evidence that 1- and 2-naphthol follow distinct excited state deactivation pathways. The deactivation of 2-naphthols, 2-naphthol water clusters, as well as of the anti conformer of 1-naphthol is mediated by the optically dark 1 πσ* state. The dynamics of the 1 πσ* surface leads to the homolytic cleavage of the OH bond. On the contrary, the excited state deactivation of syn 1-naphthol and 1-naphthol water clusters follows an uncommon reaction pathway. Upon excitation to the bright 1 ππ*(L a ) state, a highly specific excited state hydrogen transfer (ESHT) to carbon atoms C8 and C5 takes place, yielding 1,8- and 1,5-naphthoquinone methides. The ESHT pathway arises from the intrinsic electronic properties of the 1 ππ*(L a ) state of 1-naphthols. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photochemistry of Coronene in Cosmic Water Ice Analogs at Different Concentrations

DOE Office of Scientific and Technical Information (OSTI.GOV)

De Barros, A. L. F.; Mattioda, A. L.; Ricca, A.

This work presents the photochemistry of ultraviolet (UV) irradiated coronene in water ices at 15 K studied using mid-infrared Fourier transform (FTIR) spectroscopy for C{sub 24}H{sub 12}:H{sub 2}O at concentrations of (1:50), (1:150), (1:200), (1:300), and (1:400). Previous UV irradiation studies of anthracene:H{sub 2}O, pyrene:H{sub 2}O, and benzo[ghi]perylene:H{sub 2}O ices at 15 K have shown that aromatic alcohols and ketones, as well as CO{sub 2} and H{sub 2}CO, are formed at very low temperatures. Likewise, here, in addition to the coronene cation, hydroxy-, keto-, and protonated coronene (coronene H{sup +}) are formed. The rate constants for the decay of neutralmore » coronene and for the formation of photoproducts have been derived. It is shown that Polycyclic Aromatic Hydrocarbons (PAHs) and their UV induced PAH:H{sub 2}O photoproducts have mid-infrared spectroscopic signatures in the 5–8 μ m region that can contribute to the interstellar ice components described by Boogert et al. as C1–C5. Our results suggest that oxygenated and hydrogenated PAHs could be in UV-irradiated regions of the interstellar medium where water-rich ices are important.« less

Quenching of Emission and of Photochemistry for Aqueous Rh(NH3)5Cl(2+).

DTIC Science & Technology

1979-04-01

Hueneme, CalifornIa 93041 Attn: Dr. R. 3. Marcus 1 Attn: Mr. W. S. Haynes ONR Branch Offi ce Professor 0. Hein7 760 Market Street , Rm. 447...Peebles 1 WashI ngton, D.C. 20380 Directo r, Naval Research Laboratory Offi ce of Naval Researc hWashington, D.C. 20390 Arlington, VIrginia 22217

76 FR 21712 - Meeting of the Ocean Research and Resources Advisory Industry Sub-Panel

Federal Register 2010, 2011, 2012, 2013, 2014

2011-04-18

... creative problem-solving to overcome impediments to industry progress toward deploying operational projects... held at the Consortium for Ocean Leadership, 1201 New York Avenue, NW., 4th Floor, Washington, DC 20005...

A three-dimensional viscous/potential flow interaction analysis method for multi-element wings: Modifications to the potential flow code to allow part-span, high-lift devices and close-interference calculations

NASA Technical Reports Server (NTRS)

Maskew, B.

1979-01-01

The description of the modified code includes details of a doublet subpanel technique in which panels that are close to a velocity calculation point are replaced by a subpanel set. This treatment gives the effect of a higher panel density without increasing the number of unknowns. In particular, the technique removes the close approach problem of the earlier singularity model in which distortions occur in the detailed pressure calculation near panel corners. Removal of this problem allowed a complete wake relaxation and roll-up iterative procedure to be installed in the code. The geometry package developed for the new technique and also for the more general configurations is based on a multiple patch scheme. Each patch has a regular array of panels, but arbitrary relationships are allowed between neighboring panels at the edges of adjacent patches. This provides great versatility for treating general configurations.

UV photochemistry of carboxylic acids at the air-sea boundary: A relevant source of glyoxal and other oxygenated VOC in the marine atmosphere

NASA Astrophysics Data System (ADS)

Chiu, R.; Tinel, L.; Gonzalez, L.; Ciuraru, R.; Bernard, F.; George, C.; Volkamer, R.

2017-01-01

Photochemistry plays an important role in marine dissolved organic carbon (DOC) degradation, but the mechanisms that convert DOC into volatile organic compounds (VOCs) remain poorly understood. We irradiated carboxylic acids (C7-C9) on a simulated ocean surface with UV light (<320 nm) in a photochemical flow reactor and transferred the VOC products into a dark ozone reactor. Glyoxal was detected as a secondary product from heptanoic, octanoic, and nonanoic acid (NA) films, but not from octanol. Primary glyoxal emissions were not observed, nor was glyoxal formed in the absence of ozone. Addition of a photosensitizer had no noticeable effect. The concurrent detection of heptanal in the NA system suggests that the ozonolysis of 2-nonenal is the primary chemical mechanism that produces glyoxal. This source can potentially sustain tens of parts per trillion by volume (pptv) glyoxal over oceans, and helps to explain why glyoxal fluxes in marine air are directed from the atmosphere into the ocean.

75 FR 38464 - Pacific Fishery Management Council; Public Meeting

Federal Register 2010, 2011, 2012, 2013, 2014

2010-07-02

... Pacific Fishery Management Council (Pacific Council) will convene a meeting of the Ecosystem Plan... purpose of reviewing comments of the Ecosystem Advisory Subpanel (EAS) and drafting a report to the Pacific Council on initial stages of developing an Ecosystem Fishery Management Plan (EFMP). The EPDT has...

78 FR 49259 - Pacific Fishery Management Council; Public Meeting

Federal Register 2010, 2011, 2012, 2013, 2014

2013-08-13

... DEPARTMENT OF COMMERCE National Oceanic and Atmospheric Administration RIN 0648-XC805 Pacific Fishery Management Council; Public Meeting AGENCY: National Marine Fisheries Service (NMFS), National... (STT), the Salmon Advisory Subpanel (SAS), and the Model Evaluation Workgroup (MEW) by telephone...

75 FR 4348 - Pacific Fishery Management Council; Public Meeting

Federal Register 2010, 2011, 2012, 2013, 2014

2010-01-27

... Pacific Fishery Management Council (Pacific Council) will convene a joint meeting of the Ecosystem Plan Development Team (EPDT) and Ecosystem Advisory Subpanel (EAS) which is open to the public. DATES: The meeting... review Pacific Council guidance and make recommendations on implementing an ecosystem-based management...

50 CFR 660.502 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-10-01

... terms used in this subpart have the following meanings: Actively managed species (AMS) means those CPS... management according to the provisions of the FMP. Advisory Subpanel (AP) means the Coastal Pelagic Species..., by weight, of a coastal pelagic species population. The term biomass means total biomass (age 1 and...

50 CFR 660.502 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-10-01

... terms used in this subpart have the following meanings: Actively managed species (AMS) means those CPS... management according to the provisions of the FMP. Advisory Subpanel (AP) means the Coastal Pelagic Species..., by weight, of a coastal pelagic species population. The term biomass means total biomass (age 1 and...

76 FR 542 - Pacific Fishery Management Council (Council); Public Meeting

Federal Register 2010, 2011, 2012, 2013, 2014

2011-01-05

.... SUMMARY: The Pacific Fishery Management Council (Pacific Council) will convene a meeting of the Ecosystem... development of an Ecosystem Fishery Management Plan (EFMP). At the September 2010 Council meeting, the EPDT and the Ecosystem Advisory Subpanel provided an initial report on EFMP development that included a...

Photochemistry of pyrene with water at low temperature: study of atmospherical and astrochemical interest.

PubMed

Guennoun, Zohra; Aupetit, Christian; Mascetti, Joëlle

2011-03-17

Photochemistry of a polyaromatic hydrocarbon, pyrene C(16)H(10), with water has been investigated at cryogenic temperatures. Photoprocessing of this species, performed at λ > 235 nm, in argon matrices, adsorbed onto amorphous water surfaces, and trapped in solid water, led to the formation of ketonic isomers, C(16)H(10)O, and possibly quinones. These species have been identified for the first time by infrared spectroscopy with the support of isotopic substitution experiments and DFT calculations. These oxidized pyrene-like species, of atmospherical and astrochemical interest, most likely arise from a tautomeric rearrangement of their analogous hydroxylated molecules, these latter being formed by reaction of water with pyrene cations.

Photochemistry of cyclopentadiene isolated in low-temperature argon matrices

NASA Astrophysics Data System (ADS)

Miyazaki, Jun; Yamada, Yasuhiro

2004-04-01

The photochemistry of cyclopentadiene isolated in low-temperature argon matrices was studied by means of IR and UV/VIS spectroscopy. Bicyclo[2.1.0]pent-2-ene was formed by the irradiation of matrix-isolated cyclopentadiene using a super-high-pressure mercury lamp. When the matrix-isolated cyclopentadiene was irradiated with shorter wavelength using a low-pressure mercury lamp, further reactions of bicyclo[2.1.0]pent-2-ene were found to produce allylacetylene and vinylallene. While the photochemistry of cyclopentadiene to form bicyclo[2.1.0]pent-2-ene is known in a solution system, the production of allylacetylene and vinylallene in a matrix-isolated system has never been previously reported. The assignments of the species and the determination of the reaction mechanisms were performed using molecular orbital calculations.

Informal Conference on Photochemistry (15th) Held at Stanford, California on 27 June-1 July 1982

DTIC Science & Technology

1982-01-01

C-2 Photofragment Spectroscopy of Ultracold NO2 at 355nm: Internal Energy Distributions of NO A. P. Daronavski, Benjamin H . DeKoven, and H .’ Helvajian ...of C3 With Selected Olefins Over the Temperature Range 300-650 K H . Helvajian , H . H . Nelson, L. Pasternack and J. R. McDonald 11:45 H -5 Abstraction vs...of Ultracold N02 at 355nm: Internal Energy Distributions of NO A. P. Baronavski, Benjamin M. DeKovenu and H . Helvajian * Chemistry Division, Naval

Photochemical Studies of Chemistry in the Outer Solar System

NASA Technical Reports Server (NTRS)

Yung, Yuk L.

2003-01-01

The goal of the proposed science investigation is to gain a quantitative understanding of chemical processes and their coupling with atmospheric dynamics in the reducing atmospheres of the outer solar system, with a particular focus on Infrared Space Observatory (ISO) observations and future experiments such as the Cassini Mission to Saturn and Titan. The proposed work is divided into two related tasks. We have carried out a systematic comparison between atmospheric models for every giant planet and Titan, which employ a consistent set of photochemical reactions. Combined with recent observations of hydrocarbon species by ISO, this can provide the most rigorous test of our current understanding of the photochemistry of hydrocarbon in the outer solar system. The emphasis will be on the methyl radical (CH3), first detected by IS0 in the atmospheres of Saturn and Neptune (Bezard et al. 1998). CH3 is one of the most important radicals in the hydrocarbon photochemistry because it is the primary product of methane photolysis and plays an essential role in forming C2H6, the most abundant and stable C2 species. A fundamental understanding of the distribution of CH3 provides unique insights into the chemistry of hydrocarbons as well as comparative planetology.

Nitrogen and Oxygen Photochemistry following SL9

NASA Technical Reports Server (NTRS)

Moses, Julianne I.; Allen, Mark; Gladstone, G. Randall

1995-01-01

The collision of Shoemaker Levy 9 (SL9) with Jupiter caused many new molecular species to be deposited in the Jovian stratosphere. We use a photochemical model to follow the evolution of the impact derived species. Our results regarding the nitrogen and oxygen compounds are presented here. NH3 photolysis initiates the nitrogen photochemistry. Much of the nitrogen ends up in N2, nitrogen-sulfur compounds, and HCN, but NH3 and nitriles such as C2H3CN may also exist in observable quantities for a year or so after the impacts. Oxygen species survive for a long time in the Jovian stratosphere. The only major oxygen containing compounds that exhibit dramatic changes in the lower stratosphere in the first year following the impacts are SO, SO2, and OCS - H2O, CO2, and CO are comparatively stable. We discuss the important photochemical processes operating on the nitrogen and oxygen species in the Jovian stratosphere, make prediction concerning the temporal variation of the major species, and identify molecules that might act as good tracers for atmospheric dynamics.

Photochemistry in everyday life: the effect of spontaneous emulsification on the photochemistry of trans-anethole.

PubMed

Carteau, David; Brunerie, Pascal; Guillemat, Bruno; Bassani, Dario M

2007-04-01

The photochemical behaviour of spontaneously formed microemulsions obtained upon dilution of ethanolic solutions of trans-anethole (E-1-(4-methoxyphenyl)propene, t-A) with water is compared to that of homogeneous ethanolic t-A solutions. Significant differences in reactivity reflect the confined nature of the aggregated t-A which leads to reduced yields of isomerization and dimerization products. In contrast to homogeneous solutions, where a photostationary state enriched in the Z-isomer (c-A) is rapidly reached, the proportion of c-A formed upon irradiation of t-A microemulsions remains below 15%. In the presence of oxygen the formation of trans-anethole oxide is observed which, when formed in non-homogeneous environments, undergoes polymerization.

Photochemistry of Surface-Confined Organometallics: Photochemical Release of a Surface-Confined Cobalt Carbonyl Catalyst.

DTIC Science & Technology

1981-06-08

a r~ 2,2 3 ai ey, -. ar.ger, S.. :.hem. Rev., , 2, ¢9 5 Hartley, F.R.; Vezey, P.. Aav . Organo’et. , em., 1977, 7, 139. 6. Grusnka, E.; Kikta, E.J...sooctane- 1.2- hSC (C)zSIt 996 1.0 - 1991 sh 75min hzu wL 30min hzu ~0.8- 0 0.6- < 2027 0.475 11lmin hu 30 0.2- 0.0 2050 2000 1950 1900 WAVENUMBERS (cm𔃻) Q

Heterogeneous photochemistry of oxalic acid on Mauritanian sand and Icelandic volcanic ash.

PubMed

Styler, Sarah A; Donaldson, D J

2012-08-21

Teragram quantities of crustal and volcanic aerosol are released into the atmosphere on an annual basis. Although these substrates contain photoactive metal oxides, little is known about the role that they may play in catalyzing the heterogeneous phototransformation of semivolatile organic species. In the present study, we have investigated oxalic acid photochemistry at the surface of Fe(2)O(3), TiO(2), Mauritanian sand, and Icelandic volcanic ash in the presence and absence of oxygen using a photochemical Knudsen cell reactor. Illumination of all sample types resulted in the production of gas-phase CO(2). In the case of Mauritanian sand, the production of gas-phase CO(2) scaled with the loss of surface oxalic acid. In the absence of oxygen, the production of CO(2) by the sand and ash films scaled with the absorption spectrum of iron oxalate, which suggests that the reaction is at least in part iron-mediated. The presence of oxygen suppressed CO(2) production at the Fe(2)O(3) surface, enhanced CO(2) production at the Mauritanian sand surface, and did not have a net effect upon CO(2) production at the Icelandic ash surface. These different oxygen dependencies imply that oxalic acid photochemistry at the authentic surfaces under study was not solely iron-mediated. Experiments at the TiO(2) surface, which showed enhanced CO(2) production from oxalic acid in the presence of oxygen, suggest that Ti-mediated photochemistry played an important role. In summary, these results provide evidence that solid-phase aerosol photochemistry may influence the atmospheric lifetime of oxalic acid in arid regions, where its removal via wet deposition is insignificant.

Experimental and theoretical simulations of Titan's VUV photochemistry

NASA Astrophysics Data System (ADS)

Peng, Z.; Carrasco, N.; Pernot, P.

2013-12-01

A new reactor, named APSIS (Atmospheric Photochemistry SImulated by Synchrotron), has been designed to simulate planetary atmospheric photochemistry [Peng et al. JGR-E. 2013, 118, 778]. We report here a study focusing on Titan's upper atmosphere. A nitrogen-methane gas flow was irradiated by a continuous 60-350 nm VUV beam provided by the DISCO line at SOLEIL synchrotron radiation facility. The production of C2-C4 hydrocarbons as well as several nitriles (HCN, CH3 CN and C2N2) was detected by in situ mass spectrometry, in agreement with Cassini's INMS observations at Titan, and ex situ GC-MS of a cryogenic experiment. We compared the mass spectra with those obtained by a plasma experiment [Carrasco et al. Icarus. 2012, 219, 230] and with another synchrotron-based experiment [Imanaka and Smith. PNAS. 2010, 107, 12423], and with the in situ measurements of the INMS instrument onboard Cassini probing the neutral content of Titan's upper atmosphere. In spite of lower photochemical production efficiency and different environmental conditions, the APSIS reactor seems to simulate Titan's neutral composition rather well. To interpret these experimental data, we developed a fully coupled ion-neutral photochemical model of the reactor, with uncertainty management, based on the neutral model of Hébrard et al. [J. Photochem. Photobiol. A. 2006, 7, 211], the model of ion chemistry of Plessis et al. [J. Chem. Phys. 2010, 133, 134110], and a new representation of photolysis cross-sections and branching ratios [Gans et al. Icarus. 2013, 223, 330]. Compared to the measurements, the production in Cn blocks is in good agreement. Ion chemistry and the full dissociative recombination scheme have been demonstrated to be important features of the model. The photolysis was confirmed to be globally influential by sensivity analysis. We observed the importance of the addition of small (C1 or C2) units in molecular growth, as well as 3 growth families, promoted by C2H2, C2H4 and C2H5/C2H6, respectively. Among the three, the C2H2 family, in which the growth pathways of unsaturated species via ion chemistry are the most efficient, is clearly prominent. Our model was also used to interpret the results of the INMS data and Imanaka and Smith's experiments. Through variants of the reference model of the APSIS experiments, we showed that low pressure and low temperature favor the growth of unsaturated species. These conditions are fulfilled in Titan's ionosphere. The INMS neutral spectrum, in which there is mainly the signal of unsaturated species, can be well reproduced by our simulated MS. Compared to the experimental MS of the APSIS experiments and Imanaka and Smith's experiments, the simulated MS systematically underestimate the intensities of the saturated part of each band. After the consideration of the recombinations catalyzed by the reactor's walls, we improved the simulated MS significantly. This suggests the existence of wall effects in the laboratory simulation setups of atmospheric chemistry, leading to an overestimation of the saturated products compared to Titan's chemical products.

Isotopic Ordering in Atmospheric O2 as a Tracer of Ozone Photochemistry and the Tropical Atmosphere

NASA Technical Reports Server (NTRS)

Yeung, Laurence Y.; Murray, Lee T.; Ash, Jeanine L.; Young, Edward D.; Boering, Kristie A.; Atlas, Elliot L.; Schauffler, Sue M.; Lueb, Richard A.; Langenfelds, Ray L.; Krummel, Paul B.;

Atmospheric photochemistry at a fatty acid coated air/water interface

NASA Astrophysics Data System (ADS)

George, Christian; Rossignol, Stéphanie; Passananti, Monica; Tinel, Liselotte; Perrier, Sebastien; Kong, Lingdong; Brigante, Marcello; Bianco, Angelica; Chen, Jianmin; Donaldson, James

2017-04-01

Over the past 20 years, interfacial processes have become increasingly of interest in the field of atmospheric chemistry, with many studies showing that environmental surfaces display specific chemistry and photochemistry, enhancing certain reactions and acting as reactive sinks or sources for various atmospherically relevant species. Many molecules display a free energy minimum at the air-water interface, making it a favored venue for compound accumulation and reaction. Indeed, surface active molecules have been shown to undergo specific photochemistry at the air-water interface. This presentation will address some recent surprises. Indeed, while fatty acids are believed to be photochemically inert in the actinic region, complex volatile organic compounds (VOCs) are produced during illumination of an air-water interface coated solely with a monolayer of carboxylic acid. When aqueous solutions containing nonanoic acid (NA) at bulk concentrations that give rise to just over monolayer NA coverage are illuminated with actinic radiation, saturated and unsaturated aldehydes are seen in the gas phase and more highly oxygenated products appear in the aqueous phase. This chemistry is probably initiated by triplet state NA molecules excited by direct absorption of actinic light at the water surface. As fatty acids covered interfaces are ubiquitous in the environment, such photochemical processing will have a significant impact on local ozone and particle formation. In addition, it was shown recently that a heterogeneous reaction between SO2 and oleic acid (OA; an unsaturated fatty acid) takes place and leads efficiently to the formation of organosulfur products. Here, we demonstrate that this reaction proceeds photochemically on various unsaturated fatty acids compounds, and may therefore have a general environmental impact. This is probably due to the chromophoric nature of the SO2 adduct with C=C bonds, and means that the contribution of this direct addition of SO2 could be in excess of 5%.

Poster 11: Simulating the VUV photochemistry in the upper atmosphere of Titan

NASA Astrophysics Data System (ADS)

Tigrine, Sarah; Carrasco, Nathalie; Vettier, Ludovic; Cernogora, Guy

2016-06-01

The Cassini mission around Titan revealed that the interaction between the N2 and CH4 molecules and the solar VUV radiation leads to a complex chemistry above an altitude of 800 km with the detection of heavy organic molecules like benzene (C6H6). This is consistent with an initiation of the aerosols in Titan's upper atmosphere. The presence of those molecules makes Titan a natural laboratory to witness and understand prebiotic-like chemistry but despite all the data collected, all the possible photochemical processes in such a hydrocarbon-nitrogen-rich environment are not precisely understood. This is why Titan's atmospheric chemistry experiments are of high interest, especially those focusing on the photochemistry as most of the Titan-like experiments are based on N2-CH4 plasma techniques. In order to reproduce this VUV photochemistry of N2 and CH4, we designed a photochemical reactor named APSIS which is to be coupled window-less with a VUV photon source as N2 needs wavelengths shorter than 100 nm in order to be dissociated. Those wavelengths are available at synchrotron beamlines but are challenging to obtain with common laboratory discharge lamps. At LATMOS, we developed a table-top VUV window-less source using noble gases for the micro-wave discharge. We started with Neon, as it has two resonance lines at 73.6 and 74.3 nm which allow us to dissociate and/or ionize both CH4 and N2. We will present here our first experimental results obtained with APSIS coupled with this VUV source and then discuss them regarding the Cassini data and other previous laboratory photochemical studies.

77 FR 58981 - Fisheries of the South Atlantic and Gulf of Mexico; South Atlantic Fishery Management Council...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-09-25

... (NOAA), Commerce. ACTION: Notice of public meeting. SUMMARY: The SAFMC will hold a meeting of its Social... DEPARTMENT OF COMMERCE National Oceanic and Atmospheric Administration RIN 0648-XC181 Fisheries [email protected] . SUPPLEMENTARY INFORMATION: The SAFMC SEP is a sub-panel that addresses social and economic...

Photochemistry in Terrestrial Exoplanet Atmospheres. I. Photochemistry Model and Benchmark Cases

NASA Astrophysics Data System (ADS)

Hu, Renyu; Seager, Sara; Bains, William

2012-12-01

We present a comprehensive photochemistry model for exploration of the chemical composition of terrestrial exoplanet atmospheres. The photochemistry model is designed from the ground up to have the capacity to treat all types of terrestrial planet atmospheres, ranging from oxidizing through reducing, which makes the code suitable for applications for the wide range of anticipated terrestrial exoplanet compositions. The one-dimensional chemical transport model treats up to 800 chemical reactions, photochemical processes, dry and wet deposition, surface emission, and thermal escape of O, H, C, N, and S bearing species, as well as formation and deposition of elemental sulfur and sulfuric acid aerosols. We validate the model by computing the atmospheric composition of current Earth and Mars and find agreement with observations of major trace gases in Earth's and Mars' atmospheres. We simulate several plausible atmospheric scenarios of terrestrial exoplanets and choose three benchmark cases for atmospheres from reducing to oxidizing. The most interesting finding is that atomic hydrogen is always a more abundant reactive radical than the hydroxyl radical in anoxic atmospheres. Whether atomic hydrogen is the most important removal path for a molecule of interest also depends on the relevant reaction rates. We also find that volcanic carbon compounds (i.e., CH4 and CO2) are chemically long-lived and tend to be well mixed in both reducing and oxidizing atmospheres, and their dry deposition velocities to the surface control the atmospheric oxidation states. Furthermore, we revisit whether photochemically produced oxygen can cause false positives for detecting oxygenic photosynthesis, and find that in 1 bar CO2-rich atmospheres oxygen and ozone may build up to levels that have conventionally been accepted as signatures of life, if there is no surface emission of reducing gases. The atmospheric scenarios presented in this paper can serve as the benchmark atmospheres for quickly assessing the lifetime of trace gases in reducing, weakly oxidizing, and highly oxidizing atmospheres on terrestrial exoplanets for the exploration of possible biosignature gases.

VUV Photoionisation of hydrocarbon radicals

NASA Astrophysics Data System (ADS)

Alcaraz, C.; Noller, Bastian; Hemberger, Patrick; Fischer, Ingo; Gans, Bérenger; Boyé-Peronne, Séverine; Douin, Stéphane; Gauyacq, Dolorès; Soldi-Lose, Héloïse; Garcia, Gustavo

2008-09-01

Hydrocarbon radicals CxHy are constituents of various planetary atmospheres, in particular Titan, as a result of the methane photochemistry induced by the solar radiation. They contribute to the neutral chemistry, but are also important for the ionosphere through their photoionisation leading to their cations CxHy +. These cations are also produced by ion-molecule reactions starting from the reaction of the primary ions CH4 + and CH3 + which are created in the non-dissociative and dissociative photoionisation of CH4. This work aims at caracterizing the VUV photoionisation of small hydrocarbon radicals as a function of photon energy. The objective is to provide laboratory data for modelers on the spectroscopy, the thermochemistry, and the reactivity of the radicals and their cations. The hydrocarbon radicals are much less caracterized than stable molecules since they have to be produced in situ in the laboratory experiment. We have adapted at Orsay [1-3] a pyrolysis source (Figure 1) well suited to produce cold beams of hydrocarbon radicals to our experimental setups. Available now at Orsay, we have two new sources of VUV radiation, complementary in terms of tunability and resolution, that can be used for these studies. The first one is the DESIRS beamline [4] at the new french synchrotron, SOLEIL. The second one is the VUV laser developped at the Centre Laser de l'Université Paris-Sud (CLUPS) [5]. At SOLEIL, a photoelectron-photoion coincidence spectrometer is used to monitor the photoionisation on a large photon energy range. At the CLUPS, a pulsedfield ionisation (PFI-ZEKE) spectrometer allows studies at higher resolution on selected photon energies. The first results obtained with these new setups will be presented. References [1] Fischer, I., Schussler, T., Deyerl, H.J., Elhanine, M. & Alcaraz, C., Photoionization and dissociative photoionization of the allyl radical, C3H5. Int. J. Mass Spectrom., 261 (2-3), 227-233 (2007) [2] Schüßler, T., Roth, W., Gerber, T., Alcaraz, C. & Fischer, I., The vacuum ultraviolet photochemistry of radicals: C3H3 and C2H5. Phys. Chem. Chem. Phys., 7 (5), 819-825 (2005) [3] Schüßler, T., Deyerl, H. J., Dummler, S., Fischer, I., Alcaraz, C. & Elhanine, M., The vacuum ultraviolet photochemistry of the allyl radical investigated using synchrotron radiation J. Chem. Phys., 118 (20), 9077-80 (2003) [4] DESIRS, http://www.synchrotronsoleil. fr/portal/page/portal/Recherche/LignesLumiere/ DESIRS [5] CLUPS, http://www.clups.u-psud.fr/

Electronic and Ionic Transport in Processable Conducting Polymers

DTIC Science & Technology

1990-04-10

Multiangle laser light scanting molecular weight GPC studies of a number of different samples of poly(3-octylhiophenc) has shown a’variation from...photochemistry at chemically modified electrodes offers a powerful ro ute to catalyst generation at, the surface.( 0!" 20. DISTRIBUTION /AVAILABILITY OF ABSTRACT...unsymmetric molecules. Oxidative polymerization has been accomplished using both chemical (FeC13) and electrochemical methods. In the case of the 2

Thermochemistry and Photochemistry in Thick Atmospheres on Super Earths and Mini Neptunes

NASA Astrophysics Data System (ADS)

Hu, R.; Seager, S.

2013-12-01

Dectection and characterization of low-mass exoplanets is poised to accelerate in the coming decade. Some low-mass exoplanets, namely super Earths and some mini Neptunes, will likely have thick atmospheres that are not H2-dominated. We have developed a photochemistry-thermochemistry model for exploring the compositions of thick atmospheres on super Earths and mini Neptunes, applicable for both H2-dominated atmospheres and non-H2-dominated atmospheres. Using this model, we have simulated the molecular composition of thick atmospheres on warm and hot super Earths/mini Neptunes, and classified thick atmospheres into hydrogen-rich atmospheres, water-rich atmospheres, oxygen-rich atmospheres, and hydrocarbon-rich atmospheres, depending on the hydrogen abundance and the carbon to oxygen abundance ratio. We find that carbon has to be in the form of CO2 rather than CH4 or CO in an H2-depleted water-dominated thick atmosphere, and that the preferred loss of light elements from an oxygen-poor carbon-rich atmosphere leads to formation of unsaturated hydrocarbons. For future observations, we find for GJ 1214b that (1) C2H2 features at 1.0 and 1.5 μm in transmission are diagnostic for hydrocarbon-rich atmospheres; (2) a constraint on the thermal emission at 4.5 μm could differentiate water-rich atmospheres versus hydrocarbon-rich atmospheres; (3) a detection of water-vapor features and a confirmation of nonexistence of methane features would provide sufficient evidence for a water-dominated atmosphere. For a hot super Earth like 55 Cnc e, the diagnostic features of water-rich atmospheres (H2O) and the diagnostic features of hydrocarbon-rich atmospheres (CO and C2H2) are well separated in transmission spectra at 0.6-5 μm, which would enable straightforward characterization. In general, our simulations show that chemical stability has to be taken into account when interpreting the spectrum of a super Earth/mini Neptune. Theoretical transmission spectra and thermal emission spectra of non-H2-dominated atmospheres on GJ 1214b based on photochemistry-thermochemistry simulations in comparison with current observations. The simulated spectra are for an hydrogen abundance of 0.5 and a variety of carbon to oxygen ratios ranging from oxygen rich to carbon rich. The atmospheric scenarios with different carbon to oxygen ratios can be constrained via the spectral features of their hallmark molecules.

ERA: Psychological, Social and Ethical Implications for Psychology.

ERIC Educational Resources Information Center

Russo, Nancy Felipe; Hilberman, Elaine

The mental health implications of sex discrimination as considered by the Subpanel on the Mental Health of Women of the President's Commission of Mental Health are discussed. The status of women's mental health and the problems of women in the mental health delivery system are considered in relation to the larger societal context. Prevention of…

76 FR 57958 - Fisheries of the South Atlantic and Gulf of Mexico; South Atlantic Fishery Management Council...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-09-19

...) will hold meetings of its Scientific and Statistical Committee (SSC) and Socio-Economic Sub-Panel (SEP) to review fishery management plan (FMP) amendments under development, ABC control rule approaches... process. The SSC will discuss FMP amendments under development, assessments of black sea bass and tilefish...

The UV photochemistry of C2N2

NASA Technical Reports Server (NTRS)

Halpern, Joshua B.; Barts, Samuel A.

1989-01-01

The absorption, emission, and photodissociation yield spectra of C2N2 were measured in the 220 and 210 nm region near the 4(0)1 and 1(0)1 4(0)1 bands of the A 1 sigma + from the X 1 sigma + system. The emission spectrum showed very few lines which appeared in the absorption spectrum. Moreover, the emission had 660 ns lifetime and, at 210 nm a very large electronic emission quenching rate. Laser induced fluorescence was used to measure the relative yield of CN radicals as a function of photolysis wavelength. This spectrum seemed to follow the absorption spectrum below the dissociation threshold. Energy in the CN fragments appeared to be statistically distributed.

Ultrafast dynamics of the photo-excited hemes b and cn in the cytochrome b6f complex.

PubMed

Agarwal, Rachna; Chauvet, Adrien A P

2017-01-25

The dynamics of hemes b and c n within the cytochrome b 6 f complex are investigated by means of ultrafast broad-band transient absorption spectroscopy. On the one hand, the data reveal that, subsequent to visible light excitation, part of the b hemes undergoes pulse-limited photo-oxidation, with the liberated electron supposedly being transferred to one of the adjacent aromatic amino acids. Photo-oxidation is followed by charge recombination in about 8.2 ps. Subsequent to charge recombination, heme b is promoted to a vibrationally excited ground state that relaxes in about 4.6 ps. On the other hand, heme c n undergoes ultrafast ground state recovery in about 140 fs. Interestingly, the data also show that, in contrast to previous beliefs, Chl a is involved in the photochemistry of hemes. Indeed, subsequent to heme excitation, Chl a bleaches and recovers to its ground state in 90 fs and 650 fs, respectively. Chl a bleaching allegedly corresponds to the formation of a short lived Chl a anion. Beyond the previously suggested structural role, this study provides unique evidence that Chl a is directly involved in the photochemistry of the hemes.

Observations of Acyl Peroxy Nitrates During the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ)

NASA Astrophysics Data System (ADS)

Zaragoza, Jake; Callahan, Sara; McDuffie, Erin E.; Kirkland, Jeffrey; Brophy, Patrick; Durrett, Lindsi; Farmer, Delphine K.; Zhou, Yong; Sive, Barkley; Flocke, Frank; Pfister, Gabriele; Knote, Christoph; Tevlin, Alex; Murphy, Jennifer; Fischer, Emily V.

2017-11-01

We report on measurements of acyl peroxy nitrates (APNs) obtained from two ground sites and the NSF/National Center for Atmospheric Research C-130 aircraft during the 2014 Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ). The relative abundance of the APNs observed at the Boulder Atmospheric Observatory (BAO) indicates that anthropogenic emissions of volatile organic compounds (VOCs) are the dominant drivers of photochemistry during days with the most elevated peroxyacetyl nitrate (PAN). Reduced major axis regression between propionyl peroxynitrate (PPN) and PAN observed at BAO and from the C-130 produced a slope of 0.21 (R2 = 0.92). Periods of lower PPN/PAN ratios ( 0.10) were associated with cleaner background air characterized by lower ammonia and formic acid abundances. The abundance of methacryloyl peroxynitrate relative to PAN only exceeded 0.05 at BAO when PAN mixing ratios were <300 parts per trillion by volume, implying low influence of isoprene oxidation during periods with substantial local PAN production. We show an example of a day (19 July) where high O3 was not accompanied by enhanced local PAN production. The contribution of biogenic VOCs to local O3 production on the other days in July with elevated O3 (22, 23, 28, and 29 July 2014) was small; evidence is provided in the high abundance of PPN to PAN (slopes between 0.18 and 0.26). The PAN chemistry observed from surface and aircraft platforms during FRAPPÉ implies that anthropogenic VOCs played a dominant role in PAN production during periods with the most O3 and that the relative importance of biogenic hydrocarbon chemistry decreased with increasing O3 production during FRAPPÉ.

Photodissociation Cross Sections for the Production of C2 from C2H Using Laser Induced Hg Photosensitization and Tunable Ultraviolet and Visible Lasers

NASA Technical Reports Server (NTRS)

Jackson, William M.

1996-01-01

The principle goal of our research was to understand the formation of free radicals in comets. To do this we compared laboratory results with cometary observations in attempt to make sure that the cometary observations agree with what is known about the photochemistry of the proposed parent molecule. Initially we concentrated on the CS emission in an effort to show the parent of this molecule was CS2, consistent with cometary observations of the photochemical lifetime. We then started to look into the problem of the C2 formation in comets. We set out to see if we could measure all of the nascent distributions of the C2 products in the hope that they would be a characteristic signature of the formation process.

Photochemistry, mixing and transport in Jupiter's stratosphere constrained by Cassini

NASA Astrophysics Data System (ADS)

Hue, V.; Hersant, F.; Cavalié, T.; Dobrijevic, M.; Sinclair, J. A.

2018-06-01

In this work, we aim at constraining the diffusive and advective transport processes in Jupiter's stratosphere, using Cassini/CIRS observations published by Nixon et al. (2007,2010). The Cassini-Huygens flyby of Jupiter on December 2000 provided the highest spatially resolved IR observations of Jupiter so far, with the CIRS instrument. The IR spectrum contains the fingerprints of several atmospheric constituents and allows probing the tropospheric and stratospheric composition. In particular, the abundances of C2H2 and C2H6, the main compounds produced by methane photochemistry, can be retrieved as a function of latitude in the pressure range at which CIRS is sensitive to. CIRS observations suggest a very different meridional distribution for these two species. This is difficult to reconcile with their photochemical histories, which are thought to be tightly coupled to the methane photolysis. While the overall abundance of C2H2 decreases with latitude, C2H6 becomes more abundant at high latitudes. In this work, a new 2D (latitude-altitude) seasonal photochemical model of Jupiter is developed. The model is used to investigate whether the addition of stratospheric transport processes, such as meridional diffusion and advection, are able to explain the latitudinal behavior of C2H2 and C2H6. We find that the C2H2 observations are fairly well reproduced without meridional diffusion. Adding meridional diffusion to the model provides an improved agreement with the C2H6 observations by flattening its meridional distribution, at the cost of a degradation of the fit to the C2H2 distribution. However, meridional diffusion alone cannot produce the observed increase with latitude of the C2H6 abundance. When adding 2D advective transport between roughly 30 mbar and 0.01 mbar, with upwelling winds at the equator and downwelling winds at high latitudes, we can, for the first time, reproduce the C2H6 abundance increase with latitude. In parallel, the fit to the C2H2 distribution is degraded. The strength of the advective winds needed to reproduce the C2H6 abundances is particularly sensitive to the value of the meridional eddy diffusion coefficient. The coupled fate of these methane photolysis by-products suggests that an additional process is missing in the model. Ion-neutral chemistry was not accounted for in this work and might be a good candidate to solve this issue.

Comparisons of Photosynthetic Responses of Xanthium strumarium and Helianthus annuus to Chronic and Acute Water Stress in Sun and Shade 1

PubMed Central

Ben, Gui-Ying; Osmond, C. Barry; Sharkey, Thomas D.

1987-01-01

We have examined the effects of mild, chronic water stress and acute water stress on two water stress sensitive plants, Xanthium strumarium and Helianthus annuus. Using a combination of the leaf disc O2 electrode to measure the light responses of photosynthesis and 77 K fluorescence to monitor damage to the primary photochemistry, we have found the following: (a) The CO2 saturated rate of photosynthesis at high light is the most water stress sensitive parameter measured. (b) The apparent quantum yield (moles O2 per mole photons) was slightly, if at all, affected by mild water stress (>−1.5 megapascals). (c) Severe water stress (<−1.5 megapascals) reduced the quantum yield of photosynthesis regardless of whether the stress was applied in sun or shade. The light independent reduction of quantum yield was not associated with a reduction in 77 K fluorescence (Fv/Fm) indicating that the quantum yield reduction was not the result of damage to primary photochemistry. (d) The diel fluctuation in 77 K fluorescence seen in sun-exposed control leaves was greatly exaggerated in water stressed leaves because of enhanced decline in 77 K fluorescence in the morning. The rate of recovery was similar in both control and water stressed leaves. Shaded leaves showed no change in 77 K fluorescence regardless of whether water stress was imposed or not. (e) The water stress sensitive plants used in these experiments did not recover from acute water stress severe enough to reduce the quantum yield or chronic water stress which lasted long enough that light dependent damage to primary photochemistry occurred. PMID:16665465

Comparisons of Photosynthetic Responses of Xanthium strumarium and Helianthus annuus to Chronic and Acute Water Stress in Sun and Shade.

PubMed

Ben, G Y; Osmond, C B; Sharkey, T D

1987-06-01

We have examined the effects of mild, chronic water stress and acute water stress on two water stress sensitive plants, Xanthium strumarium and Helianthus annuus. Using a combination of the leaf disc O(2) electrode to measure the light responses of photosynthesis and 77 K fluorescence to monitor damage to the primary photochemistry, we have found the following: (a) The CO(2) saturated rate of photosynthesis at high light is the most water stress sensitive parameter measured. (b) The apparent quantum yield (moles O(2) per mole photons) was slightly, if at all, affected by mild water stress (>-1.5 megapascals). (c) Severe water stress (<-1.5 megapascals) reduced the quantum yield of photosynthesis regardless of whether the stress was applied in sun or shade. The light independent reduction of quantum yield was not associated with a reduction in 77 K fluorescence (F(v)/F(m)) indicating that the quantum yield reduction was not the result of damage to primary photochemistry. (d) The diel fluctuation in 77 K fluorescence seen in sun-exposed control leaves was greatly exaggerated in water stressed leaves because of enhanced decline in 77 K fluorescence in the morning. The rate of recovery was similar in both control and water stressed leaves. Shaded leaves showed no change in 77 K fluorescence regardless of whether water stress was imposed or not. (e) The water stress sensitive plants used in these experiments did not recover from acute water stress severe enough to reduce the quantum yield or chronic water stress which lasted long enough that light dependent damage to primary photochemistry occurred.

A two-dimensional study of ethane and propane oxidation in the troposphere

NASA Technical Reports Server (NTRS)

Kanakidou, M.; Valentin, K. M.; Crutzen, P. J.; Singh, H. B.

1991-01-01

The chemistry of ethane and propane is studied using a global two-dimensional 'zonally averaged' height- and latitude-dependent tropospheric model. The purpose of the study is to derive theoretical estimates of the seasonal and latitudinal distributions of a variety of intermediate organic compounds formed by the photochemical oxidation of C2H6 and C3H8. It is shown that C2H6 and C3H8 emitted at rates of 16 Tg C2H6/a and 23 Tg C3H8/a do not affect the overall photochemistry of the troposphere significantly. Major global effects on O3 and OH concentrations are suggested to be coming from the formation of peroxyacetyl nitrate by the interactions of NOx with other hydrocarbons with strong and spatially correlated anthropogenic or natural sources at the earth's surface. It is pointed out that attention should be given to organic nitrates produced by the oxidation of NMHC other than C2H6 and C3H8.

Flow photochemistry: Old light through new windows

PubMed Central

Knowles, Jonathan P; Elliott, Luke D

2012-01-01

Summary Synthetic photochemistry carried out in classic batch reactors has, for over half a century, proved to be a powerful but under-utilised technique in general organic synthesis. Recent developments in flow photochemistry have the potential to allow this technique to be applied in a more mainstream setting. This review highlights the use of flow reactors in organic photochemistry, allowing a comparison of the various reactor types to be made. PMID:23209538

Simulating the VUV photochemistry of the upper atmosphere of Titan

NASA Astrophysics Data System (ADS)

Tigrine, Sarah; Carrasco, Nathalie; Vettier, Ludovic; Chitarra, Olivia; Cernogora, Guy

2016-10-01

The Cassini mission around Titan revealed that the interaction between the N2 and CH4 molecules and the solar VUV radiation leads to a complex chemistry above an altitude of 800km with the detection of heavy organic molecules like benzene (C6H6). This is consistent with an initiation of the aerosols in Titan's upper atmosphere. The presence of those molecules makes Titan a natural laboratory to witness and understand prebiotic-like chemistry but despite all the data collected, all the possible photochemical processes in such a hydrocarbon-nitrogen-rich environment are not precisely understood.This is why Titan's atmospheric chemistry experiments are of high interest, especially those focusing on the photochemistry as most of the Titan-like experiments are based on N2-CH4 plasma techniques. In order to reproduce this VUV photochemistry of N2 and CH4, we designed a photochemical reactor named APSIS which is to be coupled window-less with a VUV photon source as N2 needs wavelengths shorter than 100 nm in order to be dissociated. Those wavelengths are available at synchrotron beamlines but are challenging to obtain with common laboratory discharge lamps. At LATMOS, we developed a table-top VUV window-less source using noble gases for the micro-wave discharge. We started with Neon, as it has two resonance lines at 73.6 and 74.3 nm which allow us to dissociate and/or ionize both CH4 and N2.We will present here our first experimental results obtained with APSIS coupled with this VUV source. A range of different pressures below 1 mbar is tested, in parallel to different methane ratio. Moreover, other wavelengths are injected by adding some other noble gases in the MO discharge (He, Kr, Xe, Ar). We will review the mass spectra obtained in those different conditions and then discuss them regarding the Cassini data and other previous laboratory photochemical studies.

Living at the margins - The response of deep-water seagrasses to light and temperature renders them susceptible to acute impacts.

PubMed

Chartrand, Kathryn M; Szabó, Milán; Sinutok, Sutinee; Rasheed, Michael A; Ralph, Peter J

2018-05-01

Seagrasses inhabit environments where light varies at different timescales, nonetheless are acutely sensitive to reductions in light beyond some conditional bounds. Two tropical deep-water seagrasses, Halophila decipiens and Halophila spinulosa, from the Great Barrier Reef were tested for their response to defined light and temperature regimes to identify their growth requirements and potential thresholds of mortality. Species were exposed to two light intensities, saturating (75 μmol photons m -2 s -1 ) and limiting (25 μmol photons m -2 s -1 ) light and two temperature treatments (26 °C and 30 °C) over a four-week period. Wavelength-specific parameters of PSII photochemistry were evaluated for seagrass leaves, as well as shoot density, gas exchange, and pigment content. Both species were sustained under saturating light levels (3.2 mol photons m -2 d -1 ) while limiting light led to decreased shoot density for H. decipiens and H. spinulosa after two and four weeks, respectively. Wavelength-specific photochemistry was also affected under light-limiting treatments for both species while the functional absorption cross section was highly conserved. Photoacclimation and physiological adjustments by either species was not adequate to compensate for reduced irradiance suggesting these plants reside at the margins of their functional limits. As such, relatively short periods of light attenuating events, like dredging or flood plumes, may be detrimental to deep-water seagrass populations. Copyright © 2018 Elsevier Ltd. All rights reserved.

A novel synthesis of polymeric CO via useful hard X-ray photochemistry

NASA Astrophysics Data System (ADS)

Pravica, Michael; Sneed, Daniel; Smith, Quinlan; Billinghurst, Brant; May, Tim; White, Melanie; Dziubek, Kamil

2016-12-01

We report on the synchrotron hard X-ray-induced decomposition of strontium oxalate (SrC2O4) pressurized to 7 GPa inside a diamond anvil cell (DAC). After some 4 h of irradiation in a white X-ray synchrotron beam, a dark reddish/brown region formed in the area of irradiation which was surrounded by a yellowish brown remainder in the rest of the sample. Upon depressurization of the sample to ambient conditions, the reacted/decomposed sample was recoverable as a dark brown/red and yellow waxy solid. Synchrotron infrared spectroscopy confirmed the strong presence of CO2 even under ambient conditions with the sample exposed to air and other strongly absorbing regions, suggesting that the sample may likely be polymerized CO (in part) with dispersed CO2 and SrO trapped within the polymer. These results will have significant implications in the ability to readily produce and trap CO2 in situ via irradiation of a simple powder for useful hard X-ray photochemistry and in the ability to easily manufacture polymeric CO (via loading of powders in a DAC or high volume press) without the need for the dangerous and complex loading of toxic CO. A novel means of X-ray-induced polymerization under extreme conditions has also been demonstrated.

Differential Acclimation of Enzymatic Antioxidant Metabolism and Photosystem II Photochemistry in Tall Fescue under Drought and Heat and the Combined Stresses

PubMed Central

Bi, Aoyue; Fan, Jibiao; Hu, Zhengrong; Wang, Guangyang; Amombo, Erick; Fu, Jinmin; Hu, Tao

2016-01-01

Quality inferiority in cool-season turfgrass due to drought, heat, and a combination of both stresses is predicted to be more prevalent in the future. Understanding the various response to heat and drought stress will assist in the selection and breeding of tolerant grass varieties. The objective of this study was to investigate the behavior of antioxidant metabolism and photosystem II (PSII) photochemistry in two tall fescue genotypes (PI 234881 and PI 578718) with various thermotolerance capacities. Wide variations were found between heat-tolerant PI 578718 and heat-sensitive PI 234881 for leaf relative water content, malondialdehyde and electrolyte leakage under drought, high-temperature or a combination of both stresses. The sensitivity of PI 234881 exposed to combined stresses was associated with lower superoxide dismutase activity and higher H2O2 accumulation than that in PI 578718. Various antioxidant enzymes displayed positive correlation with chlorophyll content, but negative with membrane injury index at most of the stages in both tall fescue genotypes. The JIP-test analysis in PI 578718 indicated a significant improvement in ABS/RC, TR0/RC, RE0/RC, RE0/ABS values as compared to the control regime, which indicated that PI 578718 had a high potential to protect the PSII system under drought and high temperature stress. And the PS II photochemistry in PI 234881 was damaged significantly compared with PI578718. Moreover, quantitative RT-PCR revealed that heat and drought stresses deduced the gene expression of psbB and psbC, but induced the expression of psbA. These findings to some extent confirmed that the various adaptations of physiological traits may contribute to breeding in cold-season turfgrass in response to drought, high-temperature, and a combination of both stresses. PMID:27148288

Rapid profiling of laser-induced photochemistry in single microdroplets using mass spectrometry.

PubMed

Tracey, Phillip J; Vaughn, Bartholomew S; Roberts, Brendon J; Poad, Berwyck L J; Trevitt, Adam J

2014-03-18

Rapid assessment of laser-induced photochemistry in single microdroplets is afforded by on-demand microdroplet generation coupled to a commercial ion-trap mass spectrometer. Single microdroplets (diameter ∼50 μm, 65 pL) fall on a steel needle held at +2 kV where they subsequently form a spray that is directed toward the inlet of an ion-trap mass spectrometer. It is demonstrated that single microdroplet mass spectra are recordable, one at a time, for methanol droplets containing 100 μM 4-iodoaniline. Extending on this, to probe laser-initiated photochemistry in single picoliter volumes, a UV laser pulse is timed to intercept the droplet before hitting the needle. Comparison of laser-on and laser-off mass spectra reveals the laser-initiated photochemical products. We demonstrate the technique by following UV laser initiated chemistry in methanol droplets containing 4-iodoaniline and 3-(iodomethyl)-N,N,N-trimethylbenzenamine and reveal numerous products within a few hundred single droplet experiments over several minutes. This technique allows for rapid detection of laser-initiated photochemistry in single picoliter volumes.

Bacillus cereus-induced food-borne outbreaks in France, 2007 to 2014: epidemiology and genetic characterisation

PubMed Central

Glasset, Benjamin; Herbin, Sabine; Guillier, Laurent; Cadel-Six, Sabrina; Vignaud, Marie-Léone; Grout, Joel; Pairaud, Sylvie; Michel, Valérie; Hennekinne, Jacques-Antoine; Ramarao, Nalini; Brisabois, Anne

2016-01-01

The aim of this study was to identify and characterise Bacillus cereus from a unique national collection of 564 strains associated with 140 strong-evidence food-borne outbreaks (FBOs) occurring in France during 2007 to 2014. Starchy food and vegetables were the most frequent food vehicles identified; 747 of 911 human cases occurred in institutional catering contexts. Incubation period was significantly shorter for emetic strains compared with diarrhoeal strains A sub-panel of 149 strains strictly associated to 74 FBOs and selected on Coliphage M13-PCR pattern, was studied for detection of the genes encoding cereulide, diarrhoeic toxins (Nhe, Hbl, CytK1 and CytK2) and haemolysin (HlyII), as well as panC phylogenetic classification. This clustered the strains into 12 genetic signatures (GSs) highlighting the virulence potential of each strain. GS1 (nhe genes only) and GS2 (nhe, hbl and cytK2), were the most prevalent GS and may have a large impact on human health as they were present in 28% and 31% of FBOs, respectively. Our study provides a convenient molecular scheme for characterisation of B. cereus strains responsible for FBOs in order to improve the monitoring and investigation of B. cereus-induced FBOs, assess emerging clusters and diversity of strains. PMID:27934583

Assessing cloud radiative effects on tropospheric photolysis rates and key oxidants during aircraft campaigns using satellite cloud observations and a global chemical transport model

NASA Astrophysics Data System (ADS)

Zhang, B.; Liu, H.; Crawford, J. H.; Chen, G.; Voulgarakis, A.; Fairlie, T. D.; Duncan, B. N.; Ham, S. H.; Kato, S.; Payer Sulprizio, M.; Yantosca, R.

2017-12-01

Clouds affect tropospheric photochemistry through modifying solar radiation that determines photolysis rates. Observational and modeling studies have indicated that photolysis rates are enhanced above and in the upper portion of cloud layers and are reduced below optically thick clouds due to their dominant backscattering effect. However, large uncertainties exist in the representation of cloud spatiotemporal (especially vertical) distributions in global models, which makes understanding of cloud radiative effects on tropospheric chemistry challenging. Our previous study using a global 3-D chemical transport model (GEOS-Chem) driven by various meteorological data sets showed that the radiative effects of clouds on photochemistry are more sensitive to the differences in the vertical distribution of clouds than to those in the magnitude of column cloud optical depths. In this work, we evaluate monthly mean cloud optical properties and distributions in the MERRA-2 reanalysis with those in C3M, a 3-D cloud data product developed at NASA Langley Research Center and merged from multiple A-Train satellite (CERES, CloudSat, CALIPSO, and MODIS) observations. We conduct tropospheric chemistry simulations for the periods of several aircraft campaigns, including ARCTAS (April, June-July, 2008), DC3 (May-June, 2012), and SEAC4RS (August-September, 2013) with GEOS-Chem driven by MERRA-2. We compare model simulations with and without constraints of cloud optical properties and distributions from C3M, and evaluate model photolysis rates (J[O1D] and J[NO2]) and key oxidants (e.g., OH and ozone) with aircraft profile measurements. We will assess whether the constraints provided by C3M improve model simulations of photolysis rates and oxidants as well as their variabilities.

UV-Photochemistry of the Disulfide Bond: Evolution of Early Photoproducts from Picosecond X-ray Absorption Spectroscopy at the Sulfur K-Edge.

PubMed

Ochmann, Miguel; Hussain, Abid; von Ahnen, Inga; Cordones, Amy A; Hong, Kiryong; Lee, Jae Hyuk; Ma, Rory; Adamczyk, Katrin; Kim, Tae Kyu; Schoenlein, Robert W; Vendrell, Oriol; Huse, Nils

2018-05-30

We have investigated dimethyl disulfide as the basic moiety for understanding the photochemistry of disulfide bonds, which are central to a broad range of biochemical processes. Picosecond time-resolved X-ray absorption spectroscopy at the sulfur K-edge provides unique element-specific insight into the photochemistry of the disulfide bond initiated by 267 nm femtosecond pulses. We observe a broad but distinct transient induced absorption spectrum which recovers on at least two time scales in the nanosecond range. We employed RASSCF electronic structure calculations to simulate the sulfur-1s transitions of multiple possible chemical species, and identified the methylthiyl and methylperthiyl radicals as the primary reaction products. In addition, we identify disulfur and the CH 2 S thione as the secondary reaction products of the perthiyl radical that are most likely to explain the observed spectral and kinetic signatures of our experiment. Our study underscores the importance of elemental specificity and the potential of time-resolved X-ray spectroscopy to identify short-lived reaction products in complex reaction schemes that underlie the rich photochemistry of disulfide systems.

Photochemistry of methane and the formation of hydrocyanic acid (HCN) in the earth's early atmosphere

NASA Technical Reports Server (NTRS)

Zahnle, K. J.

1986-01-01

A one-dimensional photochemical model is used to analyze the photochemistries of CH4 and HCN in the primitive terrestrial atmosphere. CH4, N2, and HCN photolysis are examined. The background atmosphere and boundary conditions applied in the analysis are described. The formation of HCN as a by-product of N2 and CH4 photolysis is investigated; the effects of photodissociation and rainfall on HCN is discussed. The low and high CH4 mixing ratios and radical densities are studied.

Supramolecular photochemistry and solar cells

PubMed

Iha

2000-01-01

Supramolecular photochemistry as well as solar cells are fascinating topics of current interest in Inorganic Photochemistry and very active research fields which have attracted wide attention in last two decades. A brief outline of the investigations in these fields carried out in our Laboratory of Inorganic Photochemistry and Energy Conversion is given here with no attempt of an exhaustive coverage of the literature. The emphasis is placed on recent work and information on the above mentioned subjects. Three types of supramolecular systems have been the focus of this work: (i) cage-type coordination compounds; (ii) second-sphere coordination compounds, exemplified by ion-pair photochemistry of cobalt complexes and (iii) covalently-linked systems. In the latter, modulation of the photoluminescence and photochemistry of some rhenium complexes are discussed. Solar energy conversion and development of thin-layer photoelectrochemical solar cells based on sensitization of nanocrystalline semiconductor films by some ruthenium polypyridyl complexes are presented as an important application that resulted from specifically engineered artificial assemblies.

Mechanism for the Coupled Photochemistry of Ammonia and Acetylene: Implications for Giant Planets, Comets and Interstellar Organic Synthesis

NASA Astrophysics Data System (ADS)

Keane, Thomas C.

2017-09-01

Laboratory studies provide a fundamental understanding of photochemical processes in planetary atmospheres. Photochemical reactions taking place on giant planets like Jupiter and possibly comets and the interstellar medium are the subject of this research. Reaction pathways are proposed for the coupled photochemistry of NH3 (ammonia) and C2H2 (acetylene) within the context Jupiter's atmosphere. We then extend the discussion to the Great Red Spot, Extra-Solar Giant Planets, Comets and Interstellar Organic Synthesis. Reaction rates in the form of quantum yields were measured for the decomposition of reactants and the formation of products and stable intermediates: HCN (hydrogen cyanide), CH3CN (acetonitrile), CH3CH = N-N = CHCH3 (acetaldazine), CH3CH = N-NH2 (acetaldehyde hydrazone), C2H5NH2 (ethylamine), CH3NH2 (methylamine) and C2H4 (ethene) in the photolysis of NH3/C2H2 mixtures. Some of these compounds, formed in our investigation of pathways for HCN synthesis, were not encountered previously in observational, theoretical or laboratory photochemical studies. The quantum yields obtained allowed for the formulation of a reaction mechanism that attempts to explain the observed results under varying experimental conditions. In general, the results of this work are consistent with the initial observations of Ferris and Ishikawa (1988). However, their proposed reaction pathway which centers on the photolysis of CH3CH = N-N = CHCH3 does not explain all of the results obtained in this study. The formation of CH3CH = N-N = CHCH3 by a radical combination reaction of CH3CH = N• was shown in this work to be inconsistent with other experiments where the CH3CH = N• radical is thought to form but where no CH3CH = N-N = CHCH3 was detected. The importance of the role of H atom abstraction reactions was demonstrated and an alternative pathway for CH3CH = N-N = CHCH3 formation involving nucleophilic reaction between N2H4 and CH3CH = NH is advanced.

Mechanism for the Coupled Photochemistry of Ammonia and Acetylene: Implications for Giant Planets, Comets and Interstellar Organic Synthesis.

PubMed

Keane, Thomas C

2017-09-01

Laboratory studies provide a fundamental understanding of photochemical processes in planetary atmospheres. Photochemical reactions taking place on giant planets like Jupiter and possibly comets and the interstellar medium are the subject of this research. Reaction pathways are proposed for the coupled photochemistry of NH 3 (ammonia) and C 2 H 2 (acetylene) within the context Jupiter's atmosphere. We then extend the discussion to the Great Red Spot, Extra-Solar Giant Planets, Comets and Interstellar Organic Synthesis. Reaction rates in the form of quantum yields were measured for the decomposition of reactants and the formation of products and stable intermediates: HCN (hydrogen cyanide), CH 3 CN (acetonitrile), CH 3 CH = N-N = CHCH 3 (acetaldazine), CH 3 CH = N-NH 2 (acetaldehyde hydrazone), C 2 H 5 NH 2 (ethylamine), CH 3 NH 2 (methylamine) and C 2 H 4 (ethene) in the photolysis of NH 3 /C 2 H 2 mixtures. Some of these compounds, formed in our investigation of pathways for HCN synthesis, were not encountered previously in observational, theoretical or laboratory photochemical studies. The quantum yields obtained allowed for the formulation of a reaction mechanism that attempts to explain the observed results under varying experimental conditions. In general, the results of this work are consistent with the initial observations of Ferris and Ishikawa (1988). However, their proposed reaction pathway which centers on the photolysis of CH 3 CH = N-N = CHCH 3 does not explain all of the results obtained in this study. The formation of CH 3 CH = N-N = CHCH 3 by a radical combination reaction of CH 3 CH = N• was shown in this work to be inconsistent with other experiments where the CH 3 CH = N• radical is thought to form but where no CH 3 CH = N-N = CHCH 3 was detected. The importance of the role of H atom abstraction reactions was demonstrated and an alternative pathway for CH 3 CH = N-N = CHCH 3 formation involving nucleophilic reaction between N 2 H 4 and CH 3 CH = NH is advanced.

Determination of O2(a1Delta g) and O2(b1Sigma + g) yields in the reaction O + ClO yields Cl + O2 - Implications for photochemistry in the atmosphere of Venus

NASA Technical Reports Server (NTRS)

Leu, Ming-Taun; Yung, Yuk L.

1987-01-01

A discharge flow apparatus with a chemiluminescence detector was used to investigate the reaction O + ClO yields Cl + O2(asterisk), where O2(asterisk) = O2(a1Delta g) or O2(b1Sigma + g). It is found that the observed O2(a1Delta g) airglow of Venus cannot be explained in the framework of standard photochemistry using the experimental results obtained here and those reported in the recent literature. The possibility of an alternative source of O atoms derived from SO2 photolysis in the Venus mesosphere is suggested.

Photochemical insertion of alkynes into Cp sub 2 Fe sub 2 (CO) sub 2 (. mu. -CO) sub 2 : A mechanistic study by laser flash photolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bursten, B.E.; McKee, S.D.; Platz, M.S.

1989-04-26

Cp{sub 2}Fe{sub 2}(CO){sub 2}({mu}-CO){sub 2} (1: Cp = {eta}{sup 5}-C{sub 5}H{sub 5}) has a rich and diverse photochemistry, as evidenced by the plethora of synthetic and mechanistic studies of it in the literature. Early photochemical studies of 1 have demonstrated homolysis to the radical Cp(CO){sub 2}Fe{sup {sm bullet}} (2). Recent work on metal dimers indicates that a dinuclear species is formed concomitantly. Tyler, Schmidt, and Gray (TSG) first proposed that irradiation of 1 leads to the dinuclear species 3, which they suggested was the intermediate responsible for phosphine substitution. Research by other individuals has indicated that the substitutionally active speciesmore » is the CO-loss photoproduct CpFe({mu}-CO){sub 3}FeCp (4). The authors interest in the photochemistry of 1 stemmed from their theoretical studies on piano-stool dimers. One reaction of particular concern is the photochemical insertion of alkynes into 1 to yield dimetallacyclopentenone 5. On the basis of MO calculations, the authors proposed a possible LUMO-controlled mechanism for this reaction that involved alkyne addition to the TSG transition state 3, followed by CO loss. In this contribution, they report initial experimental studies which demonstrate that 4 is the photochemical intermediate responsible for this reaction. They consider this reaction to be a paradigm for photochemical substitution and insertion reaction in such systems.« less

A novel synthesis of polymeric CO via useful hard X-ray photochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pravica, Michael; Sneed, Daniel; Smith, Quinlan

We report on the synchrotron hard X-ray-induced decomposition of strontium oxalate (SrC 2O 4) pressurized to 7 GPa inside a diamond anvil cell (DAC). After some 4 h of irradiation in a white X-ray synchrotron beam, a dark reddish/brown region formed in the area of irradiation which was surrounded by a yellowish brown remainder in the rest of the sample. Upon depressurization of the sample to ambient conditions, the reacted/decomposed sample was recoverable as a dark brown/red and yellow waxy solid. Synchrotron infrared spectroscopy confirmed the strong presence of CO 2 even under ambient conditions with the sample exposed tomore » air and other strongly absorbing regions, suggesting that the sample may likely be polymerized CO (in part) with dispersed CO 2 and SrO trapped within the polymer. These results will have significant implications in the ability to readily produce and trap CO 2 in situ via irradiation of a simple powder for useful hard X-ray photochemistry and in the ability to easily manufacture polymeric CO (via loading of powders in a DAC or high volume press) without the need for the dangerous and complex loading of toxic CO. As a result, a novel means of X-ray-induced polymerization under extreme conditions has also been demonstrated.« less

A novel synthesis of polymeric CO via useful hard X-ray photochemistry

DOE PAGES

Pravica, Michael; Sneed, Daniel; Smith, Quinlan; ...

2016-03-30

We report on the synchrotron hard X-ray-induced decomposition of strontium oxalate (SrC 2O 4) pressurized to 7 GPa inside a diamond anvil cell (DAC). After some 4 h of irradiation in a white X-ray synchrotron beam, a dark reddish/brown region formed in the area of irradiation which was surrounded by a yellowish brown remainder in the rest of the sample. Upon depressurization of the sample to ambient conditions, the reacted/decomposed sample was recoverable as a dark brown/red and yellow waxy solid. Synchrotron infrared spectroscopy confirmed the strong presence of CO 2 even under ambient conditions with the sample exposed tomore » air and other strongly absorbing regions, suggesting that the sample may likely be polymerized CO (in part) with dispersed CO 2 and SrO trapped within the polymer. These results will have significant implications in the ability to readily produce and trap CO 2 in situ via irradiation of a simple powder for useful hard X-ray photochemistry and in the ability to easily manufacture polymeric CO (via loading of powders in a DAC or high volume press) without the need for the dangerous and complex loading of toxic CO. As a result, a novel means of X-ray-induced polymerization under extreme conditions has also been demonstrated.« less

Striking differences in properties of geometric isomers of [Ir(tpy)(ppy)H](+): Experimental and computational studies on their hydricities, interaction with CO 2, and photochemistry

DOE PAGES

Garg, Komal; Fujita, Etsuko; Matsubara, Yasuo; ...

2015-11-16

Here, we prepared two geometric isomers of [Ir(tpy)(ppy)H] +, previously proposed as a key intermediate in the photochemical reduction of CO 2 to CO, and characterized their notably different ground- and excited-state interactions with CO 2 and their hydricities using experimental and computational methods. Only one isomer, C-trans-[Ir(tpy)(ppy)H] +, reacts with CO 2 to generate the formato complex in the ground state, consistent with its calculated hydricity. Under photocatalytic conditions in CH 3CN/TEOA, a common reactive C-trans-[Ir(tpy)(ppy)] 0 species, irrespective of the starting isomer or monodentate ligand (such as hydride or Cl), reacts with CO 2 and produces CO withmore » the same catalytic efficiency.« less

Informal Conference on Photochemistry Held in Atlanta, Georgia on 26 April-1 May, 1992

DTIC Science & Technology

1992-05-01

L . Rh , K . F. Willey, C. S . Yeh, J. S . Pilgrim B . J. Salcido, and M. A. I Duncan...Diode Laser Studies of Atmospheric Reaction Mechanisms" 11-20 L . Herbert, K Li, P . Sharkey, I.j& Sith, A- Defrance, J. L . Queffelec, C. Rebrion, B . R...34 3 M-28 D..Q zmn, K . K . Shen C. B . Winstead, S . IL Cobb, and J. L . Gole, "Chemi- cally Driven Continous Visible Chemical Laser Amplifiers 5 M-27 C. B

Photochemistry of Metal-Metal Bonded Transition Element Complexes

DTIC Science & Technology

1980-12-12

longest-lived metal - metal bonded complex in 298 K fluid solution is of tl.e order of _10-6 a in lifetime (7). Thus, excited state reactions of any kind must...may be greater since cage escape of Re(CO)5 radicals may be less thin unity. There is a solvent viscosity effect on the disappearance quantum yield of...M2 (CO) 1 0 in the presence of 12,consistent with a solvent cage effect (11). In polar solvents (pyridine, THF, alcohols, etc.) the photochemistry of

Transition metal ion-assisted photochemical generation of alkyl halides and hydrocarbons from carboxylic acids.

PubMed

Carraher, Jack M; Pestovsky, Oleg; Bakac, Andreja

2012-05-21

Near-UV photolysis of aqueous solutions of propionic acid and aqueous Fe(3+) in the absence of oxygen generates a mixture of hydrocarbons (ethane, ethylene and butane), carbon dioxide, and Fe(2+). The reaction becomes mildly catalytic (about five turnovers) in the presence of oxygen which converts a portion of alkyl radicals to oxidizing intermediates that reoxidize Fe(2+). The photochemistry in the presence of halide ions (X(-) = Cl(-), Br(-)) generates ethyl halides via halogen atom abstraction from FeX(n)(3-n) by ethyl radicals. Near-quantitative yields of C(2)H(5)X are obtained at ≥0.05 M X(-). Competition experiments with Co(NH(3))(5)Br(2+) provided kinetic data for the reaction of ethyl radicals with FeCl(2+) (k = (4.0 ± 0.5) × 10(6) M(-1) s(-1)) and with FeBr(2+) (k = (3.0 ± 0.5) × 10(7) M(-1) s(-1)). Photochemical decarboxylation of propionic acid in the presence of Cu(2+) generates ethylene and Cu(+). Longer-chain acids also yield alpha olefins as exclusive products. These reactions become catalytic under constant purge with oxygen which plays a dual role. It reoxidizes Cu(+) to Cu(2+), and removes gaseous olefins to prevent accumulation of Cu(+)(olefin) complexes and depletion of Cu(2+). The results underscore the profound effect that the choice of metal ions, the medium, and reaction conditions exert on the photochemistry of carboxylic acids.

Vertical sounding balloons for stratospheric photochemistry

NASA Astrophysics Data System (ADS)

Pommereau, J. P.

The use of vertical sounding balloons for stratospheric photochemistry studies is illustrated by the use of a vertical piloted gas balloon for the search of NO2 diurnal variations. It is shown that the use of montgolfieres (hot air balloons) can enhance the vertical sounding technique. Particular attention is given to a sun-heated montgolfiere and to the more sophisticated infrared montgolfiere that is able to perform three to four vertical excursions per day and to remain aloft for weeks or months.

PHOTOLYTIC HAZES IN THE ATMOSPHERE OF 51 ERI B

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zahnle, K.; Marley, M. S.; Morley, C. V.

We use a 1D model to address photochemistry and possible haze formation in the irradiated warm Jupiter, 51 Eridani b. The intended focus was to be carbon, but sulfur photochemistry turns out to be important. The case for organic photochemical hazes is intriguing but falls short of being compelling. If organic hazes form, they are likeliest to do so if vertical mixing in 51 Eri b is weaker than in Jupiter, and they would be found below the altitudes where methane and water are photolyzed. The more novel result is that photochemistry turns H{sub 2}S into elemental sulfur, here treatedmore » as S{sub 8}. In the cooler models, S{sub 8} is predicted to condense in optically thick clouds of solid sulfur particles, while in the warmer models S{sub 8} remains a vapor along with several other sulfur allotropes that are both visually striking and potentially observable. For 51 Eri b, the division between models with and without condensed sulfur is at an effective temperature of 700 K, which is within error its actual effective temperature; the local temperature where sulfur condenses is between 280 and 320 K. The sulfur photochemistry we have discussed is quite general and ought to be found in a wide variety of worlds over a broad temperature range, both colder and hotter than the 650–750 K range studied here, and we show that products of sulfur photochemistry will be nearly as abundant on planets where the UV irradiation is orders of magnitude weaker than it is on 51 Eri b.« less

Photolytic Hazes in the Atmosphere of 51 Eri b

NASA Technical Reports Server (NTRS)

Zahnle, K.; Marley, M. S.; Morley, C. V.; Moses, J. I.

2016-01-01

We use a 1D model to address photochemistry and possible haze formation in the irradiated warm Jupiter 51 Eridani b. The intended focus was to be carbon, but sulfur photochemistry turns out to be important. The case for organic photochemical hazes is intriguing but falls short of being compelling. If they form, they are likeliest to do so if vertical mixing in 51 Eri b is weaker than in Jupiter, and they would be found below the regions where methane and water are photolyzed. The more novel result is that photochemistry turns H2S into elemental sulfur, here treated as S8. In the cooler models, S8 is predicted to condense in optically thick clouds of solid sulfur particles, whilst in the warmer models S8 remains a vapor along with several other sulfur allotropes that are both visually striking and potentially observable. For 51 Eri b, the division between models with and without condensed sulfur is at an effective temperature of 700 K, which is within error its actual effective temperature; the local temperature where sulfur condenses is between 280 and 320 K. The sulfur photochemistry we have discussed is quite general and ought to be found in a wide variety of worlds over a broad temperature range, both colder and hotter than the 650-750 K range studied here, and we show that products of sulfur photochemistry will be nearly as abundant on planets where the UV irradiation is orders of magnitude weaker than it is on 51 Eri b.

Spectroscopy and photochemistry of humic acids

NASA Astrophysics Data System (ADS)

Sokolova, I. V.; Vershinin, N. O.; Skobczova, K. A.; Tchaikovskaya, O. N.; Mayer, G. V.

2018-04-01

Spectroscopy and photochemistry of humic acids are discussed. The samples of HAs fractions were obtained from Fluka Chemical Co and prepared from peat of Western Siberia region. The comparative analysis of these acids with the sample of humic acids allocated from brown coal is carried out. A specific feature of the reactor is the use of barrier discharge excilamp (KrCl) with radiation wavelength λ = 222 nm. Influence of the received humic acids on process of photodegradation of herbicide - 2.4-dichlorophenoxyacetic acid is considered.

Jovian Tropospheric Photohemistry: Constraints from Recent Cassini and Galileo Observations and from Laboratory Experiment Simulations

NASA Astrophysics Data System (ADS)

Moses, Julianne I.; Sperier, A. D.; Keane, T. C.

2008-09-01

We use the Caltech/JPL KINETICS code (Allen et al. 1981, JGR 86, 3617) to develop 1-D (in altitude) photochemical models for Jupiter's troposphere that are consistent with available Cassini, Galileo, Voyager, and Earth-based observations of ammonia and phosphine, and upper limits for HCN. As a test of the adopted chemical reaction list, we simulate laboratory experiments of coupled NH3-PH3 and NH3-C2H2 photochemistry (Ferris et al. 1984, J. Am. Chem. Soc. 106, 318; Ferris and Ishikawa 1988, J. Am. Chem. Soc. 110, 4306; Keane et al. 1996, Icarus 122, 205). We find that the vertical profile of PH3 is sensitive to the assumed tropospheric eddy diffusion coefficient and aerosol extinction, both of which are loosely constrained by observations and seem to vary with latitude. The NH3 profile is controlled by condensation and is relatively insensitive to the eddy diffusion coefficient. As was determined by previous photochemical models, the dominant products of Jovian tropospheric chemistry are P2H4, N2H4, red phosphorus, NH2PH2, and N2. All of these species except N2 will condense. Diphosphine (P2H4) is an underappreciated condensate that will likely be more important than N2H4 as an aerosol component on Jupiter as well as Saturn. Little is known about the chemistry and properties of NH2PH2, but this product could also be an important condensable constituent. Coupled NH3-C2H2 photochemistry does not readily occur in Jupiter's troposphere due to the low predicted (and observed) tropospheric C2H2 abundance. The models therefore produce only a small amount of HCN (well within upper limits), and even smaller amounts of the nitriles, hydrazones, and other organo-nitrogen molecules identified in the laboratory experiments mentioned above. This work was supported by the NASA Planetary Atmospheres Program (NNX08AF05G) and the Lunar and Planetary Institute/USRA.

Photochemistry of Aqueous C60 Clusters: Wavelength Dependency and Product Characterization

EPA Science Inventory

To construct accurate risk assessment models for engineered nanomaterials, there is urgent need for information on the reactivity (or conversely, persistence) and transformation pathways of these materials in the natural environment. As an important step toward addressing this is...

PHOTOCHEMISTRY OF SOME NATURALLY EMITTED HYDROCARBONS

EPA Science Inventory

Six C10H16 monoterpenes, p-cymene, and isoprene, all known or thought to be emitted to the atmosphere by vegetation, were irradiated in the presence of NOx. The terpenes studied included one acyclic triolefin (myrcene), two monocyclic diolefins (d-limonene, terpinolene), and thre...

Dissociative photoionization of ethyl acrylate: Theoretical and experimental insights

NASA Astrophysics Data System (ADS)

Song, Yanlin; Chen, Jun; Ding, Mengmeng; Wei, Bin; Cao, Maoqi; Shan, Xiaobin; Zhao, Yujie; Huang, Chaoqun; Sheng, Liusi; Liu, Fuyi

2015-08-01

The photoionization and dissociation of ethyl acrylate have been investigated by time-of-flight mass spectrometer with tunable vacuum ultraviolet (VUV) source in the range of 9.0-20.0 eV. The photoionization mass spectrum (PIMS) for ethyl acrylate and photoionization efficiency (PIE) curves for its major fragment ions: C5H7O2+, C4H5O2+, C3H5O2+, C3H4O+, C3H3O+, C2H5O+, C2H3O+, C2H5+ and C2H4+ have been obtained. The formation channels of main fragments are predicted by Gaussian 09 program at G3B3 level and examined via their dissociation energies from experimental results. Based on our analysis, nine main dissociative photoionization channels are proposed: C5H7O2+ + H, C4H5O2+ + CH3, C3H5O2+ + C2H3, C3H4O+ + C2H4O, C3H3O+ + C2H5O, C2H5O+ + C3H3O, C2H3O+ + C3H5O, C2H5+ + C3H3O2, C2H4+ + C3H4O2, respectively. The results of this work lead to a better understanding of photochemistry in the environment.

Space Station Workshop Commercial Missions and User Requirements: Issues and Recommendations

NASA Technical Reports Server (NTRS)

1988-01-01

The issues and recommendations of a conference on the Space Station are presented. The subjects are organized under three headings of: materials and processing in space, earth and ocean observations, and industrial services. One hundred and two issues and recommendations which resulted from the workskop are categorized for each discipline subpanel. Responses to these issues and recommendations are based on more than twenty interviews with highly qualified NASA personnel and represent the best answers available at this time.

The carbon chemistry in interstellar clouds toward moderately reddened stars

NASA Technical Reports Server (NTRS)

Federman, S. R.; Lambert, D. L.

1988-01-01

New data for C2 toward X Per, HD 206267, HD 207198, and Gamma Cep, for CH and CN toward X Per, and for CO toward HD 207198 have been obtained. The column densities of CH, C2, CN, and CO toward the stars in the Cepheus OB2 association are similar to reddened directions in Perseus and in Ophiuchus, indicating a similarity in physical conditions for the foreground clouds. The available data for other directions have been analyzed and the resulting data applied to study the transition from a photochemical regime to a chemical regime. The data for N(CN), N(C2), and N(CO) have been plotted against N(CH) to elucidate the chemistry of carbon-bearing molecules more clearly. The observed trends for CN and C2 suggest a change in slope at N(CH) of roughly 5 x 10 to the 13th/sq cm. Below this value, photodestruction is predicted to dominate and the slope is determined by the photochemistry. For directions with more N(CH), a linear correlation consistent with destruction by chemical reactions is expected.

UV-laser photochemistry of isoxazole isolated in a low-temperature matrix.

PubMed

Nunes, Cláudio M; Reva, Igor; Pinho e Melo, Teresa M V D; Fausto, Rui

2012-10-05

The photochemistry of matrix-isolated isoxazole, induced by narrowband tunable UV-light, was investigated by infrared spectroscopy, with the aid of MP2/6-311++G(d,p) calculations. The isoxazole photoreaction starts to occur upon irradiation at λ = 240 nm, with the dominant pathway involving decomposition to ketene and hydrogen cyanide. However, upon irradiation at λ = 221 nm, in addition to this decomposition, isoxazole was also found to isomerize into several products: 2-formyl-2H-azirine, 3-formylketenimine, 3-hydroxypropenenitrile, imidoylketene, and 3-oxopropanenitrile. The structural and spectroscopic assignment of the different photoisomerization products was achieved by additional irradiation of the λ = 221 nm photolyzed matrix, using UV-light with λ ≥ 240 nm: (i) irradiation in the 330 ≤ λ ≤ 340 nm range induced direct transformation of 2-formyl-2H-azirine into 3-formylketenimine; (ii) irradiation with 310 ≤ λ ≤ 318 nm light induced the hitherto unobserved transformation of 3-formylketenimine into 3-hydroxypropenenitrile and imidoylketene; (iii) irradiation with λ = 280 nm light permits direct identification of 3-oxopropanenitrile; (iv) under λ = 240 nm irradiation, tautomerization of 3-hydroxypropenenitrile to 3-oxopropanenitrile is observed. On the basis of these findings, a detailed mechanistic proposal for isoxazole photochemistry is presented.

Photochemistry of the Stilbenes in Methanol. Trapping the Common Phantom Singlet State.

PubMed

Saltiel, Jack; Gupta, Shipra

2018-06-21

A comparative study of the photochemistry of cis- and trans-stilbene in methanol shows that both isomers undergo methanol photoaddition giving similar yields of α-methoxybibenzyl in competition with cis-trans photoisomerization. Methanol addition occurs primarily following torsional relaxation of the lowest excited singlet states of each isomer, 1 c* and 1 t*, to a common twisted singlet excited state intermediate, 1 p*, initially called the phantom singlet state. The addition is consistent with the zwitterionic character of 1 p*. Ether forms by direct 1,2-addition of CH 3 OH to the central carbon atoms and by 1,1-addition following rearrangement to 1-benzyl-1-phenylcarbene. Use of CD 3 OD and GC/MS (gas chromatographic/mass spectroscopic) analysis of the ether products revealed that the ratio of carbene/direct addition pathways is higher starting from cis-stilbene. We conclude that 1 p* formed from 1 c* is hotter than 1 p* formed from 1 t*. Surprisingly, except for favoring the carbene pathway, the use of higher energy photons (254 vs 313 nm) does not affect the overall ether quantum yield starting from cis-stilbene, but significantly enhances both pathways starting from trans-stilbene. It appears that carbene formation and direct methanol addition to higher trans-stilbene excited state(s) compete with relaxation to S 1 . Substitution of D for the vinyl Hs of stilbene enhances the direct addition pathway more than two-fold and strongly suppresses the carbene insertion pathway, revealing a large, k pc d0 / k pc d2 = 6.3, primary deuterium isotope effect in the carbene rearrangement. The two-fold increase in the ether quantum yield is due primarily to a 2.75-fold increase in the lifetime of 1 p* on deuterium substitution of the vinyl hydrogens.

Inorganic Chlorine Partitioning in the Summer Lower Stratosphere: Modeled and Measured [ClONO2/HCl] During POLARIS

NASA Technical Reports Server (NTRS)

Voss, P. B.; Stimpfle, R. M.; Cohen, R. C.; Hanisco, T. F.; Bonne, G. P.; Perkins, K. K.; Lanzendorf, E. J.; Anderson, J. G.; Salawitch, R. J.

2001-01-01

We examine inorganic chlorine (Cly) partitioning in the summer lower stratosphere using in situ ER-2 aircraft observations made during the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) campaign. New steady state and numerical models estimate [ClONO2]/[HCl] using currently accepted photochemistry. These models are tightly constrained by observations with OH (parameterized as a function of solar zenith angle) substituting for modeled HO2 chemistry. We find that inorganic chlorine photochemistry alone overestimates observed [ClONO2]/[HCl] by approximately 55-60% at mid and high latitudes. On the basis of POLARIS studies of the inorganic chlorine budget, [ClO]/[ClONO2], and an intercomparison with balloon observations, the most direct explanation for the model-measurement discrepancy in Cly partitioning is an error in the reactions, rate constants, and measured species concentrations linking HCl and ClO (simulated [ClO]/[HCl] too high) in combination with a possible systematic error in the ER-2 ClONO2 measurement (too low). The high precision of our simulation (+/-15% 1-sigma for [ClONO2]/[HCl], which is compared with observations) increases confidence in the observations, photolysis calculations, and laboratory rate constants. These results, along with other findings, should lead to improvements in both the accuracy and precision of stratospheric photochemical models.

The 2.5-diacyl-1,4-dimethylbenzenes: Examples of bisphotoenol equivalents

NASA Technical Reports Server (NTRS)

Meador, Michael A.

1987-01-01

The photochemistry of 2,5-dibenzoyl(DBX)-and 2,5-diacetyl-1,4-dimethylbenzene (DAX) has been investigated. Both compounds readily undergo photoenolization similar to 0-alkylphenyl ketones. However, unlike 0-alkylphenyl ketones DAX and DBX are each capable of undergoing two tandem photoenolizations. Photoenols derived from o-alkylphenyl ketones have been successfully trapped with Diels-Alder dienophiles to provide a convenient synthesis of substituted tetralins. Similarly, Diels-Alder trapping of DBX photoenils afforded substituted tetra- and octahydro anthracenes. Further mainpulation of these photadducts provided the corresponding anthracenes in good yield. The photochemistry of DAX and DBX will be discussed, in particular their use in the synthesis of substituted anthracenes.

Lucifer's Planet: Photolytic Hazes in the Atmosphere of 51 Eri b

NASA Technical Reports Server (NTRS)

Zahnle, Kevin

2016-01-01

We use a 1D model to address photochemistry and possible haze formation in the irradiated atmosphere of 51 Eri b (2016arXiv160407388Z). The intended focus was to have been on carbon and organic hazes, but sulfur photochemistry turns out to be interesting and possibly more important. The case for organic photochemical hazes is intriguing but falls short of being compelling. If organic hazes form abundantly, they are likeliest to do so if vertical mixing in 51 Eri b is weaker than in Jupiter, and they would be found below the altitudes where methane and water are photolyzed. The more novel result is that photochemistry turns H2S into elemental sulfur, here treated as S8. In the cooler models, S8 is predicted to condense in optically significant clouds of solid sulfur particles, whilst in the warmer models S8 remains a vapor along with several other sulfur allotropes that are both visually striking and potentially observable. For 51 Eri b, the division between models with and without condensed sulfur is at an effective temperature of 700 K, which is within error its actual effective temperature; the local temperature where sulfur condenses is between 280 and 320 K. The sulfur photochemistry we discuss is quite general and ought to be found in a wide variety of worlds over a broad temperature range, both colder and hotter than the 650-750 K range studied here, and we show that products of sulfur photochemistry will be nearly as abundant on planets where the UV irradiation is orders of magnitude weaker than it is on 51 Eri b.

Modeling the Complex Photochemistry of Biomass Burning Plumes in Plume-Scale, Regional, and Global Air Quality Models

NASA Astrophysics Data System (ADS)

Alvarado, M. J.; Lonsdale, C. R.; Yokelson, R. J.; Travis, K.; Fischer, E. V.; Lin, J. C.

2014-12-01

Forecasting the impacts of biomass burning (BB) plumes on air quality is difficult due to the complex photochemistry that takes place in the concentrated young BB plumes. The spatial grid of global and regional scale Eulerian models is generally too large to resolve BB photochemistry, which can lead to errors in predicting the formation of secondary organic aerosol (SOA) and O3, as well as the partitioning of NOyspecies. AER's Aerosol Simulation Program (ASP v2.1) can be used within plume-scale Lagrangian models to simulate this complex photochemistry. We will present results of validation studies of the ASP model against aircraft observations of young BB smoke plumes. We will also present initial results from the coupling of ASP v2.1 into the Lagrangian particle dispersion model STILT-Chem in order to better examine the interactions between BB plume chemistry and dispersion. In addition, we have used ASP to develop a sub-grid scale parameterization of the near-source chemistry of BB plumes for use in regional and global air quality models. The parameterization takes inputs from the host model, such as solar zenith angle, temperature, and fire fuel type, and calculates enhancement ratios of O3, NOx, PAN, aerosol nitrate, and other NOy species, as well as organic aerosol (OA). We will present results from the ASP-based BB parameterization as well as its implementation into the global atmospheric composition model GEOS-Chem for the SEAC4RS campaign.

Photoactive High Explosives: Substituents Effects on Tetrazine Photochemistry and Photophysics

DOE PAGES

McGrane, Shawn David; Bolme, Cynthia Anne; Greenfield, Margo Torello; ...

2016-01-21

High explosives that are photoactive, i.e., can be initiated with light, offer significant advantages in reduced potential for accidental electrical initiation. In this study, we examined a series of structurally related tetrazine based photoactive high explosive materials to detail their photochemical and photophysical properties. Using photobleaching infrared absorption, we determined quantum yields of photochemistry for nanosecond pulsed excitation at 355 and 532 nm. Changes in mass spectrometry during laser irradiation in vacuum measured the evolution of gaseous products. Fluorescence spectra, quantum yields, and lifetimes were measured to observe radiative channels of energy decay that compete with photochemistry. For the 6more » materials studied, quantum yields of photochemistry ranged from <10 –5 to 0.03 and quantum yield of fluorescence ranged from <10 –3 to 0.33. In all cases, the photoexcitation nonradiatively relaxed primarily to heat, appropriate for supporting photothermal initiation processes. Lastly, the photochemistry observed was dominated by ring scission of the tetrazine, but there was evidence of more extensive multistep reactions as well.« less

Practical photochemistry: General considerations

NASA Astrophysics Data System (ADS)

Hutchison, J.

1986-05-01

Practical aspects of laboratory scale preparative photochemistry are discussed under the headings of: (1) lamps: dimensions, power ratings, spectral distributions and output intensities of different lamp types; (2) the reaction mixture: factors involved in establishing the most suitable wavelength region to use to carry out a particular reaction; the selection of the appropriate solvents, filters, and glassware; concentration of the photoactive component; (3) preparative photoreactions: immersion well, falling film, external irradiation and elliptical configurations; (4) apparatus for quantitative work: carousel and optical bench arrangements; (5) hazards: effects of ultraviolet radiation on eyes and skin and precautions to be taken.

Determination of O2(a1 delta g) and O2(b1 sigma+ g) yields in the reaction O + ClO --> Cl + O2: implications for photochemistry in the atmosphere of Venus

NASA Technical Reports Server (NTRS)

Leu, M. T.; Yung, Y. L.

1987-01-01

A discharge flow apparatus with chemiluminescence detector has been used to study the reaction O + ClO --> Cl + O2, where O2 = O2(a1 delta g) or O2(b1 sigma+ g). The measured quantum yields for producing O2(a1 delta g) and O2(b1 sigma+ g) in the above reaction are less than 2.5 x 10(-2) and equal to (4.4 +/- 1.1) x 10(-4), respectively. The observed O2(a1 delta g) airglow of Venus cannot be explained in the context of standard photochemistry using our experimental results and those reported in recent literature. The possibility of an alternative source of O atoms derived from SO2 photolysis in the mesosphere of Venus is suggested.

Photochemistry of Triton's atmosphere and ionosphere.

PubMed

Krasnopolsky, V A; Cruikshank, D P

1995-10-25

The photochemistry of 32 neutral and 21 ion species in Triton's atmosphere is considered. Parent species N2, CH4, and CO (with a mixing ratio of 3 x 10(-4) in our basic model) sublime from the ice with rates of 40, 208, and 0.3 g/cm2/b.y., respectively. Chemistry below 50 km is driven mostly by photolysis of methane by the solar and interstellar medium Lyman-alpha photons, producing hydrocarbons C2H4, C2H6, and C2H2 which form haze particles with precipitation rates of 135, 28, and 1.3 g/cm2/b.y., respectively. Some processes are discussed which increase the production of HCN (by an order of magnitude to a value of 29 g/cm2/b.y.) and involve indirect photolysis of N2 by neutrals. Reanalysis of the measured methane profiles gives an eddy diffusion coefficient K = 4 x 10(3) cm2/s above the tropopause and a more accurate methane number density near the surface, (3.1 +/- 0.8) x 10(11) cm-3. Chemistry above 200 km is driven by the solar EUV radiation (lambda < 1000 angstroms) and by precipitation of magnetospheric electrons with a total energy input of 10(8) W (based on thermal balance calculations). The most abundant photochemical species are N, H2, H, O, and C. They escape with the total rates of 7.7 x 10(24) s-1, 4.5 x 10(25) s-1, 2.4 x 10(25) s-1, 4.4 x 10(22) s-1, and 1.1 x 10(24) s-1, respectively. Atomic species are transported to a region of 50-200 km and drive the chemistry there. Ionospheric chemistry explains the formation of an E region at 150-240 km with HCO+ as a major ion, and of an F region above 240 km with a peak at 320 km and C+ as a major ion. The ionosphere above 500 km consists of almost equal densities of C+ and N+ ions. The model profiles agree with the measured atomic nitrogen and electron density profiles. A number of other models with varying rate coefficients of some reactions, differing properties of the haze particles (chemically passive or active), etc., were developed. These models show that there are four basic unknown values which have strong impacts on the composition and structure of the atmosphere and ionosphere. These values and their plausible ranges are the CO mixing ratio fco = 10(-4)-10(-3), the magnetospheric electron energy input (1 +/- 0.5) x 10(8) W, the rate coefficient of charge-exchange reaction N2(+) + C k = 10(-11)-10(-10) cm3/s, and the ion escape velocity Vi approximately equal to 150 cm/s.

Effects of climate change on surface-water photochemistry: a review.

PubMed

De Laurentiis, Elisa; Minella, Marco; Maurino, Valter; Minero, Claudio; Vione, Davide

2014-10-01

Information concerning the link between surface-water photochemistry and climate is presently very scarce as only a few studies have been dedicated to the subject. On the basis of the limited knowledge that is currently available, the present inferences can be made as follows: (1) Warming can cause enhanced leaching of ionic solutes from the catchments to surface waters, including cations and more biologically labile anions such as sulphate. Preferential sulphate biodegradation followed by removal as organic sulphides in sediment could increase alkalinity, favouring the generation of the carbonate radical, CO3 (·-). However, this phenomenon would be easily offset by fluctuations of the dissolved organic carbon (DOC), which is strongly anticorrelated with CO3 (·-). Therefore, obtaining insight into DOC evolution is a key issue in understanding the link between photochemistry and climate. (2) Climate change could exacerbate water scarcity in the dry season in some regions. Fluctuations in the water column could deeply alter photochemistry that is usually favoured in shallower waters. However, the way water is lost would strongly affect the prevailing photoinduced processes. Water outflow without important changes in solute concentration would mostly favour reactions induced by the hydroxyl and carbonate radicals (·OH and CO3 (·-)). In contrast, evaporative concentration would enhance reactions mediated by singlet oxygen ((1)O2) and by the triplet states of chromophoric dissolved organic matter ((3)CDOM*). (3) In a warmer climate, the summer stratification period of lakes would last longer, thereby enhancing photochemical reactions in the epilimnion but at the same time keeping the hypolimnion water in the dark for longer periods.

Infrared study of matrix-isolated ethyl cyanide: simulation of the photochemistry in the atmosphere of Titan.

PubMed

Toumi, A; Piétri, N; Couturier-Tamburelli, I

2015-11-11

Low-temperature Ar matrix isolation has been carried out to investigate the infrared spectrum of ethyl cyanide (CH3CH2CN), a molecule present in the atmosphere of Titan. The λ > 120 nm and λ > 230 nm photolysis reactions of ethyl cyanide in an Ar matrix were also performed in order to compare the behaviour of this compound when it is submitted to high and low energetic radiations. These different wavelengths have been used with the aim to reproduce the radiation reaching the various parts of the atmosphere. Several photoproducts have been identified during photolysis such as vinyl cyanide (CH2[double bond, length as m-dash]CHCN), cyanoacetylene (HC3N), and ethylene/hydrogen cyanide (C2H4/HCN), ethylene/hydrogen isocyanide (C2H4/HNC), acetylene/hydrogen cyanide (C2H2/HCN), acetylene/hydrogen isocyanide (C2H2/HNC), and acetylene:methylenimine (C2H2:HNCH2) complexes. Ethyl isocyanide (CH3CH2NC) and a ketenimine form (CH3CH[double bond, length as m-dash]C[double bond, length as m-dash]NH) have been identified as well. Photoproduct identification and spectral assignments were done using previous studies and density functional theory (DFT) calculations with the B3LYP/cc-pVTZ basis set.

Formaldehyde methods comparison in the remote lower troposphere during the Mauna Loa Photochemistry Experiment 2

NASA Astrophysics Data System (ADS)

Heikes, B.; McCully, B.; Zhou, X.; Lee, Y.-N.; Mopper, K.; Chen, X.; Mackay, G.; Karecki, D.; Schiff, H.; Campos, T.; Atlas, E.

1996-06-01

Five methods for the measurement of CH2O vapor were compared under remote tropospheric conditions. The techniques included an aqueous-scrubber enzyme fluorescence method (URIcoil), TDLAS (UNI), 2,4-dinitrophenylhydrazine (DNPH) impregnated-cartridges (BNL/WSUcart), an aqueous-scrubber DNPH method (BNL/WSUcoil), and an unpublished aqueous-scrubber immobilized-enzyme fluorescence method (NCARbound). This was part of the Mauna Loa Observatory Photochemistry Experiment 2 (MLOPEX 2) which was performed in four ˜30-day intensives. In MLOPEX 2a (fall 1991), the URIcoil technique indicated higher concentrations relative to the BNL/WSUcoil which were higher than UNI. The limited number of NCARbound measurements for MLOPEX 2a were greater than the other measurements and least reliable. During MLOPEX 2b (winter 1992), URIcoil, UNI, BNL/WSUcoil, and NCAR-bound gave comparable measurements of CH2O with the latter again being consistently higher than the first three methods and its performance and reliability was improved over MLOPEX 2a. URIcoil and BNL/WSUcoil were comparable in MLOPEX 2c (spring 1992) and 2d (summer 1992), whereas BNL/WSUcart was consistently higher than both for these intensives. The major source of difference between techniques was ascribed to variations in the analytical-procedural field blanks. Calibration differences were the most likely cause of URIcoil being higher than BNL/WSUcoil and BNL/WSUcoil being higher than UNI during MLOPEX 2a. Lower free troposphere median concentrations were between 100 and 150 ppt for all seasons and without a seasonal trend. These values were a factor of 2 to 3 lower than model estimates for this study site and were in keeping with earlier work.

Organic chemistry on Titan

NASA Technical Reports Server (NTRS)

Chang, S.; Scattergood, T.; Aronowitz, S.; Flores, J.

1979-01-01

Features taken from various models of Titan's atmosphere are combined in a working composite model that provides environmental constraints within which different pathways for organic chemical synthesis are determined. Experimental results and theoretical modeling suggest that the organic chemistry of the satellite is dominated by two processes: photochemistry and energetic particle bombardment. Photochemical reactions of CH4 in the upper atmosphere can account for the presence of C2 hydrocarbons. Reactions initiated at various levels of the atmosphere by cosmic rays, Saturn 'wind', and solar wind particle bombardment of a CH4-N2 atmospheric mixture can account for the UV-visible absorbing stratospheric haze, the reddish appearance of the satellite, and some of the C2 hydrocarbons. In the lower atmosphere photochemical processes will be important if surface temperatures are sufficiently high for gaseous NH3 to exist. It is concluded that the surface of Titan may contain ancient or recent organic matter (or both) produced in the atmosphere.

Structure and photochemistry of a saccharyl thiotetrazole.

PubMed

Ismael, A; Borba, A; Henriques, M S C; Paixão, J A; Fausto, R; Cristiano, M L S

2015-01-02

The molecular structure and photochemistry of 5-thiosaccharyl-1-methyltetrazole (TSMT) were studied by means of matrix-isolation FTIR spectroscopy, X-ray crystallography, and theoretical calculations. The calculations predicted two conformers of TSMT that differ in energy by more than 15 kJ mol(-1). The infrared spectrum of TSMT isolated in solid argon was fully assigned on the basis of the spectrum calculated (O3LYP/6-311++G(3df,3pd)) for the most stable conformer. In the crystal, TSMT molecules were found to assume the same conformation as for the isolated molecule, with each molecule forming four hydrogen bonds with three neighboring molecules, leading to a network of TSMT oligomers. Upon UV (λ = 265 nm) irradiation of the matrix-isolated TSMT, two photodegradation pathways were observed, both arising from cleavage of the tetrazolyl ring. Pathway a involves cleavage of the N1-N2 and N3-N4 bonds with extrusion of N2, leading to photostable diazirine and thiocarbodiimide derivatives. The photostability of the photoproduced diazirine under the conditions used precluded its rearrangement to the nitrile imine, as reported for 5-phenyltetrazole by Bégué et al. ( J. Am. Chem. Soc. 2012 , 134 , 5339 ). Pathway b involves cleavage of the C5-N1 and N4-N3 bonds, leading to a thiocyanate and methyl azide, the latter undergoing subsequent fragmentation to give CNH.

Changing concentrations of CO, CH(4), C(5)H(8), CH(3)Br, CH(3)I, and dimethyl sulfide during the Southern Ocean Iron Enrichment Experiments.

PubMed

Wingenter, Oliver W; Haase, Karl B; Strutton, Peter; Friederich, Gernot; Meinardi, Simone; Blake, Donald R; Rowland, F Sherwood

2004-06-08

Oceanic iron (Fe) fertilization experiments have advanced the understanding of how Fe regulates biological productivity and air-sea carbon dioxide (CO(2)) exchange. However, little is known about the production and consumption of halocarbons and other gases as a result of Fe addition. Besides metabolizing inorganic carbon, marine microorganisms produce and consume many other trace gases. Several of these gases, which individually impact global climate, stratospheric ozone concentration, or local photochemistry, have not been previously quantified during an Fe-enrichment experiment. We describe results for selected dissolved trace gases including methane (CH(4)), isoprene (C(5)H(8)), methyl bromide (CH(3)Br), dimethyl sulfide, and oxygen (O(2)), which increased subsequent to Fe fertilization, and the associated decreases in concentrations of carbon monoxide (CO), methyl iodide (CH(3)I), and CO(2) observed during the Southern Ocean Iron Enrichment Experiments.

Photosynthesis is improved by exogenous calcium in heat-stressed tobacco plants.

PubMed

Tan, Wei; Meng, Qing wei; Brestic, Marian; Olsovska, Katarina; Yang, Xinghong

2011-11-15

Effects of exogenous calcium chloride (CaCl(2)) (20 mM) on photosynthetic gas exchange, photosystem II photochemistry, and the activities of antioxidant enzymes in tobacco plants under high temperature stress (43°C for 2 h) were investigated. Heat stress resulted in a decrease in net photosynthetic rate (P(n)), stomatal conductance as well as the apparent quantum yield (AQY) and carboxylation efficiency (CE) of photosynthesis. Heat stress also caused a decrease of the maximal photochemical efficiency of primary photochemistry (F(v)/F(m)). On the other hand, CaCl(2) application improved P(n), AQY, and CE as well as F(v)/F(m) under high temperature stress. Heat stress reduced the activities of superoxide dismutase (SOD), catalase (CAT), ascorbate peroxidase (APX), peroxidase (POD), whereas the activities of these enzymes either decreased less or increased in plants pretreated with CaCl(2); glutathione reductase (GR) activity increased under high temperature, and it increased more in plants pretreated with CaCl(2). There was an obvious accumulation of H(2)O(2) and O(2)(-) under high temperature, but CaCl(2) application decreased the contents of H(2)O(2) and O(2)(-) under heat stress conditions. Heat stress induced the level of heat shock protein 70 (HSP70), while CaCl(2) pretreatment enhanced it. These results suggested that photosynthesis was improved by CaCl(2) application in heat-stressed plants and such an improvement was associated with an improvement in stomatal conductance and the thermostability of oxygen-evolving complex (OEC), which might be due to less accumulation of reactive oxygen species. Copyright © 2011 Elsevier GmbH. All rights reserved.

The affects on Titan atmospheric modeling by variable molecular reaction rates

NASA Astrophysics Data System (ADS)

Hamel, Mark D.

The main effort of this thesis is to study the production and loss of molecular ions in the ionosphere of Saturn's largest moon Titan. Titan's atmosphere is subject to complex photochemical processes that can lead to the production of higher order hydrocarbons and nitriles. Ion-molecule chemistry plays an important role in this process but remains poorly understood. In particular, current models that simulate the photochemistry of Titan's atmosphere overpredict the abundance of the ionosphere's main ions suggesting a flaw in the modeling process. The objective of this thesis is to determine which reactions are most important for production and loss of the two primary ions, C2H5+ and HCNH+, and what is the impact of uncertainty in the reaction rates on the production and loss of these ions. In reviewing the literature, there is a contention about what reactions are really necessary to illuminate what is occurring in the atmosphere. Approximately seven hundred reactions are included in the model used in this discussion (INT16). This paper studies what reactions are fundamental to the atmospheric processes in Titan's upper atmosphere, and also to the reactions that occur in the lower bounds of the ionosphere which are used to set a baseline molecular density for all species, and reflects what is expected at those altitudes on Titan. This research was conducted through evaluating reaction rates and cross sections available in the scientific literature and through conducting model simulations of the photochemistry in Titan's atmosphere under a range of conditions constrained by the literature source. The objective of this study is to determine the dependence of ion densities of C2H5+ and HCNH+ on the uncertainty in the reaction rates that involve these two ions in Titan's atmosphere.

Modeling ultrafast laser-induced nanocavitation around plasmonic nanoparticles (Conference Presentation)

NASA Astrophysics Data System (ADS)

Meunier, Michel; Dagallier, Adrien; Lachaine, Rémi; Boutopoulos, Christos; Boulais, Étienne

2017-03-01

Vapor nanobubbles generated around plasmonic nanoparticles (NPs) by ultrafast laser irradiation are efficient for inducing localized damage to living cells. Killing targeted cancer cells or gene delivery can therefore be envisioned using this new technology [1,2]. The extent of the damage and its non-lethal character are linked to the size of the nanobubble. Precise understanding of the mechanisms leading to bubble formation around plasmonic nanostructures is necessary to optimize the technique. In this presentation, we present a complete model that successfully describes all interactions occurring during the irradiation of plasmonics nanostructures by an ultrafast laser of various pulse widths and fluences. Nanoavitation is caused by the interplay between heat conduction at the NP-medium interface and non-linear plasmon-enhanced photoionization of a nanoplasma in the near-field [3-5], the former being dominant for in-resonance and the latter for off-resonance irradiation. Modeling of the whole laser-nanoparticle interaction, together with the help of the shadowgraphic imaging and scattering techniques [3-5], give valuable insight on the mechanisms of cavitation at the nanoscale, leading to possible optimization of the nanostructure for bubble-based nanomedicine applications. 1- E. Boulais, R. Lachaine, A. Hatef, and M. Meunier, Journal of Photochemistry and Photobiology C: Photochemistry Reviews 17, 26-49 (2013). 2- E. Bergeron, S. Patskovsky, D. Rioux, and M. Meunier, Nanoscale 7,17836-17847 (2015). 3- E. Boulais, R. Lachaine, and M. Meunier, Nano Letters 12, 4763-4769 (2012). 4- R. Lachaine, E. Boulais, and M. Meunier, ACS Photonics 1, 331-336 (2014). 5- C. Boutopoulos, A. Hatef, M. Fortin-Deschênes, and M. Meunier Nanoscale 7,11758-11765 (2015).

Photochemistry of matrix isolated (trifluoromethyl)sulfonyl azide, CF₃SO₂N₃.

PubMed

Zeng, Xiaoqing; Beckers, Helmut; Willner, Helge; Neuhaus, Patrik; Grote, Dirk; Sander, Wolfram

2015-03-19

The photochemistry of matrix isolated (trifluoromethylsulfonyl) azide, CF3SO2N3, has been studied at low temperatures. Upon ArF laser irradiation (λ = 193 nm), the azide eliminates N2 and furnishes triplet [(trifluoromethyl)sulfonyl]nitrene, CF3SO2N, which has been characterized by IR and EPR spectroscopy. Upon subsequent UV light irradiation (λ = 260-400 nm) the nitrene converts to CF3N═SO2 and CF3S(O)NO through a Curtius-type rearrangement. Further two new species CF2N═SO2F and FSNO were identified together with CF2NF, SO2, F2CO, CF3NO, and SO as side products. In addition, triplet nitrene CF3N was detected by its EPR and IR spectra. The complex stepwise photodecomposition of matrix isolated CF3SO2N3 is discussed in terms of the observed photolysis products and quantum chemical calculations.

Chemistry and spectroscopy of the Jovian atmosphere

NASA Technical Reports Server (NTRS)

Prinn, R. G.; Owen, T.

1976-01-01

A comprehensive review is given of the chemistry and spectroscopic studies of the Jovian atmosphere. Thermochemical equilibrium models for determining atmospheric composition are considered along with possible disequilibrating processes, and studies of the photochemistry of H2, CH4, NH3, H2S, and PH3 using the modeling methods are summarized. It is shown that photodissociation and advection are the major disequilibrating processes in Jupiter's atmosphere, that lightning and charged-particle bombardment are relatively minor factors in the planet's bulk chemistry, and that the existence of living organisms on the planet is highly improbable. Spectroscopic investigations of Jupiter are discussed, emphasizing recent observations of absorption bands due to CH4, NH3, H2, He, and D. Spectroscopic abundance determinations are examined for H2, HD, CH4, CH3D, NH3, C2H6, C2H2, and PH3. Upper limits are given for the abundances of several unobserved gases in the visible atmosphere, including H2S, HCl, SiH4, benzene, purines, pyrimidines, and their derivatives.

Applications of Continuous-Flow Photochemistry in Organic Synthesis, Material Science, and Water Treatment.

PubMed

Cambié, Dario; Bottecchia, Cecilia; Straathof, Natan J W; Hessel, Volker; Noël, Timothy

2016-09-14

Continuous-flow photochemistry in microreactors receives a lot of attention from researchers in academia and industry as this technology provides reduced reaction times, higher selectivities, straightforward scalability, and the possibility to safely use hazardous intermediates and gaseous reactants. In this review, an up-to-date overview is given of photochemical transformations in continuous-flow reactors, including applications in organic synthesis, material science, and water treatment. In addition, the advantages of continuous-flow photochemistry are pointed out and a thorough comparison with batch processing is presented.

Parents' reported preference scores for childhood atopic dermatitis disease states

PubMed Central

Friedman, Joëlle Y; Reed, Shelby D; Weinfurt, Kevin P; Kahler, Kristijan H; Walter, Emmanuel B; Schulman, Kevin A

2004-01-01

Background We sought to elicit preference weights from parents for health states corresponding to children with various levels of severity of atopic dermatitis. We also evaluated the hypothesis that parents with children who had been diagnosed with atopic dermatitis would assign different preferences to the health state scenarios compared with parents who did not have a child with atopic dermatitis. Methods Subjects were parents of children aged 3 months to 18 years. The sample was derived from the General Panel, Mommies Sub-Panel, and Chronic Illness Sub-Panel of Harris Interactive. Participants rated health scenarios for atopic dermatitis, asthma, and eyeglasses on a visual analog scale, imagining a child was experiencing the described state. Results A total of 3539 parents completed the survey. Twenty-nine percent had a child with a history of atopic dermatitis. Mean preference scores for atopic dermatitis were as follows: mild, 91 (95% confidence interval [CI], 90.7 to 91.5); mild/moderate, 84 (95%CI, 83.5 to 84.4); moderate, 73 (95%CI, 72.5 to 73.6); moderate/severe, 61 (95%CI, 60.6 to 61.8); severe, 49 (95% CI, 48.7 to 50.1); asthma, 58 (95%CI, 57.4 to 58.8); and eyeglasses, 87(95%CI, 86.3 to 87.4). Conclusions Parents perceive that atopic dermatitis has a negative effect on quality of life that increases with disease severity. Estimates of parents' preferences can provide physicians with insight into the value that parents place on their children's treatment and can be used to evaluate new medical therapies for atopic dermatitis. PMID:15491500

Orbital Engineering: Photoactivation of an Organofunctionalized Polyoxotungstate.

PubMed

Cameron, Jamie M; Fujimoto, Satomi; Kastner, Katharina; Wei, Rong-Jia; Robinson, David; Sans, Victor; Newton, Graham N; Oshio, H Hiroki

2017-01-01

Tungsten-based polyoxometalates (POMs) have been employed as UV-driven photo-catalysts for a range of organic transformations. Their photoactivity is dependent on electronic transitions between frontier orbitals and thus manipulation of orbital energy levels provides a promising means of extending their utility into the visible regime. Herein, an organic-inorganic hybrid polyoxometalate, K 6 [P 2 W 17 O 57 (PO 5 H 5 C 7 ) 2 ]⋅6 C 4 H 9 NO, was found to exhibit enhanced redox behaviour and photochemistry compared to its purely inorganic counterparts. Hybridization with electron-withdrawing moieties was shown to tune the frontier orbital energy levels and reduce the HOMO-LUMO gap, leading to direct visible-light photoactivation of the hybrid and establishing a simple, cheap and effective approach to the generation of visible-light-activated hybrid nanomaterials. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Compact Solid-State 213 nm Laser Enables Standoff Deep Ultraviolet Raman Spectrometer: Measurements of Nitrate Photochemistry.

PubMed

Bykov, Sergei V; Mao, Michael; Gares, Katie L; Asher, Sanford A

2015-08-01

We describe a new compact acousto-optically Q-switched diode-pumped solid-state (DPSS) intracavity frequency-tripled neodymium-doped yttrium vanadate laser capable of producing ~100 mW of 213 nm power quasi-continuous wave as 15 ns pulses at a 30 kHz repetition rate. We use this new laser in a prototype of a deep ultraviolet (UV) Raman standoff spectrometer. We use a novel high-throughput, high-resolution Echelle Raman spectrograph. We measure the deep UV resonance Raman (UVRR) spectra of solid and solution sodium nitrate (NaNO3) and ammonium nitrate (NH4NO3) at a standoff distance of ~2.2 m. For this 2.2 m standoff distance and a 1 min spectral accumulation time, where we only monitor the symmetric stretching band, we find a solid state NaNO3 detection limit of ~100 μg/cm(2). We easily detect ~20 μM nitrate water solutions in 1 cm path length cells. As expected, the aqueous solutions UVRR spectra of NaNO3 and NH4NO3 are similar, showing selective resonance enhancement of the nitrate (NO3(-)) vibrations. The aqueous solution photochemistry is also similar, showing facile conversion of NO3(-) to nitrite (NO2(-)). In contrast, the observed UVRR spectra of NaNO3 and NH4NO3 powders significantly differ, because their solid-state photochemistries differ. Whereas solid NaNO3 photoconverts with a very low quantum yield to NaNO2, the NH4NO3 degrades with an apparent quantum yield of ~0.2 to gaseous species.

Distributions and Seasonal Variations of Tropospheric Ethene (C2H4) from Atmospheric Chemistry Experiment (ACE-FTS) Solar Occultation Spectra

NASA Technical Reports Server (NTRS)

Herbin, H.; Hurtmans, D.; Clarisse, L.; Turquety, S.; Clerbaux, C.; Rinsland, Curtis P.; Boone, C.; Bernath, P. F.; Coheur, P.-F.

2009-01-01

This work reports the first measurements of ethene (C2H4) distributions in the upper troposphere. These are obtained by retrieving vertical profiles from 5 to 20 km from infrared solar occultation spectra recorded in 2005 and 2006 by the Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS). Background volume mixin^ ratios (vmrs) ranging from a few to about 50 pptv (10(exp -1) are measured at the different altitudes, while for certain occultations, vmrs as high as 200 pptv are observed. Zonal distributions and vertically resolved latitudinal distributions are derived for the two year period analyzed, highlighting spatial - including a North-South gradient - as well as seasonal variations. We show the latter to be more pronounced at the highest latitudes, presumably as a result of less active photochemistry during winter. The observation of C2H4 enhancements in remote Arctic regions at high latitudes is consistent with the occurrence of fast transport processes of gaseous pollution from the continents leading to Arctic haze. Citation: Herbin, H., D. Hurtmans, L. Clarisse, S. Turquety, C. Clerbaux, C. P. Rinsland, C. Boone, P. F. Bernath, and P.-F. Colieur (2009), Distributions and seasonal variations of tropospheric ethene (C2H4) from Atmospheric Chemistry Experiment (ACE-FTS) solar occultation spectra,

On the Composition of Young, Directly Imaged Giant Planets

NASA Technical Reports Server (NTRS)

Moses, J. I.; Marley, M. S.; Zahnle, K.; Line, M. R.; Fortney, J. J.; Barman, T. S.; Visscher, C.; Lewis, N. K.; Wolff, M. J.

2016-01-01

The past decade has seen significant progress on the direct detection and characterization of young, self-luminous giant planets at wide orbital separations from their host stars. Some of these planets show evidence for disequilibrium processes like transport-induced quenching in their atmospheres; photochemistry may also be important, despite the typically large orbital distances. Disequilibrium chemical processes such as these can alter the expected composition, spectral behavior, thermal structure, and cooling history of the planets, and can potentially confuse determinations of bulk elemental ratios, which provide important insights into planet-formation mechanisms. Using a thermo/photochemical kinetics and transport model, we investigate the extent to which disequilibrium chemical processes affect the composition and spectra of directly imaged giant exoplanets. Results for specific "young Jupiters" such as HR 8799 b and c and 51 Eri b are presented, as are general trends as a function of planetary effective temperature, surface gravity, incident ultraviolet flux, and strength of deep atmospheric convection. We find that quenching is very important on young Jupiters, leading to CO/CH4 and N2/NH3 ratios much greater than; and H2O mixing ratios a factor of a few less than chemical equilibrium predictions. Photochemistry can also be important on such planets, with CO2 and HCN being key photochemical products. Carbon dioxide becomes a particularly major constituent when stratospheric temperatures are low and recycling of water following H2O photolysis becomes stifled. Young Jupiters with effective temperatures less than 700 degrees Kelvin are in a particularly interesting photochemical regime that differs from both transiting hot Jupiters and our own solar-system giant planets.

High winter ozone pollution from carbonyl photolysis in an oil and gas basin.

PubMed

Edwards, Peter M; Brown, Steven S; Roberts, James M; Ahmadov, Ravan; Banta, Robert M; deGouw, Joost A; Dubé, William P; Field, Robert A; Flynn, James H; Gilman, Jessica B; Graus, Martin; Helmig, Detlev; Koss, Abigail; Langford, Andrew O; Lefer, Barry L; Lerner, Brian M; Li, Rui; Li, Shao-Meng; McKeen, Stuart A; Murphy, Shane M; Parrish, David D; Senff, Christoph J; Soltis, Jeffrey; Stutz, Jochen; Sweeney, Colm; Thompson, Chelsea R; Trainer, Michael K; Tsai, Catalina; Veres, Patrick R; Washenfelder, Rebecca A; Warneke, Carsten; Wild, Robert J; Young, Cora J; Yuan, Bin; Zamora, Robert

2014-10-16

The United States is now experiencing the most rapid expansion in oil and gas production in four decades, owing in large part to implementation of new extraction technologies such as horizontal drilling combined with hydraulic fracturing. The environmental impacts of this development, from its effect on water quality to the influence of increased methane leakage on climate, have been a matter of intense debate. Air quality impacts are associated with emissions of nitrogen oxides (NOx = NO + NO2) and volatile organic compounds (VOCs), whose photochemistry leads to production of ozone, a secondary pollutant with negative health effects. Recent observations in oil- and gas-producing basins in the western United States have identified ozone mixing ratios well in excess of present air quality standards, but only during winter. Understanding winter ozone production in these regions is scientifically challenging. It occurs during cold periods of snow cover when meteorological inversions concentrate air pollutants from oil and gas activities, but when solar irradiance and absolute humidity, which are both required to initiate conventional photochemistry essential for ozone production, are at a minimum. Here, using data from a remote location in the oil and gas basin of northeastern Utah and a box model, we provide a quantitative assessment of the photochemistry that leads to these extreme winter ozone pollution events, and identify key factors that control ozone production in this unique environment. We find that ozone production occurs at lower NOx and much larger VOC concentrations than does its summertime urban counterpart, leading to carbonyl (oxygenated VOCs with a C = O moiety) photolysis as a dominant oxidant source. Extreme VOC concentrations optimize the ozone production efficiency of NOx. There is considerable potential for global growth in oil and gas extraction from shale. This analysis could help inform strategies to monitor and mitigate air quality impacts and provide broader insight into the response of winter ozone to primary pollutants.

High winter ozone pollution from carbonyl photolysis in an oil and gas basin

NASA Astrophysics Data System (ADS)

Edwards, Peter M.; Brown, Steven S.; Roberts, James M.; Ahmadov, Ravan; Banta, Robert M.; Degouw, Joost A.; Dubé, William P.; Field, Robert A.; Flynn, James H.; Gilman, Jessica B.; Graus, Martin; Helmig, Detlev; Koss, Abigail; Langford, Andrew O.; Lefer, Barry L.; Lerner, Brian M.; Li, Rui; Li, Shao-Meng; McKeen, Stuart A.; Murphy, Shane M.; Parrish, David D.; Senff, Christoph J.; Soltis, Jeffrey; Stutz, Jochen; Sweeney, Colm; Thompson, Chelsea R.; Trainer, Michael K.; Tsai, Catalina; Veres, Patrick R.; Washenfelder, Rebecca A.; Warneke, Carsten; Wild, Robert J.; Young, Cora J.; Yuan, Bin; Zamora, Robert

2014-10-01

The United States is now experiencing the most rapid expansion in oil and gas production in four decades, owing in large part to implementation of new extraction technologies such as horizontal drilling combined with hydraulic fracturing. The environmental impacts of this development, from its effect on water quality to the influence of increased methane leakage on climate, have been a matter of intense debate. Air quality impacts are associated with emissions of nitrogen oxides (NOx = NO + NO2) and volatile organic compounds (VOCs), whose photochemistry leads to production of ozone, a secondary pollutant with negative health effects. Recent observations in oil- and gas-producing basins in the western United States have identified ozone mixing ratios well in excess of present air quality standards, but only during winter. Understanding winter ozone production in these regions is scientifically challenging. It occurs during cold periods of snow cover when meteorological inversions concentrate air pollutants from oil and gas activities, but when solar irradiance and absolute humidity, which are both required to initiate conventional photochemistry essential for ozone production, are at a minimum. Here, using data from a remote location in the oil and gas basin of northeastern Utah and a box model, we provide a quantitative assessment of the photochemistry that leads to these extreme winter ozone pollution events, and identify key factors that control ozone production in this unique environment. We find that ozone production occurs at lower NOx and much larger VOC concentrations than does its summertime urban counterpart, leading to carbonyl (oxygenated VOCs with a C = O moiety) photolysis as a dominant oxidant source. Extreme VOC concentrations optimize the ozone production efficiency of NOx. There is considerable potential for global growth in oil and gas extraction from shale. This analysis could help inform strategies to monitor and mitigate air quality impacts and provide broader insight into the response of winter ozone to primary pollutants.

Atmospheric chemistry of ethane and ethylene

NASA Technical Reports Server (NTRS)

Aikin, A. C.; Herman, J. R.; Maier, E. J.; Mcquillan, C. J.

1982-01-01

It is shown by a study of ethane and ethylene photochemistry that the loss of ethane is controlled by OH in the troposphere and Cl in the stratosphere. Ethane observations indicating free Cl concentrations below 30 km that are only 10% of the value predicted by the present model calculations cannot be explained by heterogeneous aerosol concentration processes, and contradict current stratospheric photochemistry. The chemical destruction of ethane and ethylene leads to the generation of such compounds as carbon monoxide and formaldehyde, and it is found that the tropospheric concentrations of the latter are enhanced by nearly a factor of three for an ethylene mixing ratio of 2 ppb.

Exogenous Calcium Enhances the Photosystem II Photochemistry Response in Salt Stressed Tall Fescue.

PubMed

Wang, Guangyang; Bi, Aoyue; Amombo, Erick; Li, Huiying; Zhang, Liang; Cheng, Cheng; Hu, Tao; Fu, Jinmin

2017-01-01

Calcium enhances turfgrass response to salt stress. However, little is known about PSII photochemical changes when exogenous calcium was applied in salinity-stressed turfgrass. Here, we probe into the rearrangements of PSII electron transport and endogenous ion accumulation in tall fescue ( Festuca arundinacea Schreber) treated with exogenous calcium under salt stress. Three-month-old seedlings of genotype "TF133" were subjected to the control (CK), salinity (S), salinity + calcium nitrate (SC), and salinity + ethylene glycol tetraacetic acid (SE). Calcium nitrate and ethylene glycol tetraacetic acid was used as exogenous calcium donor and calcium chelating agent respectively. At the end of a 5-day duration treatment, samples in SC regime had better photochemistry performance on several parameters than salinity only. Such as the Area (equal to the plastoquinone pool size), N (number of [Formula: see text] redox turnovers until F m is reached), ψE 0 , or δRo (Efficiencdy/probability with which a PSII trapped electron is transferred from Q A to Q B or PSI acceptors), ABS/RC (Absorbed photon flux per RC). All the above suggested that calcium enhanced the electron transfer of PSII (especially beyond [Formula: see text]) and prevented reaction centers from inactivation in salt-stressed tall fescue. Furthermore, both grass shoot and root tissues generally accumulated more C, N, Ca 2+ , and K + in the SC regime than S regime. Interrelated analysis indicated that ψE 0 , δRo, ABS/RC, C, and N content in shoots was highly correlated to each other and significantly positively related to Ca 2+ and K + content in roots. Besides, high salt increased ATP6E and CAMK2 transcription level in shoot at 1 and 5 day, respectively while exogenous calcium relieved it. In root, CAMK2 level was reduced by Salinity at 5 day and exogenous calcium recovered it. These observations involved in electron transport capacity and ion accumulation assist in understanding better the protective role of exogenous calcium in tall fescue under salt stress.

Chemistry and Photochemistry at the Surface of Urban Road Dust and Photoactive Minerals

NASA Astrophysics Data System (ADS)

Styler, S. A.; Abou-Ghanem, M.; Wickware, B.

2017-12-01

Each year, over a billion tons of dust are released into the atmosphere from arid regions. After its emission, dust can undergo efficient long-range transport to urban centres, where it can interact with local pollution sources. Another source of dust in urban regions is road dust resuspension, which is the largest anthropogenic source of primary particulate matter in both Canada and the United States. Since dust contains light-absorbing components, including iron- and titanium-containing minerals, dust-catalyzed photochemical processes have the potential to influence both the lifetime of pollutants present at the dust surface and the composition of the surrounding atmosphere. To date, most studies of dust photochemistry have focused on TiO2-mediated processes, and no studies have explored trace gas uptake at the surface of road dust. Here, we present first results from aerosol and coated-wall flow tube investigations of ozone uptake at the surface of a suite of titanium-containing minerals and road dust collected in Edmonton, Alberta. Together, this work represents a significant advance in our understanding of chemistry and photochemistry at realistic environmental interfaces.

Exogenous Calcium Enhances the Photosystem II Photochemistry Response in Salt Stressed Tall Fescue

PubMed Central

Wang, Guangyang; Bi, Aoyue; Amombo, Erick; Li, Huiying; Zhang, Liang; Cheng, Cheng; Hu, Tao; Fu, Jinmin

2017-01-01

Calcium enhances turfgrass response to salt stress. However, little is known about PSII photochemical changes when exogenous calcium was applied in salinity-stressed turfgrass. Here, we probe into the rearrangements of PSII electron transport and endogenous ion accumulation in tall fescue (Festuca arundinacea Schreber) treated with exogenous calcium under salt stress. Three-month-old seedlings of genotype “TF133” were subjected to the control (CK), salinity (S), salinity + calcium nitrate (SC), and salinity + ethylene glycol tetraacetic acid (SE). Calcium nitrate and ethylene glycol tetraacetic acid was used as exogenous calcium donor and calcium chelating agent respectively. At the end of a 5-day duration treatment, samples in SC regime had better photochemistry performance on several parameters than salinity only. Such as the Area (equal to the plastoquinone pool size), N (number of QA- redox turnovers until Fm is reached), ψE0, or δRo (Efficiencdy/probability with which a PSII trapped electron is transferred from QA to QB or PSI acceptors), ABS/RC (Absorbed photon flux per RC). All the above suggested that calcium enhanced the electron transfer of PSII (especially beyond QA-) and prevented reaction centers from inactivation in salt-stressed tall fescue. Furthermore, both grass shoot and root tissues generally accumulated more C, N, Ca2+, and K+ in the SC regime than S regime. Interrelated analysis indicated that ψE0, δRo, ABS/RC, C, and N content in shoots was highly correlated to each other and significantly positively related to Ca2+ and K+ content in roots. Besides, high salt increased ATP6E and CAMK2 transcription level in shoot at 1 and 5 day, respectively while exogenous calcium relieved it. In root, CAMK2 level was reduced by Salinity at 5 day and exogenous calcium recovered it. These observations involved in electron transport capacity and ion accumulation assist in understanding better the protective role of exogenous calcium in tall fescue under salt stress. PMID:29250091

The stratcom 8 effort. [stratospheric photochemistry

NASA Technical Reports Server (NTRS)

Reed, E. I. (Editor)

1980-01-01

The ozone-nitrogen oxides ultraviolent flux interactions were investigated to obtain data on stratospheric photochemistry. The balloon, rocket, and aircraft operations are described along with the instruments, parameter measurements, and payloads.

Atmospheric carbon dioxide changes photochemical activity, soluble sugars and volatile levels in broccoli (Brassica oleracea var. italica).

PubMed

Krumbein, Angelika; Kläring, Hans-Peter; Schonhof, Ilona; Schreiner, Monika

2010-03-24

Atmospheric carbon dioxide (CO(2)) concentration is an environmental factor currently undergoing dramatic changes. The objective of the present study was to determine the effect of doubling the ambient CO(2) concentration on plant photochemistry as measured by photochemical quenching coefficient (qP), soluble sugars and volatiles in broccoli. Elevated CO(2) concentration increased qP values in leaves by up to 100% and 89% in heads, while glucose and sucrose in leaves increased by about 60%. Furthermore, in broccoli heads elevated CO(2) concentration induced approximately a 2-fold increase in concentrations of three fatty acid-derived C(7) aldehydes ((E)-2-heptenal, (E,Z)-2,4-heptadienal, (E,E)-2,4-heptadienal), two fatty acid-derived C(5) alcohols (1-penten-3-ol, (Z)-2-pentenol), and two amino acid-derived nitriles (phenyl propanenitrile, 3-methyl butanenitrile). In contrast, concentrations of the sulfur-containing compound 2-ethylthiophene and C(6) alcohol (E)-2-hexenol decreased. Finally, elevated CO(2) concentration increased soluble sugar concentrations due to enhanced photochemical activity in leaves and heads, which may account for the increased synthesis of volatiles.

Cross-continental triple oxygen isotope analysis of tropospheric CO2

NASA Astrophysics Data System (ADS)

Liang, M. C.; Rangarajan, R.; Newman, S.; Laskar, A. H.

2016-12-01

The abundance variations of near surface atmospheric CO2 isotopologues (primarily 16O12C16O, 16O13C16O, 17O12C16O, and 18O12C16O) represent an integrated signal from anthropogenic/biogeochemical processes, including fossil fuel burning, biospheric photosynthesis and respiration, hydrospheric isotope exchange with water, and stratospheric photochemistry. Oxygen isotopes, in particular, are affected by the carbon and water cycles. Being a useful tracer that directly probes governing processes in CO2 biogeochemical cycles, D17O (= ln(1+d17O) - 0.516´ln(1+d18O)) provides an alternative constraint on the strengths of the associated cycles involving CO2. Here, we report more than one year of data obtained from Taiwan (Taipei), South China Sea, and USA (Pasadena, CA and Palos Verdes, CA). On average, the D17O values from these locations are similar and show no significant influence from the 2014-2016 El Nino event, in contrast to what has been reported for the 1997-1998 El Nino from the CO2 data collected from La Jolla, CA. Implications for utilizing the new tracer D17O for carbon cycling studies will be made.

Ablative heat shield design for space shuttle

NASA Technical Reports Server (NTRS)

Seiferth, R. W.

1973-01-01

Ablator heat shield configuration optimization studies were conducted for the orbiter. Ablator and reusable surface insulation (RSI) trajectories for design studies were shaped to take advantage of the low conductance of ceramic RSI and high temperature capability of ablators. Comparative weights were established for the RSI system and for direct bond and mechanically attached ablator systems. Ablator system costs were determined for fabrication, installation and refurbishment. Cost penalties were assigned for payload weight penalties, if any. The direct bond ablator is lowest in weight and cost. A mechanically attached ablator using a magnesium subpanel is highly competitive for both weight and cost.

Solar Flares and Coronal Physics Using P/OF as a Research Tool

NASA Technical Reports Server (NTRS)

Tandberg, E. (Editor); Wilson, R. M. (Editor); Hudson, R. M. (Editor)

1986-01-01

This NASA Conference Publication contains the proceedings of the Workshop on Solar High-Resolution Astrophysics Using the Pinhole/Occulter Facility held at NASA Marshall Space Flight Center, Alabama, on May 8 to 10, 1985. These proceedings include primarily the invited tutorial papers, extended abstracts of contributed poster papers, and summaries of subpanel (X-Ray and Coronal Physics) discussions. Both observational and theoretical results are presented. Although the emphasis of the Workshop was focused primarily on topics peculiar to solar physics, one paper is included that discusses the P/0F as a tool for X-ray astronomy.

Structural investigation of Titan tholins by solution-state 1H, 13C, and 15N NMR: one-dimensional and decoupling experiments.

PubMed

He, Chao; Lin, Guangxin; Upton, Kathleen T; Imanaka, Hiroshi; Smith, Mark A

2012-05-17

Titan, the largest moon of Saturn, is enveloped in a reddish brown organic haze. Titan haze is presumed to be formed from methane and nitrogen (CH(4) and N(2)) in Titan's upper atmosphere through energetic photochemistry and particle bombardment. Though Titan haze has been directly investigated using methods including the Cassini mission, its formation mechanism and the contributing chemical structures and prebiotic potential are still not well developed. We report here the structural investigation of the (13)C and (15)N labeled, simulated Titan haze aerosol (tholin) by solution-state NMR. The one-dimensional (1)H, (13)C, and (15)N NMR spectra and decoupling experiments indicate that the tholin sample contains amine, nitrile, imine, and N-heteroaromatic compounds of tremendous import in understanding complex organic chemistry in anaerobic, extraterrestrial environments.

COMPUTATION OF GLOBAL PHOTOCHEMISTRY WITH SMVGEAR II (R823186)

EPA Science Inventory

A computer model was developed to simulate global gas-phase photochemistry. The model solves chemical equations with SMVGEAR II, a sparse-matrix, vectorized Gear-type code. To obtain SMVGEAR II, the original SMVGEAR code was modified to allow computation of different sets of chem...

Methane photochemistry and methane production on Neptune

NASA Technical Reports Server (NTRS)

Romani, P. N.; Atreya, S. K.

1988-01-01

The Neptune stratosphere's methane photochemistry is presently studied by means of a numerical model in which the observed mixing ratio of methane prompts photolysis near the CH4 homopause. Haze generation by methane photochemistry has its basis in the formation of hydrocarbon ices and polyacetylenes; the hazes can furnish the requisite aerosol haze at the appropriate pressure levels required by observations of Neptune in the visible and near-IR. Comparisons of model predictions with Uranus data indicate a lower ratio of polyacetylene production to hydrocarbon ice, as well as a lower likelihood of UV postprocessing of the acetylene ice to polymers on Neptune, compared to Uranus.

The 2140 cm(exp -1) (4.673 Microns) Solid CO Band: The Case for Interstellar O2 and N2 and the Photochemistry of Non-Polar Interstellar Ice Analogs

NASA Technical Reports Server (NTRS)

Elsila, Jamie; Allamandola, Louis J.; Sandford, Scott A.; Witteborn, Fred C. (Technical Monitor)

1996-01-01

The infrared spectra of CO frozen in non-polar ices containing N2, CO2, O2, and H2O, and the ultraviolet photochemistry of these interstellar/precometary ice analogs are reported. The spectra are used to test the hypothesis that the narrow 2140/cm (4.673 micrometer) interstellar absorption feature attributed to solid CO might be produced by CO frozen in ices containing non-polar species such as N2 and O2. It is shown that mixed molecular ices containing CO, N2, O2, and CO2 provide a very good match to the interstellar band at all temperatures between 12 and 30 K both before and after photolysis. The optical constants (real and imaginary parts of the index of refraction) in the region of the solid CO feature are reported for several of these ices.

The (α-4) photoconjugates of 5-methylcytosine, 1,5-dimethylcytosine, 1-methylthymine and thymidine.

PubMed

Shetlar, Martin D; Chung, Janet

2012-01-01

The pyrimidine nucleobases contained in DNA undergo a variety of photoinduced reactions in which two moieties become joined to form a product (e.g. formation of cyclobutane dimers and [6-4] adducts). Herein, we describe a new type of photoconjugation reaction that has been shown to occur for 5-methylcytosine (5-MeC), 1,5-dimethylcytosine (1,5-diMeC), 1-methylthymine and thymidine; in this reaction the 5-methyl group of one nucleobase (or nucleoside) becomes attached to the 4-position of the second moiety. For example, 5-MeC forms α-4'-(5'-methylpyrimidin-2'-one)-5-methylcytosine. The various (α-4) conjugates are produced upon irradiation of the parent compound in frozen aqueous solution at -78.5°C. The UV spectra of these compounds display a characteristic "double humped" profile, similar to that expected from overlaying the spectrum of parent nucleobase with that of a 2'-pyrimidone moiety. Preliminary results suggest that thymine and 5-methyl-2'-deoxycytidine (5-MedCyd) form analogous photoproducts. A variety of other previously unreported photoproducts are described as well for the 5-MeC, 1,5-diMeC and 5-MedCyd systems. © 2011 Wiley Periodicals, Inc. Photochemistry and Photobiology © 2011 The American Society of Photobiology.

Increased temperature mitigates the effects of ocean acidification on the calcification of juvenile Pocillopora damicornis, but at a cost

NASA Astrophysics Data System (ADS)

Jiang, Lei; Zhang, Fang; Guo, Ming-Lan; Guo, Ya-Juan; Zhang, Yu-Yang; Zhou, Guo-Wei; Cai, Lin; Lian, Jian-Sheng; Qian, Pei-Yuan; Huang, Hui

2018-03-01

This study tested the interactive effects of increased seawater temperature and CO2 partial pressure ( pCO2) on the photochemistry, bleaching, and early growth of the reef coral Pocillopora damicornis. New recruits were maintained at ambient or high temperature (29 or 30.8 °C) and pCO2 ( 500 and 1100 μatm) in a full-factorial experiment for 3 weeks. Neither a sharp decline in photochemical efficiency (Fv/Fm) nor evident bleaching was observed at high temperature and/or high pCO2. Furthermore, elevated temperature greatly promoted lateral growth and calcification, while polyp budding exhibited temperature-dependent responses to pCO2. High pCO2 depressed calcification by 28% at ambient temperature, but did not impact calcification at 30.8 °C. Interestingly, elevated temperature in concert with high pCO2 significantly retarded the budding process. These results suggest that increased temperature can mitigate the adverse effects of acidification on the calcification of juvenile P. damicornis, but at a substantial cost to asexual budding.

Photochemistry of Triton's Atmosphere and Ionosphere

NASA Technical Reports Server (NTRS)

Krasnopolsky, Vladimir A.; Cruikshank, Dale P.

1995-01-01

The photochemistry of 32 neutral and 21 ion species in Triton's atmosphere is considered. Parent species N2, CH4, and CO (with a mixing ratio of 3 x 10(exp -4) in our basic model) sublime from the ice with rates of 40, 208, and 0.3 g/sq cm/b.y., respectively. Chemistry below 50 km is driven mostly by photolysis of methane by the solar and interstellar medium Lyman-alpha photons, producing hydrocarbons C2H4, C2H6, and C2H2 which form haze particles with precipitation rates of 135, 28, and 1.3 g/sq cm/b.y., respectively. Some processes are discussed which increase the production of HCN (by an order of magnitude to a value of 29 g/sq cm/b.y.) and involve indirect photolysis of N2 by neutrals. Reanalysis of the measured methane profiles gives an eddy diffusion coefficient K = 4 x 10(exp 3)sq cm/s above the tropopause and a more accurate methane number density near the surface, (3.1 +/- 0.8)x IO(exp 11)/cu cm. Chemistry above 200 km is driven by the solar EUV radiation (lambda less than 1000 A) and by precipitation of magnetospheric electrons with a total energy input of 10(exp 8) W (based on thermal balance calculations). The most abundant photochemical species are N, H2, H, 0, and C. They escape with the total rates of 7.7 x 10(exp 24)/ s, 4.5 x 10(exp 25)/s, 2.4 x 10(exp 25)/s, 4.4 x 10(exp 22)/s, and 1.1 x 10(exp 24), respectively. Atomic species are transported to a region of 50-200 km and drive the chemistry there. Ionospheric chemistry explains the formation of an E region at 150-240 km with HCO(+) as a major ion, and of an F region above 240 km with a peak at 320 km and C(+) as a major ion. The ionosphere above 500 km consists of almost equal densities of C(+) and N(+) ions. The model profiles agree with the measured atomic nitrogen and electron density profiles. A number of other models with varying rate coefficients of some reactions, differing properties of the haze particles (chemically passive or active), etc., were developed. These models show that there are four basic unknown values which have strong impacts on the composition and structure of the atmosphere and ionosphere. These values and their plausible ranges are the CO mixing ratio f(sub co) = 10(exp -4) - 10(exp -3), the magnetospheric electron energy input (1 +/- 0.5) x 10(exp 8) W, the rate coefficient of charge-exchange reaction N2(+) + C(kappa) = 10(exp -11) - 10(exp -10)cu cm/s, and the ion escape velocity upsilon(sub i) approx. equals 150 cm/s.

Chemistry in the Thermosphere and Ionosphere.

ERIC Educational Resources Information Center

Roble, Raymond G.

1986-01-01

An informative review which summarizes information about chemical reactions in the thermosphere and ionosphere. Topics include thermal structure, ultraviolet radiation, ionospheric photochemistry, thermospheric photochemistry, chemical heating, thermospheric circulation, auroral processes and ionospheric interactions. Provides suggested followup…

Summertime C1-C5 alkyl nitrates over Beijing, northern China: Spatial distribution, regional transport, and formation mechanisms

NASA Astrophysics Data System (ADS)

Sun, Jingjing; Li, Zeyuan; Xue, Likun; Wang, Tao; Wang, Xinfeng; Gao, Jian; Nie, Wei; Simpson, Isobel J.; Gao, Rui; Blake, Donald R.; Chai, Fahe; Wang, Wenxing

2018-05-01

Alkyl nitrates (RONO2) are an important class of nitrogen oxides reservoirs in the atmosphere and play a key role in tropospheric photochemistry. Despite the increasing concern for photochemical air pollution over China, the knowledge of characteristics and formation mechanisms of alkyl nitrates in this region is limited. We analyzed C1-C5 alkyl nitrates measured in Beijing at a polluted urban site in summer 2008 and at a downwind rural site in summers of both 2005 and 2008. Although the abundances of NOx and hydrocarbons were much lower at the rural site, the mixing ratios of RONO2 were comparable between both sites, emphasizing the regional nature of alkyl nitrate pollution. Regional transport of urban plumes governed the elevated RONO2 levels at the rural site. The concentrations of C1-C2 RONO2 were significantly higher at the rural site in 2008 compared to 2005 despite a decline in NOx and anthropogenic VOCs, mainly owing to enhanced contributions from biogenic VOCs. The photochemical formation regimes of RONO2 were evaluated by both a simplified sequential reaction model and a detailed master chemical mechanism box model. The observed C4-C5 RONO2 levels can be well explained by the photochemical degradation of n-butane and n-pentane, while the sources of C1-C3 RONO2 were rather complex. In addition to the C1-C3 alkanes, biogenic VOCs and reactive aromatics were also important precursors of methyl nitrate, and alkenes and long-chain alkanes contributed to the formation of C2-C3 RONO2. This study provides insights into the spatial distribution, inter-annual variation and photochemical formation mechanisms of alkyl nitrate pollution over the Beijing area.

Use of Proteomic and Hematology Biomarkers for Prediction of Hematopoietic Acute Radiation Syndrome Severity in Baboon Radiation Models.

PubMed

Blakely, William F; Bolduc, David L; Debad, Jeff; Sigal, George; Port, Matthias; Abend, Michael; Valente, Marco; Drouet, Michel; Hérodin, Francis

2018-07-01

Use of plasma proteomic and hematological biomarkers represents a promising approach to provide useful diagnostic information for assessment of the severity of hematopoietic acute radiation syndrome. Eighteen baboons were evaluated in a radiation model that underwent total-body and partial-body irradiations at doses of Co gamma rays from 2.5 to 15 Gy at dose rates of 6.25 cGy min and 32 cGy min. Hematopoietic acute radiation syndrome severity levels determined by an analysis of blood count changes measured up to 60 d after irradiation were used to gauge overall hematopoietic acute radiation syndrome severity classifications. A panel of protein biomarkers was measured on plasma samples collected at 0 to 28 d after exposure using electrochemiluminescence-detection technology. The database was split into two distinct groups (i.e., "calibration," n = 11; "validation," n = 7). The calibration database was used in an initial stepwise regression multivariate model-fitting approach followed by down selection of biomarkers for identification of subpanels of hematopoietic acute radiation syndrome-responsive biomarkers for three time windows (i.e., 0-2 d, 2-7 d, 7-28 d). Model 1 (0-2 d) includes log C-reactive protein (p < 0.0001), log interleukin-13 (p < 0.0054), and procalcitonin (p < 0.0316) biomarkers; model 2 (2-7 d) includes log CD27 (p < 0.0001), log FMS-related tyrosine kinase 3 ligand (p < 0.0001), log serum amyloid A (p < 0.0007), and log interleukin-6 (p < 0.0002); and model 3 (7-28 d) includes log CD27 (p < 0.0012), log serum amyloid A (p < 0.0002), log erythropoietin (p < 0.0001), and log CD177 (p < 0.0001). The predicted risk of radiation injury categorization values, representing the hematopoietic acute radiation syndrome severity outcome for the three models, produced least squares multiple regression fit confidences of R = 0.73, 0.82, and 0.75, respectively. The resultant algorithms support the proof of concept that plasma proteomic biomarkers can supplement clinical signs and symptoms to assess hematopoietic acute radiation syndrome risk severity.

The photochemistry of pyrimidine in realistic astrophysical ices and the production of nucleobases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nuevo, Michel; Materese, Christopher K.; Sandford, Scott A., E-mail: michel.nuevo-1@nasa.gov

2014-10-01

Nucleobases, together with deoxyribose/ribose and phosphoric acid, are the building blocks of DNA and RNA for all known life. The presence of nucleobase-like compounds in carbonaceous chondrites delivered to the Earth raises the question of an extraterrestrial origin for the molecules that triggered life on our planet. Whether these molecules are formed in interstellar/protostellar environments, in small parent bodies in the solar system, or both, is currently unclear. Recent experiments show that the UV irradiation of pyrimidine (C{sub 4}H{sub 4}N{sub 2}) in H{sub 2}O-rich ice mixtures that contain NH{sub 3}, CH{sub 3}OH, or CH{sub 4} leads to the formation ofmore » the pyrimidine-based nucleobases uracil, cytosine, and thymine. In this work, we discuss the low-temperature UV irradiation of pyrimidine in realistic astrophysical ice mixtures containing H{sub 2}O, CH{sub 3}OH, and NH{sub 3}, with or without CH{sub 4}, to search for the production of nucleobases and other prebiotic compounds. These experiments show the presence of uracil, urea, glycerol, hexamethylenetetramine, small amino acids, and small carboxylic acids in all samples. Cytosine was only found in one sample produced from ices irradiated with a higher UV dose, while thymine was not found in any sample, even after irradiation with a higher UV dose. Results are discussed to evaluate the role of the photochemistry of pyrimidine in the inventory of organic molecules detected in meteorites and their astrophysical/astrobiological implications.« less

Ozone photochemistry in an oil and natural gas extraction region during winter: simulations of a snow-free season in the Uintah Basin, Utah

NASA Astrophysics Data System (ADS)

Edwards, P. M.; Young, C. J.; Aikin, K.; deGouw, J. A.; Dubé, W. P.; Geiger, F.; Gilman, J. B.; Helmig, D.; Holloway, J. S.; Kercher, J.; Lerner, B.; Martin, R.; McLaren, R.; Parrish, D. D.; Peischl, J.; Roberts, J. M.; Ryerson, T. B.; Thornton, J.; Warneke, C.; Williams, E. J.; Brown, S. S.

2013-03-01

The Uintah Basin in northeastern Utah, a region of intense oil and gas extraction, experienced ozone (O3) concentrations above levels harmful to human health for multiple days during the winters of 2009-2010 and 2010-2011. These wintertime O3 pollution episodes occur during cold, stable periods when the ground is snowcovered, and have been linked to emissions from the oil and gas extraction process. The Uintah Basin Winter Ozone Study (UBWOS) was a field intensive in early 2012, whose goal was to address current uncertainties in the chemical and physical processes that drive wintertime O3 production in regions of oil and gas development. Although elevated O3 concentrations were not observed during the winter of 2011-2012, the comprehensive set of observations tests of our understanding of O3 photochemistry in this unusual emissions environment. A box model, constrained to the observations and using the explicit Master Chemical Mechanism (MCM) V3.2 chemistry scheme, has been used to investigate the sensitivities of O3 production during UBWOS 2012. Simulations identify the O3 production photochemistry to be highly radical limited. Production of OH from O3 photolysis (through reaction of O(1D) with water vapor) contributed only 170 pptv day-1, 8% of the total primary radical source on average. Other radical sources, including the photolysis of formaldehyde (HCHO, 52%), nitrous acid (HONO, 26%), and nitryl chloride (ClNO2, 13%) were larger. O3 production was also found to be highly sensitive to aromatic volatile organic compound (VOC) concentrations, due to radical amplification reactions in the oxidation scheme of these species. Radical production was shown to be small in comparison to the emissions of nitrogen oxides (NOx), such that NOx acted as the primary radical sink. Consequently, the system was highly VOC sensitive, despite the much larger mixing ratio of total non-methane hydrocarbons (230 ppbv (2080 ppbC), 6 week average) relative to NOx (5.6 ppbv average). However, the importance of radical sources which are themselves derived from NOx emissions and chemistry, such as ClNO2 and HONO, make the response of the system to changes in NOx emissions uncertain. These box model simulations provide useful insight into the chemistry controlling winter O3 production in regions of oil and gas extraction.

Adsorption, Mobility and Organisation of Organic Molecules at Clay Surfaces Probed by Photophysics and Photochemistry

DTIC Science & Technology

1989-06-15

and refluxed at 100 0 C during 24 hours. This basic hydrolysis results in the formation of polymethacrylic acid , which is soluble in basic media. The...from the supernatant solution by adding 3M HC The I.R.spectrum of the obtained polymer is identical to the I.R. spectrum of the polymethacrylic acid (8

Feasibility of an orbital simulator of stratospheric photochemistry

NASA Technical Reports Server (NTRS)

Matloff, G. L.; Hoffert, M. I.

1978-01-01

It is proposed that a stratospheric photochemistry simulator could be created in sun-synchronous orbit, so that diffusion and photochemistry could be decoupled and uncertainties in photochemical reaction rates could be substantially reduced. The proposed test chamber is described, and it is suggested that the technology of superpressure balloons seems to be the best short-term solution to the construction of the proposed facility. Both unreinforced polyester films and gelatin films are considered as candidate chamber coatings. It is noted that the experiments can be performed early in the space-manufacturing era and that at least three dedicated Shuttle launches will be required to establish the proposed facility.

Organic chemistry on Titan

NASA Technical Reports Server (NTRS)

Chang, S.; Scattergood, T.; Aronowitz, S.; Flores, J.

1978-01-01

Observations of nonequilibrium phenomena on the Saturn satellite Titan indicate the occurrence of organic chemical evolution. Greenhouse and thermal inversion models of Titan's atmosphere provide environmental constraints within which various pathways for organic chemical synthesis are assessed. Experimental results and theoretical modeling studies suggest that the organic chemistry of the satellite may be dominated by two atmospheric processes: energetic-particle bombardment and photochemistry. Reactions initiated in various levels of the atmosphere by cosmic ray, Saturn wind, and solar wind particle bombardment of a CH4 - N2 atmospheric mixture can account for the C2-hydrocarbons, the UV-visible-absorbing stratospheric haze, and the reddish color of the satellite. Photochemical reactions of CH4 can also account for the presence of C2-hydrocarbons. In the lower Titan atmosphere, photochemical processes will be important if surface temperatures are sufficiently high for gaseous NH3 to exist. Hot H-atom reactions initiated by photo-dissociation of NH3 can couple the chemical reactions of NH3 and CH4 and produce organic matter.

MONTE CARLO SIMULATION OF METASTABLE OXYGEN PHOTOCHEMISTRY IN COMETARY ATMOSPHERES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bisikalo, D. V.; Shematovich, V. I.; Gérard, J.-C.

2015-01-01

Cometary atmospheres are produced by the outgassing of material, mainly H{sub 2}O, CO, and CO{sub 2} from the nucleus of the comet under the energy input from the Sun. Subsequent photochemical processes lead to the production of other species generally absent from the nucleus, such as OH. Although all comets are different, they all have a highly rarefied atmosphere, which is an ideal environment for nonthermal photochemical processes to take place and influence the detailed state of the atmosphere. We develop a Monte Carlo model of the coma photochemistry. We compute the energy distribution functions (EDF) of the metastable O({supmore » 1}D) and O({sup 1}S) species and obtain the red (630 nm) and green (557.7 nm) spectral line shapes of the full coma, consistent with the computed EDFs and the expansion velocity. We show that both species have a severely non-Maxwellian EDF, that results in broad spectral lines and the suprathermal broadening dominates due to the expansion motion. We apply our model to the atmosphere of comet C/1996 B2 (Hyakutake) and 103P/Hartley 2. The computed width of the green line, expressed in terms of speed, is lower than that of the red line. This result is comparable to previous theoretical analyses, but in disagreement with observations. We explain that the spectral line shape does not only depend on the exothermicity of the photochemical production mechanisms, but also on thermalization, due to elastic collisions, reducing the width of the emission line coming from the O({sup 1}D) level, which has a longer lifetime.« less

Synthesis and photochemistry of pH-sensitive GFP chromophore analogues

USDA-ARS?s Scientific Manuscript database

Nobel GFP chromophore analogues containing 2-thienyl-, 5-methyl-2-furyl-, 2-pyrryl, and 6-methyl-2-pyridyl-groups were synthesized, and their fluorescence spectra were recorded across pH range of 1 to 7. The GFP chromophores prevent photoisomerizaiton in acidic media and increase their fluorescent a...

A Theoretical Study of the Photodissociation Mechanism of Cyanoacetylene in Its Lowest Singlet and Triplet Excited States

NASA Astrophysics Data System (ADS)

Luo, Cheng; Du, Wei-Na; Duan, Xue-Mei; Li, Ze-Sheng

2008-11-01

Cyanoacetylene (H5-C4 ≡ C3-C2 ≡ N1) is a minor constituent of the atmosphere of Titan, and its photochemistry plays an important role in the formation of the haze surrounding the satellite. In this paper, the complete active space self-consistent field (CASSCF) and multiconfigurational second-order perturbation (CASPT2) approaches are employed to investigate the photochemical processes for cyanoacetylene in its first singlet and triplet excited states with the cc-pVTZ basis set. Fissions of the C4-H5 and C2-C3 bonds in S1 yield H(2S) + CCCN(A2Π) and HCC(A2Π) + CN(X2Σ+), respectively. In T1, the corresponding dissociation products are H(2S) + CCCN(X2Σ+) and HCC(X2Σ) + CN(X2Σ+). At the CASPT2(14,13)//CASSCF(14,13) + ZPE level, the barriers for the adiabatic dissociation of the C4-H5 and C2-C3 bonds are 6.11 and 6.94 eV in S1 and 5.71 and 6.39 eV in T1, respectively, taking the energy of S0 minimum as reference. Based on the calculated potential energy surfaces, the existence of a metastable excited molecule is anticipated upon 260-230 nm photoexcitation, which provides a probable approach for cyanoacetylene to polymerize. The internal conversion (IC) process through vibronic interaction followed by C4-H5 fission in the ground state is found to account for the observed diffuse character in the UV absorption spectrum below 240 nm.

Development of a mechanism for nitrate photochemistry in snow.

PubMed

Bock, Josué; Jacobi, Hans-Werner

2010-02-04

A reaction mechanism to reproduce photochemical processes in the snow is reported. We developed a box model to represent snow chemistry. Constrained by laboratory experiments carried out with artificial snow, we deduced first a reaction mechanism for N-containing species including 13 reactions. An optimization tool was developed to adjust systematically unknown photolysis rates of nitrate and nitrite (NO(2)(-)) and transfer rates of nitrogen oxides from the snow to the gas phase resulting in an optimum fit with respect to the experimental data. Further experiments with natural snow samples are presented, indicating that NO(2)(-) concentrations were much lower than in the artificial snow experiments. These observations were used to extend the reaction mechanism into a more general scheme including hydrogen peroxide (H(2)O(2)) and formaldehyde (HCHO) chemistry leading to a set of 18 reactions. The simulations indicate the importance of H(2)O(2) and HCHO as either a source or sink of hydroxyl radicals in the snow photochemistry mechanism. The addition of H(2)O(2) and HCHO in the mechanism allows the reproduction of the observed low NO(2)(-) concentration.

[A Study of Data From the Photochemistry of Ozone Loss in the Arctic Region In Summer (POLARIS) Mission

NASA Technical Reports Server (NTRS)

Newman, Paul A.; Fahey, David W.; Brune, William H.; Kurylo, Michael J.; Kawa, S. Randolph

1999-01-01

The Photochemistry of Ozone Loss in the Arctic Region In Summer (POLARIS) mission was designed to investigate the natural summer decrease of stratospheric ozone levels. Both polar regions have large and distinct annual cycles of ozone column amounts. In northern spring, the average level is over 450 Dobson units (DU), decreasing to less than 275 DU by September. In order to cover this period of ozone decrease, POLARIS was conducted in three deployment phases from Fairbanks, Alaska, (650N) during the summer of 1997. The principal measurement platforms were the NASA ER-2 high-altitude aircraft and stratospheric balloons. Additional measurements were provided by ground-based instruments, sondes, and satellites. POLARIS observations included ozone, meteorological variables, particles, long-lived chemicals, and short-lived radicals. During the field deployments, several modeling and theoretical groups participated in flight planning and data evaluation activities. The interpretive studies in this Special Section of the Journal of Geophysical Research are a first comprehensive examination of the POLARIS data set, addressing stratospheric ozone abundances and its changes; the role of aerosols; details of the photochemistry of reactive species; transport of stratospheric air and the correlations of long-lived species; and measurement intercomparisons.

Explaining a Consistent Morning NOx Maximum in the Clean Air Forest Boundary Layer

NASA Astrophysics Data System (ADS)

Shepson, P. B.; Alaghmand, M.; Bertman, S. B.; Carroll, M.; Edburg, S. L.; Jobson, B. T.; Keutsch, F. N.; Lamb, B. K.; Starn, T.; Stevens, P. S.; Wallace, W.; Zhou, X.

2010-12-01

Measurements of nitrogen oxides (NOx) at continental surface sites have frequently revealed the presence of an early morning maximum in the NOx concentration. While this observation has most often been interpreted as the result of downward mixing associated with breakup of the nocturnal inversion, the morning NOx peak often occurs earlier than the NBL breakup. Given the importance of NOx to boundary layer photochemistry near forested environments, it is essential that this phenomenon be well understood. Here we examine a variety of measurements, including NOx measurements at various heights, during the 1998, 2001, 2008, and 2009 (CABINEX) summer intensives of the Program for Research on Oxidants: PHotochemistry, Emissions and Transport (PROPHET), at the University of Michigan Biological Station in Northern Michigan. We will discuss the results, in terms of the extent to which the observations support/refute each of the potential drivers of the morning NOx peak: 1) downward mixing, 2) photochemistry on the various surfaces present, 3) soil emissions, and 4) local and long range transport of anthropogenic NOx, and we will report on our conclusions as to the predominant/likely explanation(s) for this phenomenon.

Calculation of two dimensional vortex/surface interference using panel methods

NASA Technical Reports Server (NTRS)

Maskew, B.

1980-01-01

The application of panel methods to the calculation of vortex/surface interference characteristics in two dimensional flow was studied over a range of situations starting with the simple case of a vortex above a plane and proceeding to the case of vortex separation from a prescribed point on a thick section. Low order and high order panel methods were examined, but the main factor influencing the accuracy of the solution was the distance between control stations in relation to the height of the vortex above the surface. Improvements over the basic solutions were demonstrated using a technique based on subpanels and an applied doublet distribution.

Construction of a Visible Diode Laser Source for Free Radical Photochemistry and Spectroscopy Experiments

NASA Technical Reports Server (NTRS)

Newman, Bronjelyn; Halpern, Joshua B.

1997-01-01

Tunable diode lasers are reliable sources of narrow-band light and comparatively cheap. Optical feedback simplifies frequency tuning of the laser diodes. We are building an inexpensive diode laser system incorporating optical feedback from a diffraction grating. The external optical cavity can be used with lasers that emit between 2 and 100 mW, and will also work if they are pulsed, although this will significantly degrade the bandwidth. The diode laser output power and bandwidth are comparable to CW dye lasers used in kinetics and dynamics experiments. However, their cost and maintenance will be much less as will alignment time. We intend to use the diode lasers to investigate CN and C2 kinetics as well as to study dissociation dynamics of atmospherically important molecules.

Operational efficiency subpanel advanced mission control

NASA Technical Reports Server (NTRS)

Friedland, Peter

1990-01-01

Herein, the term mission control will be taken quite broadly to include both ground and space based operations as well as the information infrastructure necessary to support such operations. Three major technology areas related to advanced mission control are examined: (1) Intelligent Assistance for Ground-Based Mission Controllers and Space-Based Crews; (2) Autonomous Onboard Monitoring, Control and Fault Detection Isolation and Reconfiguration; and (3) Dynamic Corporate Memory Acquired, Maintained, and Utilized During the Entire Vehicle Life Cycle. The current state of the art space operations are surveyed both within NASA and externally for each of the three technology areas and major objectives are discussed from a user point of view for technology development. Ongoing NASA and other governmental programs are described. An analysis of major research issues and current holes in the program are provided. Several recommendations are presented for enhancing the technology development and insertion process to create advanced mission control environments.

ROLE OF CANOPY-SCALE PHOTOCHEMISTRY IN MODIFYING BIOGENIC-ATMOSPHERE EXCHANGE OF REACTIVE TERPENE SPECIES: RESULTS FROM THE CELTIC FIELD STUDY

EPA Science Inventory

A one-dimensional canopy model was used to quantify the impact of photochemistry in modifying biosphere-atmosphere exchange of trace gases. Canopy escape efficiencies, defined as the fraction of emission that escapes into the well-mixed boundary layer, were calculated for reactiv...

Ultraviolet Absorption Induces Hydrogen-Atom Transfer in G⋅C Watson-Crick DNA Base Pairs in Solution.

PubMed

Röttger, Katharina; Marroux, Hugo J B; Grubb, Michael P; Coulter, Philip M; Böhnke, Hendrik; Henderson, Alexander S; Galan, M Carmen; Temps, Friedrich; Orr-Ewing, Andrew J; Roberts, Gareth M

2015-12-01

Ultrafast deactivation pathways bestow photostability on nucleobases and hence preserve the structural integrity of DNA following absorption of ultraviolet (UV) radiation. One controversial recovery mechanism proposed to account for this photostability involves electron-driven proton transfer (EDPT) in Watson-Crick base pairs. The first direct observation is reported of the EDPT process after UV excitation of individual guanine-cytosine (G⋅C) Watson-Crick base pairs by ultrafast time-resolved UV/visible and mid-infrared spectroscopy. The formation of an intermediate biradical species (G[-H]⋅C[+H]) with a lifetime of 2.9 ps was tracked. The majority of these biradicals return to the original G⋅C Watson-Crick pairs, but up to 10% of the initially excited molecules instead form a stable photoproduct G*⋅C* that has undergone double hydrogen-atom transfer. The observation of these sequential EDPT mechanisms across intermolecular hydrogen bonds confirms an important and long debated pathway for the deactivation of photoexcited base pairs, with possible implications for the UV photochemistry of DNA. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Excited state dynamics of thiophene and bithiophene: new insights into theoretically challenging systems.

PubMed

Prlj, Antonio; Curchod, Basile F E; Corminboeuf, Clémence

2015-06-14

The computational elucidation and proper description of the ultrafast deactivation mechanisms of simple organic electronic units, such as thiophene and its oligomers, is as challenging as it is contentious. A comprehensive excited state dynamics analysis of these systems utilizing reliable electronic structure approaches is currently lacking, with earlier pictures of the photochemistry of these systems being conceived based upon high-level static computations or lower level dynamic trajectories. Here a detailed surface hopping molecular dynamics of thiophene and bithiophene using the algebraic diagrammatic construction to second order (ADC(2)) method is presented. Our findings illustrate that ring puckering plays an important role in thiophene photochemistry and that the photostability increases when going upon dimerization into bithiophene.

Hydrocarbon ratios during PEM-WEST A: A model perspective

NASA Astrophysics Data System (ADS)

McKeen, S. A.; Liu, S. C.; Hsie, E.-Y.; Lin, X.; Bradshaw, J. D.; Smyth, S.; Gregory, G. L.; Blake, D. R.

1996-01-01

A useful application of the hydrocarbon measurements collected during the Pacific Exploratory Mission (PEM-West A) is as markers or indices of atmospheric processing. Traditionally, ratios of particular hydrocarbons have been interpreted as photochemical indices, since much of the effect due to atmospheric transport is assumed to cancel by using ratios. However, an ever increasing body of observatonial and theoretical evidence suggests that turbulent mixing associated with atmospheric transport influences certain hydrocarbon ratios significantly. In this study a three-dimensional mesoscale photochemical model is used to study the interaction of photochemistry and atmospheric mixing on select hydrocarbons. In terms of correlations and functional relationships between various alkanes, the model results and PEM-West A hydrocarbon observations share many similar characteristics as well as explainable differences. When the three-dimensional model is applied to inert tracers, hydrocarbon ratios andother relationships exactly follow those expected by simple dilution with model-imposed "background air," and the three-dimensional results for reactive hydrocarbons are quite consistent with a combined influence of photochemistry and simple dilution. Analogous to these model results, relationships between various hydrocarbons collected during the PEM-West A experiment appear to be consistent with this simplified picture of photochemistry and dilution affecting individual air masses. When hydrocarbons are chosen that have negligible contributions to clean background air, unambiguous determinations of the relative contributions to photochemistry and dilution can be estimated from the hydrocarbon samples. Both the three-dimensional model results and the observations imply an average characteristic lifetime for dilution with background air roughly equivalent to the photochemical lifetime of butane for the western Pacific lower troposphere. Moreover, the dominance of OH as the primary photochemical oxidant downwind of anthropogenic source regions can be inferred from correlations between the highly reactive alkane ratios. By incorporating back-trajectory information within the three-dimensional model analysis, a correspondence between time and a particular hydrocarbon or hydrocarbon ratio can be determined, and the influence of atmospheric mixing or photochemistry can be quantified. Results of the three-dimensional model study are compared and applied to the PEM-West A hydrocarbon dataset, yielding a practical methodology for determining average OH concentrations and atmospheric mixing rates from the hydrocarbon measurements. Aircraft data taken below 2 km during wall flights east of Japan imply a diurnal average OH concentration of ˜3 × 106 cm-3. The characteristic time for dilution with background air is estimated to be ˜2.5 days for the two study areas examined in this work.

Photochemistry of bromoacetylene - Formation of HBr and quenching of excited Br/4 2P 0 1/2/

NASA Technical Reports Server (NTRS)

Laufer, A. H.

1979-01-01

The photolysis of bromacetylene is examined by means of vacuum ultraviolet flash photolysis-kinetic spectroscopy, with attention given to the production of Br atoms in the 2P 0 3/2 and 2P 0 1/2 states, the production of HBr, and UV absorption attributable to the ethynyl radical. Although Br(2P 0 1/2) and Br(2P 0 3/2) were both directly observed at the shortest delay time after the flash, strongly indicating the presence of the ethynyl radical, transient absorption by C2H was not detected in the range 125 to 180 nm. Quenching rate constants for the decay of the 2P 0 1/2 state of Br, which is observed to form concurrently with the ground state, are derived for quenching by He, CH2Br, CF4, and D2 from the pseudo-first-order decay rates. HBr was observed as a secondary photolysis product, and a model of its formation by the exothermic reaction of ground-state atoms with C2HBR, coupled with the secondary production of Br atoms, is found to agree well with the experiment.

Photochemistry and Transmission Pump-Probe Spectroscopy of 2-Azidobiphenyls in Aqueous Nanocrystalline Suspensions: Simplified Kinetics in Crystalline Solids.

PubMed

Chung, Tim S; Ayitou, Anoklase J-L; Park, Jin H; Breslin, Vanessa M; Garcia-Garibay, Miguel A

2017-04-20

Aqueous nanocrystalline suspensions provide a simple and efficient medium for performing transmission spectroscopy measurements in the solid state. In this Letter we describe the use of laser flash photolysis methods to analyze the photochemistry of 2-azidobiphenyl and several aryl-substituted derivatives. We show that all the crystalline compounds analyzed in this study transform quantitatively into carbazole products via a crystal-to-crystal reconstructive phase transition. While the initial steps of the reaction cannot be followed within the time resolution of our instrument (ca. 8 ns), we detected the primary isocarbazole photoproducts and analyzed the kinetics of their formal 1,5-H shift reactions, which take place in time scales that range from a few nanoseconds to several microseconds. It is worth noting that the high reaction selectivity observed in the crystalline state translates into a clean and simple kinetic process compared to that in solution.

The role of molecular hydrogen and methane oxidation in the water vapour budget of the stratosphere

NASA Technical Reports Server (NTRS)

Le Texier, H.; Solomon, S.; Garcia, R. R.

1988-01-01

The detailed photochemistry of methane oxidation has been studied in a coupled chemical/dynamical model of the middle atmosphere. The photochemistry of formaldehyde plays an important role in determining the production of water vapor from methane oxidation. At high latitudes, the production and transport of molecular hydrogen is particularly important in determining the water vapor distribution. It is shown that the ratio of the methane vertical gradient to the water vapor vertical gradient at any particular latitude should not be expected to be precisely 2, due both to photochemical and dynamical effects. Modeled H2O profiles are compared with measurements from the Limb Infrared Monitor of the Stratosphere (LIMS) experiment at various latitudes. Molecular hydrogen is shown to be responsible for the formation of a secondary maximum displayed by the model water vapor profiles in high latitude summer, a feature also found in the LIMS data.

Dust ablation on the giant planets: Consequences for stratospheric photochemistry

NASA Astrophysics Data System (ADS)

Moses, Julianne I.; Poppe, Andrew R.

2017-11-01

Ablation of interplanetary dust supplies oxygen to the upper atmospheres of Jupiter, Saturn, Uranus, and Neptune. Using recent dynamical model predictions for the dust influx rates to the giant planets (Poppe et al., 2016), we calculate the ablation profiles and investigate the subsequent coupled oxygen-hydrocarbon neutral photochemistry in the stratospheres of these planets. We find that dust grains from the Edgeworth-Kuiper Belt, Jupiter-family comets, and Oort-cloud comets supply an effective oxygen influx rate of 1.0-0.7+2.2 ×107 O atoms cm-2 s-1 to Jupiter, 7.4-5.1+16 ×104 cm-2 s-1 to Saturn, 8.9-6.1+19 ×104 cm-2 s-1 to Uranus, and 7.5-5.1+16 ×105 cm-2 s-1 to Neptune. The fate of the ablated oxygen depends in part on the molecular/atomic form of the initially delivered products, and on the altitude at which it was deposited. The dominant stratospheric products are CO, H2O, and CO2, which are relatively stable photochemically. Model-data comparisons suggest that interplanetary dust grains deliver an important component of the external oxygen to Jupiter and Uranus but fall far short of the amount needed to explain the CO abundance currently seen in the middle stratospheres of Saturn and Neptune. Our results are consistent with the theory that all of the giant planets have experienced large cometary impacts within the last few hundred years. Our results also suggest that the low background H2O abundance in Jupiter's stratosphere is indicative of effective conversion of meteoric oxygen to CO during or immediately after the ablation process - photochemistry alone cannot efficiently convert the H2O into CO on the giant planets.

Spectroscopic studies of non-volatile residue formed by photochemistry of solid C4N2: A model of condensed aerosol formation on Titan

NASA Astrophysics Data System (ADS)

Couturier-Tamburelli, Isabelle; Gudipati, Murthy S.; Lignell, Antti; Jacovi, Ronen; Piétri, Nathalie

2014-05-01

Following our recent communication (Gudipati, M.S. et al. [2013]. Nat. Commun. 4, 1648. http://dx.doi.org/10.1038/ncomms2649) on the discovery of condensed-phase non-volatile polymeric material with similar spectral features as tholins, we present here a comprehensive spectroscopic study of photochemical formation of polymeric material from condensed dicyanoacetylene (C4N2) ice films. C4N2 is chosen as starting material for the laboratory simulations because of the detection of this and similar molecules (nitriles and cyanoacetylenes) in Titan’s atmosphere. UV-Vis and infrared spectra obtained during long-wavelength (>300 nm) photon irradiation and subsequent warming of the ice films are used to analyze changes in C4N2 ice, evolution of tholins, and derive photopolymerization mechanisms. Our data analysis revealed that many processes occur during the photolysis of condensed Titan’s aerosol analogs, including isomerization and polymerization leading to the formation of long-chain as well as aromatic cyclic polymer molecules. In the light of tremendous new data from the Cassini mission on the seasonal variations in Titan’s atmosphere, our laboratory study and its results provide fresh insight into the formation and evolution of aerosols and haze in Titan’s atmosphere.

Quinone Photoreactivity: An Undergraduate Experiment in Photochemistry

ERIC Educational Resources Information Center

Vaughan, Pamela P.; Cochran, Michael; Haubrich, Nicole

2010-01-01

An experiment exploring the photochemical properties of quinones was developed. Their unique photochemistry and highly reactive nature make them an ideal class of compounds for examining structure-activity relationships. For several substituted quinones, photochemical reactivity was related to structure and ultimately to the Gibbs energy for…

The Effect of Aerosols on Pluto's C2 Hydrocarbon Chemistry

NASA Astrophysics Data System (ADS)

Luspay-Kuti, Adrienn; Mandt, Kathleen; Jessup, Kandis-Lea; Hue, Vincent; Kammer, Joshua; Filwett, Rachael; Hamel, Mark

2017-10-01

On July 14, 2015 the New Horizons spacecraft flew through the Pluto system, providing critical details about Pluto’s atmosphere. The vertical profiles of N2 and CH4, C2H2, C2H4, and C2H6 derived from New Horizons Alice transmission data allow the more accurate modeling of Pluto’s atmosphere than in the pre-New Horizons era, and help better understand the physical and photochemical processes in Pluto’s atmosphere. All the measured C2 hydrocarbon densities showed an unexpected inversion between ~100 and 400 km, which suggests that processes other than chemistry play an important role in shaping their vertical profiles. We present here a state-of-the-art Pluto Ion-Neutral-Photochemistry (Pluto INP) model that includes the condensation onto and incorporation into aerosol particles, and evaluate the dominant production and loss processes of C2 hydrocarbons with a special emphasis on the role of aerosol interaction. We found that in order to reproduce the C2 profiles measured by New Horizons, they must stick to and be permanently removed by aerosols - a process different from condensation. We determined through empirical fits to the New Horizons data that the sticking efficiency of C2 hydrocarbons and the stickiness of the aerosol particles are inversely related to the available aerosol surface area, which has been inferred from observation to increase as altitude decreases. This counterintuitive relationship between sticking efficiency and available aerosol surfaces indicates that similarly to Titan, Pluto’s aerosols must harden and become less sticky as they age. Such hardening with ageing is both necessary and sufficient to explain the vertical profiles of C2 hydrocarbons in Pluto’s atmosphere.

Kinetics and Photochemistry of Ruthenium Bisbipyridine Diacetonitrile Complexes: An Interdisciplinary Inorganic and Physical Chemistry Laboratory Exercise.

PubMed

Rapp, Teresa L; Phillips, Susan R; Dmochowski, Ivan J

2016-12-13

The study of ruthenium polypyridyl complexes can be widely applied across disciplines in the undergraduate curriculum. Ruthenium photochemistry has advanced many fields including dye-sensitized solar cells, photoredox catalysis, light-driven water oxidation, and biological electron transfer. Equally promising are ruthenium polypyridyl complexes that provide a sterically bulky, photolabile moiety for transiently "caging" biologically active molecules. Photouncaging involves the use of visible (1-photon) or near-IR (2-photon) light to break one or more bonds between ruthenium and coordinated ligand(s), which can occur on short time scales and in high quantum yields. In this work we demonstrate the use of a model "caged" acetonitrile complex, Ru(2,2'-bipyridine) 2 (acetonitrile) 2 , or RuMeCN in an advanced synthesis and physical chemistry laboratory. Students made RuMeCN in an advanced synthesis laboratory course and performed UV-vis spectroscopy and electrochemistry. The following semester students investigated RuMeCN photolysis kinetics in a physical chemistry laboratory. These two exercises may also be combined to create a 2-week module in an advanced undergraduate laboratory course.

Kinetics and Photochemistry of Ruthenium Bisbipyridine Diacetonitrile Complexes: An Interdisciplinary Inorganic and Physical Chemistry Laboratory Exercise

PubMed Central

2016-01-01

The study of ruthenium polypyridyl complexes can be widely applied across disciplines in the undergraduate curriculum. Ruthenium photochemistry has advanced many fields including dye-sensitized solar cells, photoredox catalysis, light-driven water oxidation, and biological electron transfer. Equally promising are ruthenium polypyridyl complexes that provide a sterically bulky, photolabile moiety for transiently “caging” biologically active molecules. Photouncaging involves the use of visible (1-photon) or near-IR (2-photon) light to break one or more bonds between ruthenium and coordinated ligand(s), which can occur on short time scales and in high quantum yields. In this work we demonstrate the use of a model “caged” acetonitrile complex, Ru(2,2′-bipyridine)2(acetonitrile)2, or RuMeCN in an advanced synthesis and physical chemistry laboratory. Students made RuMeCN in an advanced synthesis laboratory course and performed UV–vis spectroscopy and electrochemistry. The following semester students investigated RuMeCN photolysis kinetics in a physical chemistry laboratory. These two exercises may also be combined to create a 2-week module in an advanced undergraduate laboratory course. PMID:28649139

Research | Chemistry and Nanoscience Research | NREL

Science.gov Websites

organic batteries Hydrogen and Fuel Cells Fuel cells Testing and fabrication Hydrogen production H2@Scale Photovoltaics Organic photovoltaics Perovskites Quantum dot solar cells Dynamic windows Solar Photochemistry

The Effect of Copper and Selenium Nanocarboxylates on Biomass Accumulation and Photosynthetic Energy Transduction Efficiency of the Green Algae Chlorella Vulgaris

NASA Astrophysics Data System (ADS)

Mykhaylenko, Natalia F.; Zolotareva, Elena K.

2017-02-01

Nanoaquachelates, the nanoparticles with the molecules of water and/or carboxylic acids as ligands, are used in many fields of biotechnology. Ultra-pure nanocarboxylates of microelements are the materials of spatial perspective. In the present work, the effects of copper and selenium nanoaquachelates carboxylated with citric acid on biomass accumulation of the green algae Chlorella vulgaris were examined. Besides, the efficiency of the reactions of the light stage of photosynthesis was estimated by measuring chlorophyll a fluorescence. The addition of 0.67-4 mg L-1 of Cu nanocarboxylates resulted in the increase in Chlorella biomass by ca. 20%; however, their concentrations ranging from 20 to 40 mg L-1 strongly inhibited algal growth after the 12th day of cultivation. Se nanocarboxylates at 0.4-4 mg L-1 concentrations also stimulated the growth of C. vulgaris, and the increase in biomass came up to 40-45%. The addition of Se nanocarboxylates at smaller concentrations (0.07 or 0.2 mg L-1) at first caused the retardation of culture growth, but that effect disappeared after 18-24 days of cultivation. The addition of 2-4 mg L-1 of Cu nanocarboxylates or 0.4-4 mg L-1 of Se nanocarboxylates caused the evident initial increase in such chlorophyll a fluorescence parameters as maximal quantum yield of photosystem II photochemistry ( F v/ F m) and the quantum yield of photosystem II photochemistry in the light-adapted state ( F v'/ F m'). Photochemical fluorescence quenching coefficients declined after 24 days of growth with Cu nanocarboxylates, but they increased after 6 days of the addition of 2 or 4 mg L-1 Se nanocarboxylates. Those alterations affected the overall quantum yield of the photosynthetic electron transport in photosystem II.

Kinetics and Photochemistry of Ruthenium Bisbipyridine Diacetonitrile Complexes: An Interdisciplinary Inorganic and Physical Chemistry Laboratory Exercise

ERIC Educational Resources Information Center

Rapp, Teresa L.; Phillips, Susan R.; Dmochowski, Ivan J.

2016-01-01

The study of ruthenium polypyridyl complexes can be widely applied across disciplines in the undergraduate curriculum. Ruthenium photochemistry has advanced many fields including dye-sensitized solar cells, photoredox catalysis, lightdriven water oxidation, and biological electron transfer. Equally promising are ruthenium polypyridyl complexes…

Acquisition of a Nanosecond Laser Flash Photolysis Spectrometer to Enhance Understanding of Photochemistry and Reaction Kinetics in Undergraduate Research/Curriculum

DTIC Science & Technology

2016-03-31

photolysis # Compound # Compound 1 1,4-Dinitrobenzene 9 Azulene 2 1,2-Dinitrobenzene 10 4-Cyanophenol 3 Ferrocene 11 2-Nitrotoluene 4 4-Phenylphenol 12...Anthracene 4-Hydroxy-3-methoxybenzoic acid Cyclohexane Dithieno[3,2-b:2’,3’-d] thiophene Ferrocene Dimthylaniline Benzene 1,4- Diazabicyclo[2.2.2

Transient isomers in the photodissociation of bromoiodomethane

NASA Astrophysics Data System (ADS)

Marcellini, Moreno; Nasedkin, Alexandr; Zietz, Burkhard; Petersson, Jonas; Vincent, Jonathan; Palazzetti, Federico; Malmerberg, Erik; Kong, Qingyu; Wulff, Michael; van der Spoel, David; Neutze, Richard; Davidsson, Jan

2018-04-01

The photochemistry of halomethanes is fascinating for the complex cascade reactions toward either the parent or newly synthesized molecules. Here, we address the structural rearrangement of photodissociated CH2IBr in methanol and cyclohexane, probed by time-resolved X-ray scattering in liquid solution. Upon selective laser cleavage of the C-I bond, we follow the reaction cascade of the two geminate geometrical isomers, CH2I-Br and CH2Br-I. Both meta-stable isomers decay on different time scales, mediated by solvent interaction, toward the original parent molecule. We observe the internal rearrangement of CH2Br-I to CH2I-Br in cyclohexane by extending the time window up to 3 μs. We track the photoproduct kinetics of CH2Br-I in methanol solution where only one isomer is observed. The effect of the polarity of solvent on the geminate recombination pathways is discussed.

Photochemistry of Fe(Iii)-Carboxylates in Polysaccharide-Based Materials with Tunable Mechanical Properties

NASA Astrophysics Data System (ADS)

Giammanco, Giuseppe E.

We present the formulation and study of light-responsive materials based on carboxylate-containing polysaccharides. The functional groups in these natural polymers allow for strong interactions with transition metal ions such as Fe(III). The known photochemistry of hydroxycarboxylic acids in natural waters inspired us in exploring the visible light induced photochemistry of the carboxylates in these polysaccharides when coordinated to Fe(III) ions. Described in this dissertation are the design and characterization of the Fe(III)-polysaccharide materials, specifically the mechanistic aspects of the photochemistry and the effects that these reactions have on the structure of the polymer materials. We present a study of the quantitative photochemistry of different polysaccharide systems, where the presence of uronic acids was important for the photoreaction to take place. Alginate (Alg), pectate (Pec), hyaluronic acid (Hya), xanthan gum (Xan), and a polysaccharide extracted from the Noni fruit (NoniPs), were among the natural uronic acid-containing polysaccharide (UCPS) systems we analyzed. Potato starch, lacking of uronate groups, did not present any photochemistry in the presence of Fe(III); however, we were able to induce a photochemical response in this polysaccharide upon chemical manipulation of its functional groups. Important structure-function relationships were drawn from this study. The uronate moiety present in these polysaccharides is then envisioned as a tool to induce response to light in a variety of materials. Following this approach, we report the formulation of materials for controlled drug release, able to encapsulate and release different drug models only upon illumination with visible light. Furthermore, hybrid hydrogels were prepared from UPCS and non-responsive polymers. Different properties of these materials could be tuned by controlling the irradiation time, intensity and location. These hybrid gels were evaluated as scaffolds for tissue engineering showing great promise, as changes in the behavior of the growing cells were observed as a result of the photochemical treatment of the material. We present these natural and readily available, polysaccharide-based, metal-coordination materials as convenient building blocks in the formulation of new stimuli responsive materials. The photochemical methods developed here can be used as convenient tools for creating advanced materials with tailored patterns and gradients of mechanical properties.

Low-Temperature Hydrocarbon Photochemistry: CH3 + CH3 Recombination in Giant Planet Atmospheres

NASA Technical Reports Server (NTRS)

Smith, Gregory P.; Huestis, David L.

2002-01-01

Planetary emissions of the methyl radical CH3 were observed for the first time in 1998 on Saturn and Neptune by the ISO (Infrared Space Observatory) mission satellite. CH3 is produced by VUV photolysis of CH4 and is the key photochemical intermediate leading complex organic molecules on the giant planets and moons. The CH3 emissions from Saturn were unexpectedly weak. A suggested remedy is to increase the rate of the recombination reaction CH3 + CH3 + H2 --> C2H6 + H2 at 140 K to a value at least 10 times that measured at room temperature in rare gases, but within the range of disagreeing theoretical expressions at low temperature. We are performing laboratory experiments at low temperature and very low pressure. The experiments are supported by RRKM theoretical modeling that is calibrated using the extensive combustion literature.

Side Group Addition to the PAH Coronene by UV Photolysis in Cosmic Ice Analogs

NASA Technical Reports Server (NTRS)

Bernstein, Max P.; Elsila, Jamie E.; Dworkin, Jason P.; Sandford, Scott A.; Allamandola, Louis J.; Zare, Richard N.; DeVincenzi, D. (Technical Monitor)

2002-01-01

Ultraviolet photolysis of various ice mixtures at low temperature and pressure caused the addition of amino (-NH2), methyl (-CH3), methoxy (-OCH3), and cyano (-CN) functional groups to the polycyclic aromatic hydrocarbon (PAH) coronene (C22H12). The implications of these results for interstellar and meteoritic chemistry are discussed. Previously only simple PAH photo-oxidation had been reported. This work represents the first experimental evidence that ice photochemistry may have contributed to aromatics bearing carbon and nitrogen containing side groups that are detected in primitive meteorites and interplanetary dust particles. Furthermore, these results suggest a wider range of modified PAHs should be expected in interstellar lees and materials predating solar system formation.

Solution and solid trinitrotoluene (TNT) photochemistry: persistence of TNT-like ultraviolet (UV) resonance Raman bands.

PubMed

Gares, Katie L; Bykov, Sergei V; Godugu, Bhaskar; Asher, Sanford A

2014-01-01

We examined the 229 nm deep-ultraviolet resonance Raman (DUVRR) spectra of solution and solid-state trinitrotoluene (TNT) and its solution and solid-state photochemistry. Although TNT photodegrades with a solution quantum yield of ϕ ∼ 0.015, the initial photoproducts show DUVRR spectra extraordinarily similar to pure TNT, due to the similar photoproduct enhancement of the -NO2 stretching vibrations. This results in TNT-like DUVRR spectra even after complete TNT photolysis. These ultraviolet resonance Raman spectral bands enable DUVRR of trace as well as DUVRR standoff TNT detection. We determined the structure of various initial TNT photoproducts by using liquid chromatography-mass spectrometry and tandem mass spectrometry. Similar TNT DUVRR spectra and photoproducts are observed in the solution and solid states.

Interactions Between Temperature and Intercellular CO2 Concentration in Controlling Leaf Isoprene Emission Rates

NASA Technical Reports Server (NTRS)

Monson, Russell K.; Neice, Amberly A.; Trahan, Nicole A.; Shiach, Ian; McCorkel, Joel T.; Moore, David J. P.

2016-01-01

Plant isoprene emissions have been linked to several reaction pathways involved in atmospheric photochemistry. Evidence exists from a limited set of past observations that isoprene emission rate (I(sub s)) decreases as a function of increasing atmospheric CO2 concentration, and that increased temperature suppresses the CO2 effect. We studied interactions between intercellular CO2 concentration (C(sub I)) and temperature as they affect I(sub s) in field-grown hybrid poplar trees in one of the warmest climates on earth - the Sonoran Desert of the southwestern United States. We observed an unexpected midsummer down regulation of I(sub s) despite the persistence of relatively high temperatures. High temperature suppression of the I(sub s):C(sub I) relation occurred at all times during the growing season, but sensitivity of I(sub s) to increased C(sub I) was greatest during the midsummer period when I(subs) was lowest. We interpret the seasonal down regulation of I(sub s) and increased sensitivity of I(sub s) to C(sub I) as being caused by weather changes associated with the onset of a regional monsoon system. Our observations on the temperature suppression of the I(sub s):C(sub I) relation are best explained by the existence of a small pool of chloroplastic inorganic phosphate, balanced by several large, connected metabolic fluxes, which together, determine the C(sub I) and temperature dependencies of phosphoenolpyruvate import into the chloroplast.

Laboratory observations of the photochemistry of parent molecules: A review

NASA Technical Reports Server (NTRS)

Jackson, W. M.

1976-01-01

The photochemistry of possible parent molecules of comets has been reviewed. Quantum yields for many of the primary processes are unknown. Energy partitioning among the fragments has not been extensively investigated. A few of the studies have been performed as a function of the number of collisions that the excited molecules undergo, so that possible differences that may occur in a cometary environment may be ascertained.

Impacts of Brown Carbon from Biomass Burning on Surface UV and Ozone Photochemistry in the Amazon Basin

NASA Technical Reports Server (NTRS)

Mok, Jungbin; Krotkov, Nickolay A.; Arola, Antti; Torres, Omar; Jethva, Hiren; Andrade, Marcos; Labow, Gordon; Eck, Thomas F.; Li, Zhangqing; Dickerson, Russell R.;

Impacts of brown carbon from biomass burning on surface UV and ozone photochemistry in the Amazon Basin.

PubMed

Mok, Jungbin; Krotkov, Nickolay A; Arola, Antti; Torres, Omar; Jethva, Hiren; Andrade, Marcos; Labow, Gordon; Eck, Thomas F; Li, Zhanqing; Dickerson, Russell R; Stenchikov, Georgiy L; Osipov, Sergey; Ren, Xinrong

2016-11-11

The spectral dependence of light absorption by atmospheric particulate matter has major implications for air quality and climate forcing, but remains uncertain especially in tropical areas with extensive biomass burning. In the September-October 2007 biomass-burning season in Santa Cruz, Bolivia, we studied light absorbing (chromophoric) organic or "brown" carbon (BrC) with surface and space-based remote sensing. We found that BrC has negligible absorption at visible wavelengths, but significant absorption and strong spectral dependence at UV wavelengths. Using the ground-based inversion of column effective imaginary refractive index in the range 305-368 nm, we quantified a strong spectral dependence of absorption by BrC in the UV and diminished ultraviolet B (UV-B) radiation reaching the surface. Reduced UV-B means less erythema, plant damage, and slower photolysis rates. We use a photochemical box model to show that relative to black carbon (BC) alone, the combined optical properties of BrC and BC slow the net rate of production of ozone by up to 18% and lead to reduced concentrations of radicals OH, HO 2 , and RO 2 by up to 17%, 15%, and 14%, respectively. The optical properties of BrC aerosol change in subtle ways the generally adverse effects of smoke from biomass burning.

Acrylonitrile characterization and high energetic photochemistry at Titan temperatures

NASA Astrophysics Data System (ADS)

Toumi, A.; Piétri, N.; Chiavassa, T.; Couturier-Tamburelli, I.

2016-05-01

Laboratory infrared spectra of amorphous and crystalline acrylonitrile (C2H3CN) ices were recorded between 4000 and 650 cm-1. Heating up the acrylonitrile sample to 160 K shows details on the transition between amorphous and crystalline ice at ∼94 K. This molecule can be used as an indicator of the surface temperature of Titan since it is known also to be ∼94 K. The desorption energy of acrylonitrile was determined using two methods (IRTF and mass spectrometries) to be around 35 kJ mol-1. Solid phase acrylonitrile was irradiated with vacuum ultraviolet (VUV) light at low temperatures (20, 70, 95 and 130 K) using a microwave-discharge hydrogen flow lamp. Isoacrylonitrile, cyanoacetylene (HC3N), isocyanoacetylene (HC2NC), acetylene (C2H2) and hydrogen cyanide (HCN) were identified as photoproducts by using FTIR spectroscopy. The branching ratio of each pathway has been calculated for the different temperatures. We have estimated the acrylonitrile, HCN and HC3N νCtbnd N stretching band strengths to be respectively A = 3.98 ×10-18 , A = 1.38 ×10-18 and A = 2.92 ×10-18cmmolecule-1 .

Origin of Coverage Dependence in Photoreactivity of Carboxylate on TiO2(110): Hindering by Charged Coadsorbed Hydroxyls

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Zhitao; Henderson, Michael A.; Lyubinetsky, Igor

2015-09-30

The influence of reactant coverage on photochemical activity was explored using scanning tunneling microscopy (STM) and ultraviolet photoelectron spectroscopy (UPS). We observed diminished reactivity of carboxylate species (trimethyl acetate, TMA) on TiO2(110) as a function of increasing coverage. This effect was not linked to intermolecular interactions of TMA but to the accumulation of the coadsorbed bridging hydroxyls (HOb) deposited during (thermal) dissociative adsorption of the parent, trimethylacetic acid (TMAA). Confirmation of the hindering influence of HOb groups was obtained by the observation that HOb species originated from H2O dissociation at O-vacancy sites have a similar hindering effect on TMA photochemistry.more » Though HOb’s are photoinactive on TiO2(110) under ultrahigh vacuum conditions, UPS results show that these sites trap photoexcited electrons, which in turn likely (electrostatically) attract and neutralize photoexcited holes, thus suppressing the hole-mediated photoreactivity of TMA. This negative influence of surface hydroxyls on hole-mediated photochemistry is likely a major factor in other anaerobic photochemical processes on reducible oxide surfaces.« less

Developing Tighter Constraints on Exoplanet Biosignatures by Modeling Atmospheric Haze

NASA Astrophysics Data System (ADS)

Felton, R.; Neveu, M.; Domagal-Goldman, S. D.; Desch, S. J.; Arney, G. N.

2017-12-01

As we increase our capacity to resolve the atmospheric composition of exoplanets, we must continue to refine our ability to distinguish true biosignatures from false positives in order to ultimately distinguish a life-bearing from a lifeless planet. Of the possible true and false biosignatures, methane (CH4) and carbon dioxide (CO2) are of interest, because on Earth geological and biological processes can produce them on large scales. To identify a biotic, Earth-like exoplanet, we must understand how these biosignatures shape their atmospheres. High atmospheric abundances of CH4 produce photochemical organic haze, which dramatically alters the photochemistry, climate, and spectrum of a planet. Arney et al. (2017) have suggested that haze-bearing atmospheres rich in CO2 may be a type of biosignature because the CH4 flux required to produce the haze is similar to the amount of biogenic CH4 on modern Earth. Atmospheric CH4 and CO2 both affect haze-formation photochemistry, and the potential for hazes to form in Earth-like atmospheres at abiotic concentrations of these gases has not been well studied. We will explore a wide range of parameter space of abiotic concentration levels of these gases to determine what spectral signatures are possible from abiotic environments and look for measurable differences between abiotic and biotic atmospheres. We use a 1D photochemical model with an upgraded haze production mechanism to compare Archean and modern Earth atmospheres to abiotic versions while varying atmospheric CH4 and CO2 levels and atmospheric pressure. We will vary CO2 from a trace gas to an amount such that it dominates atmospheric chemistry. For CH4, there is uncertainty regarding the amount of abiotic CH4 that comes from serpentinizing systems. To address this uncertainty, we will model three cases: 1) assume all CH4 comes from photochemistry; 2) use estimates of modern-day serpentinizing fluxes, assuming they are purely abiotic; and 3) assume serpentinizing systems saturate oceans with methane.

Developing Tighter Constraints on Exoplanet Biosignatures by Modeling Atmospheric Haze

NASA Astrophysics Data System (ADS)

Felton, Ryan; Neveu, Marc; Domagal-Goldman, Shawn David; Desch, Steven; Arney, Giada

2018-01-01

As we increase our capacity to resolve the atmospheric composition of exoplanets, we must continue to refine our ability to distinguish true biosignatures from false positives in order to ultimately distinguish a life-bearing from a lifeless planet. Of the possible true and false biosignatures, methane (CH4) and carbon dioxide (CO2) are of interest, because on Earth geological and biological processes can produce them on large scales. To identify a biotic, Earth-like exoplanet, we must understand how these biosignatures shape their atmospheres. High atmospheric abundances of CH4 produce photochemical organic haze, which dramatically alters the photochemistry, climate, and spectrum of a planet. Arney et al. (2017) have suggested that haze-bearing atmospheres rich in CO2 may be a type of biosignature because the CH4 flux required to produce the haze is similar to the amount of biogenic CH4 on modern Earth. Atmospheric CH4 and CO2 both affect haze-formation photochemistry, and the potential for hazes to form in Earth-like atmospheres at abiotic concentrations of these gases has not been well studied. We will explore a wide range of parameter space of abiotic concentration levels of these gases to determine what spectral signatures are possible from abiotic environments and look for measurable differences between abiotic and biotic atmospheres. We use a 1D photochemical model with an upgraded haze production mechanism to compare Archean and modern Earth atmospheres to abiotic versions while varying atmospheric CH4 and CO2 levels and atmospheric pressure. We will vary CO2 from a trace gas to an amount such that it dominates atmospheric chemistry. For CH4, there is uncertainty regarding the amount of abiotic CH4 that comes from serpentinizing systems. To address this uncertainty, we will model three cases: 1) assume all CH4 comes from photochemistry; 2) use estimates of modern-day serpentinizing fluxes, assuming they are purely abiotic; and 3) assume serpentinizing systems saturate oceans with methane.

Substrate driven photochemistry of CdSe quantum dot films: charge injection and irreversible transformations on oxide surfaces.

PubMed

Tvrdy, Kevin; Kamat, Prashant V

2009-04-23

The photochemical behavior of CdSe quantum dots anchored to different surfaces was probed through their deposition on glass, SiO2, and TiO2 films. Following visible light irradiation under ambient conditions, CdSe quantum dots deposited on semiconducting TiO2 surface degraded, where no such degradation was observed when deposited on inert SiO2 surface or glass. Fluorescence decay and transient absorption experiments confirmed that charge injection from excited CdSe into TiO2 occurs with an apparent rate constant of 5.62 x 10(8) s(-1) and is the primary event responsible for photodegradation. In the presence of air, injected electrons are scavenged by surface adsorbed oxygen leaving behind reactive holes which induce anodic corrosion of CdSe quantum dots. In a vacuum environment, minimal CdSe degradation was observed as electron scavenging by oxygen is replaced with charge recombination between injected electrons and holes in CdSe nanocrystals. Spectroscopic measurements presented in this study highlight the role of both substrate and medium in dictating the photochemistry of CdSe quantum dots.

Provenance effect on carbon assimilation, photochemistry and leaf morphology in Mediterranean Cistus species under chilling stress.

PubMed

Puglielli, G; Cuevas Román, F J; Catoni, R; Moreno Rojas, J M; Gratani, L; Varone, L

2017-07-01

The potential resilience of shrub species to environmental change deserves attention in those areas threatened by climate change, such as the Mediterranean Basin. We asked if leaves produced under different climate conditions through the winter season to spring can highlight the leaf traits involved in determining potential resilience of three Cistus spp. to changing environmental conditions and to what extent intraspecific differences affect such a response. We analysed carbon assimilation, maximum quantum efficiency of PSII photochemistry (F v /F m ) and leaf morphological control of the photosynthetic process in leaves formed through the winter season into spring in C. creticus subsp. eriocephalus (CE), C. salvifolius (CS) and C. monspeliensis (CM) grown from seed of different provenances under common garden conditions. Intraspecific differences were found in F v /F m for CE and CS. Carbon assimilation-related parameters were not affected by provenance. Moreover, our analysis highlighted that the functional relationships investigated can follow seasonal changes and revealed patterns originating from species-specific differences in LMA arising during the favourable period. Cistus spp. have great ability to modify the structure and function of their leaves in the mid-term in order to cope with changing environmental conditions. The F v /F m response to chilling reveals that susceptibility to photoinhibition is a trait under selection in Cistus species. Concerning carbon assimilation, differing ability to control stomatal opening was highlighted between species. Moreover, seasonal changes of the functional relationships investigated can have predictable consequences on species leaf turnover strategies. © 2017 German Botanical Society and The Royal Botanical Society of the Netherlands.

Solar UV Radiation and the Origin of Life on Earth

NASA Technical Reports Server (NTRS)

Heap, Sara R.; Hubeny, Ivan; Lanz, Thierry; Gaidos, Eric; Kasting, James; Fisher, Richard R. (Technical Monitor)

2000-01-01

We have started a comprehensive, interdisciplinary study of the influence of solar ultraviolet radiation on the atmosphere of of the early Earth. We plan to model the chemistry of the Earth atmosphere during its evolution, using observed UV flux distributions of early solar analogs as boundary conditions in photochemical models of the Earth's atmosphere. The study has four distinct but interlinked parts: (1) Establishing the radiation of the early Sun; (2) Determining the photochemistry of the early Earth's atmosphere; (3) Estimating the rates of H2 loss from the atmosphere; and (4) Ascertaining how sensitive is the photochemistry to the metallicity of the Sun. We are currently using STIS and EUVE to obtain high-quality far-UV and extreme-UV observations of three early-solar analogs. We will perform a detailed non-LTE study of each stars, and construct theoretical model photosphere, and an empirical model chromospheres, which can be used to extrapolate the continuum to the Lyman continuum region. Given a realistic flux distribution of the early Sun, we will perform photochemical modeling of weakly reducing primitive atmospheres to determine the lifetime and photochemistry of CH4. In particular, we will make estimates of the amount of CH4 present in the prebiotic atmosphere, and estimate the atmospheric CH4 concentration during the Late Archean (2.5-3.0 b.y. ago) and determine whether it would have been sufficiently abundant to help offset reduced solar luminosity at that time. Having obtained a photochemical model, we will solve for the concentrations of greenhouse gasses and important pre-biotic molecules, and perform a detailed radiative transfer calculations to compute the UV flux reaching the surface.

Does Cu(acac)2 Quench Benzene Fluorescence? A Physical Chemistry Experiment.

ERIC Educational Resources Information Center

Marciniak, Bronislaw

1986-01-01

Describes a laboratory experiment in which benzene fluorescence is quenched by bis(acetylacetonato) copper(II). Discusses how this experiment can demonstrate a special technique used in the field of photochemistry. Provides an outline of the experimental procedure and discusses its results. (TW)

Drought induced changes of leaf-to-root relationships in two tomato genotypes.

PubMed

Moles, Tommaso Michele; Mariotti, Lorenzo; De Pedro, Leandro Federico; Guglielminetti, Lorenzo; Picciarelli, Piero; Scartazza, Andrea

2018-07-01

Water deficit triggers a dynamic and integrated cross-talk between leaves and roots. Tolerant plants have developed several physiological and molecular mechanisms to establish new cell metabolism homeostasis, avoiding and/or escaping from permanent impairments triggered by drought. Two tomato genotypes (a Southern Italy landrace called Ciettaicale and the well-known commercial cultivar Moneymaker) were investigated at vegetative stage to assess leaf and root metabolic strategies under 20 days of water deficit. Physiological and metabolic changes, in terms of ABA, IAA, proline, soluble sugars and phenols contents, occurred in both tomato genotypes under water stress. Overall, our results pointed out the higher plasticity of Ciettaicale to manage plant water status under drought in order to preserve the source-sink relationships. This aim was achieved by maintaining a more efficient leaf photosystem II (PSII) photochemistry, as suggested by chlorophyll fluorescence parameters, associated with a major investment towards root growth and activity to improve water uptake. On the contrary, the higher accumulation of carbon compounds, resulting from reduced PSII photochemistry and enhanced starch reserve mobilization, in leaves and roots of Moneymaker under drought could play a key role in the osmotic adjustment, although causing a feedback disruption of the source-sink relations. This hypothesis was also supported by the different drought-induced redox unbalance, as suggested by H 2 O 2 and MDA contents. This could affect both PSII photochemistry and root activity, leading to a major involvement of NPQ and antioxidant system in response to drought in Moneymaker than Ciettaicale. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

Oxygen isotope anomaly in tropospheric CO2 and implications for CO2 residence time in the atmosphere and gross primary productivity.

PubMed

Liang, Mao-Chang; Mahata, Sasadhar; Laskar, Amzad H; Thiemens, Mark H; Newman, Sally

2017-10-13

The abundance variations of near surface atmospheric CO 2 isotopologues (primarily 16 O 12 C 16 O, 16 O 13 C 16 O, 17 O 12 C 16 O, and 18 O 12 C 16 O) represent an integrated signal from anthropogenic/biogeochemical processes, including fossil fuel burning, biospheric photosynthesis and respiration, hydrospheric isotope exchange with water, and stratospheric photochemistry. Oxygen isotopes, in particular, are affected by the carbon and water cycles. Being a useful tracer that directly probes governing processes in CO 2 biogeochemical cycles, Δ 17 O (=ln(1 + δ 17 O) - 0.516 × ln(1 + δ 18 O)) provides an alternative constraint on the strengths of the associated cycles involving CO 2 . Here, we analyze Δ 17 O data from four places (Taipei, Taiwan; South China Sea; La Jolla, United States; Jerusalem, Israel) in the northern hemisphere (with a total of 455 measurements) and find a rather narrow range (0.326 ± 0.005‰). A conservative estimate places a lower limit of 345 ± 70 PgC year -1 on the cycling flux between the terrestrial biosphere and atmosphere and infers a residence time of CO 2 of 1.9 ± 0.3 years (upper limit) in the atmosphere. A Monte Carlo simulation that takes various plant uptake scenarios into account yields a terrestrial gross primary productivity of 120 ± 30 PgC year -1 and soil invasion of 110 ± 30 PgC year -1 , providing a quantitative assessment utilizing the oxygen isotope anomaly for quantifying CO 2 cycling.

Probing nitrobenzhydrol uncaging mechanisms using FerriCast.

PubMed

Kennedy, Daniel P; Brown, Daniel C; Burdette, Shawn C

2010-10-15

The FerriCast derivative FC-NDBF was synthesized from 3-methyl-2-nitrodibenzofuran (NDBF). The photochemistry of the target Fe(3+) photocage and several related congeners provides mechanistic insight into the uncaging quantum yields of nitrobenzhydrol-derived ligands.

Photochemical electron transfer in chlorophyll-porphyrin-quinone triads. The role of the porphyrin-bridging molecule

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, D.G.; Niemczyk, M.P.; Minsek, D.W.

1993-06-30

The photochemistry of four chlorophyll-porphyrin-naphthoquinone molecules possessing both fixed distances and orientations between the three components is described. These molecules consist of a methyl pyropheophorbide a or pyrochlorophyllide a that is directly bonded at its 3-position to the 5-position of a 2,8,12,18-tetraethyl-3,7,13,-17-tetramethylporphyrin, which is in turn bonded at its 15-position to a 2-triptycenenaphthoquinone. In addition, porphyrin-quinone compounds in which the chlorins are replaced by a p-tolyl group were also prepared as reference compounds. Selective metalation of the macrocycles with zinc gives the series ZCHPNQ, ZCZPNQ, HCZPNQ, HCHPNQ, HPNQ, and ZPNQ, where H, Z, C, P, and NQ denote free base,more » Zn derivative, chlorophyll, porphyrin, and naphthoquinone, respectively. Selective excitation of ZC in ZCZPNQ and ZCHPNQ, and HC in HCHPNQ dissolved in butyronitrile yields ZC[sup +]ZPNQ[sup [minus

Spectroscopic and computational studies of matrix-isolated iso-CHBr{sub 3}: Structure, properties, and photochemistry of iso-bromoform

DOE Office of Scientific and Technical Information (OSTI.GOV)

George, Lisa; Kalume, Aimable; Wagner, James

Iso-polyhalomethanes are known reactive intermediates that play a pivotal role in the photochemistry of halomethanes in condensed phases. In this work, iso-bromoform (iso-CHBr{sub 3}) and its deuterated isotopomer were characterized by matrix isolation infrared and UV/visible spectroscopy, supported by ab initio and density functional theory calculations, to further probe the structure, spectroscopy, and photochemistry of this important intermediate. Selected wavelength laser irradiation of CHBr{sub 3} isolated in Ar or Ne matrices at {approx}5 K yielded iso-CHBr{sub 3}; the observed infrared and UV/visible absorptions are in excellent agreement with computational predictions, and the energies of various stationary points on the CHBr{submore » 3} potential energy surface were characterized computationally using high-level methods in combination with correlation consistent basis sets. These calculations show that, while the corresponding minima lie {approx}200 kJ/mol above the global CHBr{sub 3} minimum, the isomer is bound by some 60 kJ/mol in the gas phase with respect to the CHBr{sub 2}+ Br asymptote. The photochemistry of iso-CHBr{sub 3} was investigated by selected wavelength laser irradiation into the intense S{sub 0}{yields} S{sub 3} transition, which resulted in back photoisomerization to CHBr{sub 3}. Intrinsic reaction coordinate calculations confirmed the existence of a first-order saddle point connecting the two isomers, which lies energetically below the threshold of the radical channel. Subsequently, natural bond orbital analysis and natural resonance theory were used to characterize the important resonance structures of the isomer and related stationary points, which demonstrate that the isomerization transition state represents a crossover from dominantly covalent to dominantly ionic bonding. In condensed phases, the ion-pair dominated isomerization transition state structure is preferentially stabilized, so that the barrier to isomerization is lowered.« less

History of Suction-Type Laminar-Flow Control with Emphasis on Flight Resrearch: Monographs in Aerospace History Number 13

NASA Technical Reports Server (NTRS)

Braslow, A. L.

1999-01-01

The paper contains the following sections: Foreword; Preface; Laminar-Flow Control Concepts and Scope of Monograph; Early Research on Suction-Type Laminar-Flow Control (Research from the 1930s through the War Years; Research from after World War II to the Mid-1960s); Post X-21 Research on Suction-Type Laminar-Flow Control; Status of Laminar-Flow Control Technology in the Mid-1990s; Glossary; Document 1-Aeronautics Panel, AACB, R&D Review, Report of the Subpanel on Aeronautic Energy Conservation/Fuels; Document 2-Report of Review Group on X-21A Laminar Flow Control Program; Document 3-Langley Research Center Announcement, Establishment of Laminar Flow Control Working Group; Document 4-Intercenter Agreement for Laminar Flow Control Leading Edge Glove Flights, LaRC and DFRC; Document 5-Flight Report NLF-144, of AFTIF-111 Aircraft with the TACT Wing Modified by a Natural Laminar Flow Glove; Document 6-Flight Record, F-16XL Supersonic Laminar Flow Control Aircraft; Index; and About the Author.

Photolysis of 4-Phenyl-1,3-dioxolan-2-one: An Undergraduate Experiment in Free Radical Chemistry.

ERIC Educational Resources Information Center

White, Rick C.; Ma, Sha

1988-01-01

Describes a photochemistry experiment designed to introduce photochemical techniques and experience free radical chemistry. Selects Nuclear Magnetic Resonance spectroscopy for the analysis. This activity is suggested for use in an upper level undergraduate organic course. (MVL)

Nanosecond step-scan FT-infrared absorption spectroscopy in photochemistry and catalysis

NASA Astrophysics Data System (ADS)

Frei, H.

1998-06-01

Time-resolved step-scan FT-IR absorption spectroscopy has been expanded to a resolution of 20 nanosecond. Following a description of the experimental set-up, applications in four research areas are presented. In the first project, we discuss a reversible isomerization, namely the bacteriorhodopsin photocycle. Main results are the discovery of 2 processes with distinct kinetics on the nanosecond time scale not detected by previous spectroscopic techniques, and observation of an instantaneous response of the protein environment to chromophore dynamics within the nanosecond laser pulse duration. In a second project, alkane C-H bond activation by a transition metal complex in room temperature solution is investigated and the first measurement of the formation of a C-H insertion product reported (alkyl hydride). Then, a nanosecond study of a pericyclic reaction, the ring-opening of cyclohexadiene, is discussed. The fourth example describes the first observation of a transient molecule in a zeolite matrix, a triplet excited quinone, by time-resolved infrared spectroscopy.

In-Situ Formation of Cobalt-Phosphate Oxygen-Evolving Complex-Anchored Reduced Graphene Oxide Nanosheets for Oxygen Reduction Reaction

PubMed Central

Zhao, Zhi-Gang; Zhang, Jing; Yuan, Yinyin; Lv, Hong; Tian, Yuyu; Wu, Dan; Li, Qing-Wen

2013-01-01

Oxygen conversion process between O2 and H2O by means of electrochemistry or photochemistry has lately received a great deal of attention. Cobalt-phosphate (Co-Pi) catalyst is a new type of cost-effective artificial oxygen-evolving complex (OEC) with amorphous features during photosynthesis. However, can such Co-Pi OEC also act as oxygen reduction reaction (ORR) catalyst in electrochemical processes? The question remains unanswered. Here for the first time we demonstrate that Co-Pi OEC does be rather active for the ORR. Particularly, Co-Pi OEC anchoring on reduced graphite oxide (rGO) nanosheet is shown to possess dramatically improved electrocatalytic activities. Differing from the generally accepted role of rGO as an “electron reservoir”, we suggest that rGO serves as “peroxide cleaner” in enhancing the electrocatalytic behaviors. The present study may bridge the gap between photochemistry and electrochemistry towards oxygen conversion. PMID:23877331

Solvent and substituent effects on the photochemistry of norbornadiene-diarylacetylene Pauson-Khand adducts.

PubMed

Ji, Yining; Verdaguer, Xavier; Riera, Antoni

2011-03-28

The photochemistry of Pauson-Khand cycloadducts of norbornadiene with a series of bis-aryl alkynes has been studied. Two types of photochemical transformation take place: photorearrangement to tricyclic ketones or photochemical 6π electrocyclization. High selectivity levels have been attained for each pathway, controlled by the polarity of the solvent, irradiation wavelength, and presence (or absence) of oxygen. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Internal Targeting and External Control: Phototriggered Targeting in Nanomedicine.

PubMed

Arrue, Lily; Ratjen, Lars

2017-12-07

The photochemical control of structure and reactivity bears great potential for chemistry, biology, and life sciences. A key feature of photochemistry is the spatiotemporal control over secondary events. Well-established applications of photochemistry in medicine are photodynamic therapy (PDT) and photopharmacology (PP). However, although both are highly localizable through the application of light, they lack cell- and tissue-specificity. The combination of nanomaterial-based drug delivery and targeting has the potential to overcome limitations for many established therapy concepts. Even more privileged seems the merger of nanomedicine and cell-specific targeting (internal targeting) controlled by light (external control), as it can potentially be applied to many different areas of medicine and pharmaceutical research, including the aforementioned PDT and PP. In this review a survey of the interface of photochemistry, medicine and targeted drug delivery is given, especially focusing on phototriggered targeting in nanomedicine. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterization of NOx, SO2, ethene, and propene from industrial emission sources in Houston, Texas

NASA Astrophysics Data System (ADS)

Washenfelder, R. A.; Trainer, M.; Frost, G. J.; Ryerson, T. B.; Atlas, E. L.; de Gouw, J. A.; Flocke, F. M.; Fried, A.; Holloway, J. S.; Parrish, D. D.; Peischl, J.; Richter, D.; Schauffler, S. M.; Walega, J. G.; Warneke, C.; Weibring, P.; Zheng, W.

2010-08-01

The Houston-Galveston-Brazoria urban area contains industrial petrochemical sources that emit volatile organic compounds and nitrogen oxides, resulting in rapid and efficient ozone production downwind. During September to October 2006, the NOAA WP-3D aircraft conducted research flights as part of the second Texas Air Quality Study (TexAQS II). We use measurements of NOx, SO2, and speciated hydrocarbons from industrial sources in Houston to derive source emission ratios and compare these to emission inventories and the first Texas Air Quality Study (TexAQS) in 2000. Between 2000 and 2006, NOx/CO2 emission ratios changed by an average of -29% ± 20%, while a significant trend in SO2/CO2 emission ratios was not observed. We find that high hydrocarbon emissions are routine for the isolated petrochemical facilities. Ethene (C2H4) and propene (C3H6) are the major contributors to ozone formation based on calculations of OH reactivity for organic species including C2-C10 alkanes, C2-C5 alkenes, ethyne, and C2-C5 aldehydes and ketones. Measured ratios of C2H4/NOx and C3H6/NOx exceed emission inventory values by factors of 1.4-20 and 1-24, respectively. We examine trends in C2H4/NOx and C3H6/NOx ratios between 2000 and 2006 for the isolated petrochemical sources and estimate a change of -30% ± 30%, with significant day-to-day and within-plume variability. Median ambient mixing ratios of ethene and propene in Houston show decreases of -52% and -48%, respectively, between 2000 and 2006. The formaldehyde, acetaldehyde, and peroxyacetyl nitrate products produced by alkene oxidation are observed downwind, and their time evolution is consistent with the rapid photochemistry that also produces ozone.

Research impact in the community-based health sciences: an analysis of 162 case studies from the 2014 UK Research Excellence Framework.

PubMed

Greenhalgh, Trisha; Fahy, Nick

2015-09-21

The 2014 UK Research Excellence Framework (REF2014) generated a unique database of impact case studies, each describing a body of research and impact beyond academia. We sought to explore the nature and mechanism of impact in a sample of these. The study design was manual content analysis of a large sample of impact case studies (producing mainly quantitative data), plus in-depth interpretive analysis of a smaller sub-sample (for qualitative detail), thereby generating both breadth and depth. For all 162 impact case studies submitted to sub-panel A2 in REF2014, we extracted data on study design(s), stated impacts and audiences, mechanisms of impact, and efforts to achieve impact. We analysed four case studies (selected as exemplars of the range of approaches to impact) in depth, including contacting the authors for their narratives of impact efforts. Most impact case studies described quantitative research (most commonly, trials) and depicted a direct, linear link between research and impact. Research was said to have influenced a guideline in 122 case studies, changed policy in 88, changed practice in 84, improved morbidity in 44 and reduced mortality in 25. Qualitative and participatory research designs were rare, and only one case study described a co-production model of impact. Eighty-two case studies described strong and ongoing linkages with policymakers, but only 38 described targeted knowledge translation activities. In 40 case studies, no active efforts to achieve impact were described. Models of good implementation practice were characterised by an ethical commitment by researchers, strong institutional support and a proactive, interdisciplinary approach to impact activities. REF2014 both inspired and documented significant efforts by UK researchers to achieve impact. But in contrast with the published evidence on research impact (which depicts much as occurring indirectly through non-linear mechanisms), this sub-panel seems to have captured mainly direct and relatively short-term impacts one step removed from patient outcomes. Limited impacts on morbidity and mortality, and researchers' relatively low emphasis on the processes and interactions through which indirect impacts may occur, are concerns. These findings have implications for multi-stakeholder research collaborations such as UK National Institute for Health Research Collaborations for Leadership in Applied Health Research and Care, which are built on non-linear models of impact.

STRATCOM-8 scientific objectives and mission orginization

NASA Technical Reports Server (NTRS)

Reed, E. I. (Compiler)

1977-01-01

Stratospheric photochemistry was studied, with emphasis on the Ozone-NOx-ultraviolet flux interactions, but also including members of the chlorine, water vapor, and carbon-containing families. Secondary objectives include: (1) study of the balloon environment, (2) comparison of independent measurements of ozone and of NO, (3) development of new sensor systems; and (4) some measurements for exploratory purposes. Most, but not all, systems and instruments performed as planned, and it is believed that data are available to achieve most of the planned scientific and engineering objectives. The emphasis on photochemistry in the 35 to 40 km region is greater than anticipated, and observations are more complete for sunset than for sunrise. The planned instruments and a summary of the flight operations is discussed partly for the mutual information of those participating and partly for the wider scientific community.

Photochemistry of fluorinated 4-iodophenylnitrenes: matrix isolation and spectroscopic characterization of phenylnitrene-4-yls.

PubMed

Grote, Dirk; Sander, Wolfram

2009-10-02

The photochemistry of a series of fluorinated p-iodophenyl azides 2 has been investigated using matrix isolation IR and EPR spectroscopy. In all cases, the corresponding phenylnitrenes 1 were formed as primary photoproducts. Further irradiation of the nitrenes 1 resulted in the formation of azirines 3, ketenimines 4, and nitreno radicals 5. The yield of 5 depends on the number of ortho fluorine substituents: with two ortho fluorine atoms the highest yield is observed, whereas without fluorine atoms the yield is too low for IR spectroscopic detection. The interconversion between the isomers 1, 3, and 4 proved to be rather complex. If the fluorine atoms are distributed unsymmetrically, two isomers of azirines 3 and ketenimines 4 can be formed. The yields of these isomers depend critically on the irradiation conditions.

Thermally and vibrationally induced conformational isomerizations, infrared spectra, and photochemistry of gallic acid in low-temperature matrices

NASA Astrophysics Data System (ADS)

Justino, Licínia L. G.; Reva, Igor; Fausto, Rui

2016-07-01

Near-infrared (near-IR) narrowband selective vibrational excitation and annealing of gallic acid (3,4,5-trihydroxybenzoic acid) isolated in cryogenic matrices were used to induce interconversions between its most stable conformers. The isomerizations were probed by infrared spectroscopy. An extensive set of quantum chemical calculations, carried out at the DFT(B3LYP)/6-311++G(d,p) level of approximation, was used to undertake a detailed analysis of the ground state potential energy surface of the molecule. This investigation of the molecule conformational space allowed extracting mechanistic insights into the observed annealing- or near-IR-induced isomerization processes. The infrared spectra of the two most stable conformers of gallic acid in N2, Xe, and Ar matrices were fully assigned. Finally, the UV-induced photochemistry of the matrix isolated compound was investigated.

Atmospherically Related Studies of O(D-1) and O2 (b'Sigma(sub g, sup +)

NASA Technical Reports Server (NTRS)

Slanger, Tom G.

1998-01-01

For the third year of the grant, we propose to investigate the (beta)'(Sigma)(sub g, sup +). Our earlier value of 0.77 +/- 0.23, which has been used for a long time, should be updated, and the error limits reduced. Current measurements in J. Barker's group at the University of Michigan have assigned a value closer to 0.9, and we will conduct a new evaluation. The goals of this project are to investigate various aspects of the photochemistry of O('D) and O2(beta)'(Sigma)(sub g, sup +) that are of relevance to the photochemistry and energy balance of the terrestrial atmosphere. Over the last six months, we have obtained new sky spectra data files from the Keck telescope via Don Osterbrock at UC Santa Cruz, and now 120 hours of data have been accumulated. Thus, we have been able to make large signal/noise improvements of the O2(b'(Sigma)(sub g, sup +) - X(sup 3)(Sigma)(Sub g, sup -) Atmospheric Band data that we are collecting.

Suboptimal care and perinatal mortality in ten European regions: methodology and evaluation of an international audit.

PubMed

Richardus, J H; Graafmans, W C; Bergsjø, P; Lloyd, D J; Bakketeig, L S; Bannon, E M; Borkent-Polet, M; Davidson, L L; Defoort, P; Leitão, A Esparteiro; Langhoff-Roos, J; Garcia, A Moral; Papantoniou, N E; Wennergren, M; Amelink-Verburg, M P; Verloove-Vanhorick, S P; Mackenbach, J P

2003-10-01

A European concerted action (the EuroNatal study) investigated differences in perinatal mortality between countries of Europe. This report describes the methods used in the EuroNatal international audit and discusses the validity of the results. Perinatal deaths between 1993 and 1998 in regions of ten European countries were identified. The categories of death chosen for the study were singleton fetal deaths at 28 or more weeks of gestational age, all intrapartum deaths at 28 or more weeks of gestational age and neonatal deaths at 34 or more weeks of gestational age. Deaths with major congenital anomalies were excluded. An international audit panel used explicit criteria to review all cases, which were blinded for region. Subjective interpretation was used in cases of events or interventions where explicit criteria did not exist. Suboptimal factors were identified in the antenatal, intrapartum and neonatal periods, and classified as 'maternal/social', due to 'infrastructure/service organization', or due to 'professional care delivery'. The contribution of each suboptimal factor to the fatal outcome was listed and consensus was reached on a final grade using a procedure that included correspondence and plenary meetings. In all regions combined, 90% of all known or estimated cases in the selected categories were included in the audit. In total, 1619 cases of perinatal death were audited. Consensus was reached in 1543 (95%) cases. In 75% of all cases, the grade was based on explicit criteria. In the remaining cases, consensus was reached within subpanels without reference to predefined criteria. There was reasonable to good agreement between and within subpanels, and within panel members. The international audit procedure proved feasible and led to consistent results. The results that relate to suboptimal care will need to be studied in depth in order to reach conclusions about their implications for assessing the quality of perinatal care in the individual regions.

An overview of MAP/GLOBUS NO(x)

NASA Technical Reports Server (NTRS)

Pommereau, J. P.

1989-01-01

GLOBUS NO(x) is a combined observation of nitrogen compounds by more than 20 experiments, from satellites, remote and in situ instruments on board balloons and ground observatories, within a short time period. Held in September 1985 above Southern France, the field campaign has been a technical success. Most of the observations were achieved as anticipated. NO, NO2 and relevant species and physical parameters involved in their photochemistry, were measured between 5 and 40 km at several periods of the day. A first step of data interpretation which consists of instrumental intercomparisons, is now achieved. Several systematic biases between data of various origins which have appeared in the past, are now understood and reduced. A second step which deals with atmospheric photochemistry issues like diurnal cycles and budget, is now on its way. It will be the object of a close exchange between experimenters involved in the campaign and modelers.

Photochemistry and photophysics of the amino and imino tautomers of 1-methylcytosine: tautomerisation as a side product of the radiationless decay.

PubMed

Li, Quansong; Blancafort, Lluís

2013-08-01

The photochemistry and photophysics of the amino-oxo (AO) and imino-oxo (IO) tautomers of 1-methylcytosine are investigated with ab initio calculations, using the CASPT2//CASSCF approach. Our aim is to rationalize recent experimental results which show that the AO tautomer has an excited state lifetime of about 1 ps, similar to cytosine (J.-W. Ho, H.-C. Yen, W.-K. Chou, C.-N. Weng, L.-H. Cheng, H.-Q. Shi, S.-H. Lai and P.-Y. Cheng, J. Phys. Chem. A, 2011, 115, 8406-8418), and that irradiation with wavelengths shorter than 308 nm induces the AO→IO tautomerization (I. Reva, M. J. Nowak, L. Lapinski and R. Fausto, J. Phys. Chem. B, 2012, 116, 5703-5710). For the canonical AO tautomer we find two analogous decay mechanisms to those described previously for cytosine, involving a conical intersection of ethylenic type and one where the amino group is bent out of plane. Decay through these intersections provides an unreactive return path to the AO ground state species. More importantly, we have identified new decay paths that lead from the two intersections to the trans-IO tautomer, without a barrier. These paths provide the possibility of forming the IO tautomer, presumably in small yields, as a side product of the radiationless decay. Thus, we have established for the first time computationally the mechanism of the UV-induced tautomerization, which is compatible with the well-established decay mechanism for cytosine. For the IO tautomer, we also find a mechanism for the excited state interconversion of the cis and trans forms and for efficient radiationless decay through a conical intersection where the imino group is perpendicular to the ring and bent out of the plane. These results are likely to be valid also for cytosine.

Exploring the nonequilibrium reactivity of molecules with platinum(111)

NASA Astrophysics Data System (ADS)

Dewitt, Kristin Marie

Various aspects of the nonequilibrium reactivity of several, catalytically important, small molecules with Pt(111)were explored. The effect of alkali metal promotion on the thermal chemistry and photochemistry of CH4,N 2, and CO2 was studied. Dissociative sticking coefficients for methane and ethane were measured as a function of gas temperature ( Tg) and surface temperature (Ts) using effusive molecular beam and angle-integrated gas dosing methods. Coupled with physisorbed complex microcanonical unimolecular rate theory these measurements provide a predictive understanding for the kinetics of these C-H bond activation reactions, i.e. allowing us to predict the sticking coefficient of CH 4 and C2H6 for any combination of T s and Tg. Work function thermal programmed desorption was used to examine the correlation between surface structure and surface work function for CH3Br and CO2. Preliminary two-photon photoemission and broad-band infrared-visible sum frequency generation experiments introduce these nonlinear spectroscopy techniques to the arsenal of surface characterization techniques available in our group. All of the disparate components of this work are tied together by one overall theme, developing an improved molecular-level understanding of the reaction dynamics of catalysis.

Wintertime ozone and nitrogen oxide photochemistry and nighttime chemistry in a Western oil and gas basin

NASA Astrophysics Data System (ADS)

Brown, S. S.; Edwards, P. M.; Patel, S.; Dube, W. P.; Williams, E. J.; Roberts, J. M.; McLaren, R.; Kercher, J. P.; Gilman, J. B.; Lerner, B. M.; Warneke, C.; Geiger, F.; De Gouw, J. A.; Tsai, C.; Stutz, J.; Young, C. J.; Washenfelder, R. A.; Parrish, D. D.

2012-12-01

Oil and gas development in mountain basins of the Western United States has led to frequent exceedences of National Ambient Air Quality Standards for ozone during the winter season. The Uintah Basin Winter Ozone Study took place during February and March 2012 in northeast Utah with the goal of providing detailed chemical and meteorological data to understand this phenomenon. Although snow and cold pool stagnation conditions that lead to winter ozone buildup were not encountered during the study period, the detailed measurements did provide a unique data set to understand the chemistry of key air pollutants in a desert environment during winter. This presentation will examine both the photochemistry and the nighttime chemistry of nitrogen oxides, ozone and VOCs, with the goal of understanding the observed photochemistry and its relationship to nighttime chemistry through a set of box models. The photochemical box model is based on the master chemical mechanism (MCM), a detailed model for VOC degradation and ozone production. The presentation will examine the sensitivity of ozone photochemistry to different parameters, including pollutant concentrations likely to be characteristic of cold pool conditions, and the strength of radical sources derived from heterogeneous chemical reactions. The goal of the analysis will be to identify the factors most likely to be responsible for the higher ozone events that have been observed during colder years with less detailed chemical measurements.

Formation of nitrogenated organic aerosols in the Titan upper atmosphere.

PubMed

Imanaka, Hiroshi; Smith, Mark A

2010-07-13

Many aspects of the nitrogen fixation process by photochemistry in the Titan atmosphere are not fully understood. The recent Cassini mission revealed organic aerosol formation in the upper atmosphere of Titan. It is not clear, however, how much and by what mechanism nitrogen is incorporated in Titan's organic aerosols. Using tunable synchrotron radiation at the Advanced Light Source, we demonstrate the first evidence of nitrogenated organic aerosol production by extreme ultraviolet-vacuum ultraviolet irradiation of a N(2)/CH(4) gas mixture. The ultrahigh-mass-resolution study with laser desorption ionization-Fourier transform-ion cyclotron resonance mass spectrometry of N(2)/CH(4) photolytic solid products at 60 and 82.5 nm indicates the predominance of highly nitrogenated compounds. The distinct nitrogen incorporations at the elemental abundances of H(2)C(2)N and HCN, respectively, are suggestive of important roles of H(2)C(2)N/HCCN and HCN/CN in their formation. The efficient formation of unsaturated hydrocarbons is observed in the gas phase without abundant nitrogenated neutrals at 60 nm, and this is confirmed by separately using (13)C and (15)N isotopically labeled initial gas mixtures. These observations strongly suggest a heterogeneous incorporation mechanism via short lived nitrogenated reactive species, such as HCCN radical, for nitrogenated organic aerosol formation, and imply that substantial amounts of nitrogen is fixed as organic macromolecular aerosols in Titan's atmosphere.

Formation of nitrogenated organic aerosols in the Titan upper atmosphere

PubMed Central

Imanaka, Hiroshi; Smith, Mark A.

2010-01-01

Many aspects of the nitrogen fixation process by photochemistry in the Titan atmosphere are not fully understood. The recent Cassini mission revealed organic aerosol formation in the upper atmosphere of Titan. It is not clear, however, how much and by what mechanism nitrogen is incorporated in Titan’s organic aerosols. Using tunable synchrotron radiation at the Advanced Light Source, we demonstrate the first evidence of nitrogenated organic aerosol production by extreme ultraviolet–vacuum ultraviolet irradiation of a N2/CH4 gas mixture. The ultrahigh-mass-resolution study with laser desorption ionization-Fourier transform-ion cyclotron resonance mass spectrometry of N2/CH4 photolytic solid products at 60 and 82.5 nm indicates the predominance of highly nitrogenated compounds. The distinct nitrogen incorporations at the elemental abundances of H2C2N and HCN, respectively, are suggestive of important roles of H2C2N/HCCN and HCN/CN in their formation. The efficient formation of unsaturated hydrocarbons is observed in the gas phase without abundant nitrogenated neutrals at 60 nm, and this is confirmed by separately using 13C and 15N isotopically labeled initial gas mixtures. These observations strongly suggest a heterogeneous incorporation mechanism via short lived nitrogenated reactive species, such as HCCN radical, for nitrogenated organic aerosol formation, and imply that substantial amounts of nitrogen is fixed as organic macromolecular aerosols in Titan’s atmosphere. PMID:20616074

Singlet Oxygen Production by Illuminated Road Dust and Winter Street Sweepings

NASA Astrophysics Data System (ADS)

Schneider, S.; Gan, L.; Gao, S.; Hoy, K. S.; Kwasny, J. R.; Styler, S. A.

2017-12-01

Road dust is an important urban source of primary particulate matter, especially in cities where sand and other traction materials are applied to roadways in winter. Although the composition and detrimental health effects of road dust are reasonably well characterized, little is currently known regarding its chemical behaviour. Motivated by our previous work, in which we showed that road dust is a photochemical source of singlet oxygen (1O2), we investigated 1O2 production by bulk winter street sweepings and by road dust collected in a variety of urban, industrial, and suburban locations in both autumn and spring. In all cases, the production of 1O2 by road dust was greater than that by Arizona test dust and desert-sourced dust, which highlights the unique photochemical environment afforded by this substrate. Mechanistically, we observed correlations between 1O2 production and the UV absorbance properties of dust extracts, which suggests the involvement of chromophoric dissolved organic matter in the observed photochemistry. Taken together, this work provides evidence that road dust-mediated photochemistry may influence the environmental lifetime of pollutants that react via 1O2-mediated pathways, including polycyclic aromatic hydrocarbons.

Origin of Ozone NO(x) in the Tropical Troposphere: A Photochemical Analysis of Aircraft Observations Over the South Atlantic Basin

NASA Technical Reports Server (NTRS)

Jacob, D. J.; Heikes, B. G.; Fan, S.-M.; Logan, J. A.; Mauzerall, D. L.; Bradshaw, J. D.; Singh, H. B.; Gregory, G. L.; Talbot, R. W.; Blake, D. R.;

Photochemical synthesis of simple organic free radicals on simulated planetary surfaces - An ESR study

NASA Technical Reports Server (NTRS)

Tseng, S.-S.; Chang, S.

1975-01-01

Electron spin resonance (ESR) spectroscopy provided evidence for formation of hydroxyl radicals during ultraviolet photolysis (254 nm) at -170 C of H2O adsorbed on silica gel or of silica gel alone. The carboxyl radical was observed when CO or CO2 or a mixture of CO and CO2 adsorbed on silica gel at -170 C was irradiated. The ESR signals of these radicals slowly disappeared when the irradiated samples were warmed to room temperature. However, reirradiation of CO or CO2, or the mixture CO and CO2 on silica gel at room temperature then produced a new species, the carbon dioxide anion radical, which slowly decayed and was identical with that produced by direct photolysis of formic acid adsorbed on silica gel. The primary photochemical process may involve formation of hydrogen and hydroxyl radicals. Subsequent reactions of these radicals with adsorbed CO or CO2 or both yield carboxyl radicals, CO2H, the precursors of formic acid. These results confirm the formation of formic acid under simulated Martian conditions and provide a mechanistic basis for gauging the potential importance of gas-solid photochemistry for chemical evolution on other extraterrestrial bodies, on the primitive earth, and on dust grains in the interstellar medium.

Isomerization Intermediates In Solution Phase Photochemistry Of Stilbenes

NASA Astrophysics Data System (ADS)

Doany, F. E.; Hochstrasser, R. M.; Greene, B. I.

1985-04-01

Picosecond and subpicosecond spectroscopic studies have revealed evidence for an isomerization intermediate between cis and trans in the photoinduced isomerism of both stilbene and biindanyledene ("stiff" stilbene). In stiff stilbene, a transient absorption at 351 nm displays time evolution and viscosity dependence consistent with absorption by a twisted intermediate ("phantom" state) with a lOps lifetime. An analagous bottleneck state with a life-time of 4ps is also consistent with the ground state recovery dynamics of t-stilbene following excitation of c-stilbene when monitored with 0.1ps resolution.

Formation of reactive nitrogen oxides from urban grime photochemistry

NASA Astrophysics Data System (ADS)

Baergen, Alyson M.; Donaldson, D. James

2016-05-01

Impervious surfaces are ubiquitous in urban environments and constitute a substrate onto which atmospheric constituents can deposit and undergo photochemical and oxidative processing, giving rise to "urban grime" films. HNO3 and N2O5 are important sinks for NOx in the lower atmosphere and may be deposited onto these films, forming nitrate through surface hydrolysis. Although such deposition has been considered as a net loss of NOx from the atmosphere, there is increasing evidence that surface-associated nitrate undergoes further reaction. Here, we examine the gas phase products of the photochemistry of real, field-collected urban grime using incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS). Gas phase nitrogen oxides are emitted upon illumination of grime samples and their production increases with ambient relative humidity (RH) up to 35 % after which the production becomes independent of RH. These results are discussed in the context of water uptake onto and evaporation from grime films.

The effect of photochemical models on calculated equilibria and cooling rates in the stratosphere

NASA Technical Reports Server (NTRS)

Blake, D.; Lindzen, R. S.

1973-01-01

Simplified models were developed for radiative heating and cooling and for ozone photochemistry in the region 22-60 km. The latter permit the inclusion of nitrogen and hydrogen reactions in addition to simple oxygen reactions. The simplicity of the scheme facilitates the use of a wide variety of cooling and reaction rates. It is shown that joint radiative-photochemical equilibrium is appropriate to the mean state of the atmosphere between 35 and 60 km. The relaxation of perturbations from joint radiative-photochemical equilibrium was also investigated. In all cases the coupling between temperature dependent ozone photochemistry and radiation lead to a reduction of the thermal relaxation time from its purely radiative value. The latter, which amounts to about 10 days, is reduced to 2-4 days at heights of 31-35 km. This greatly enhances the dissipation of waves traveling through the stratosphere.

Development of a chlorine chemistry module for the Master Chemical Mechanism

NASA Astrophysics Data System (ADS)

Xue, L. K.; Saunders, S. M.; Wang, T.; Gao, R.; Wang, X. F.; Zhang, Q. Z.; Wang, W. X.

2015-06-01

The chlorine atom (Cl·) has a high potential to perturb atmospheric photochemistry by oxidizing volatile organic compounds (VOCs), but the exact role it plays in the polluted troposphere remains unclear. The Master Chemical Mechanism (MCM) is a near explicit mechanism that has been widely applied in the atmospheric chemistry research. While it addresses comprehensively the chemistry initiated by the OH, O3 and NO3 radicals, its representation of the Cl· chemistry is incomplete as it only considers the reactions for alkanes. In this paper, we develop a more comprehensive Cl· chemistry module that can be directly incorporated within the MCM framework. A suite of 199 chemical reactions describes the Cl·-initiated degradation of alkenes, aromatics, aldehydes, ketones, alcohols, and some organic acids and nitrates, along with the inorganic chemistry involving Cl· and its precursors. To demonstrate the potential influence of the new chemistry module, it was incorporated into a MCM box model to evaluate the impacts of nitryl chloride (ClNO2), a product of nocturnal halogen activation by nitrogen oxides (NOx), on the following-day's atmospheric photochemistry. With constraints of recent observations collected at a coastal site in Hong Kong, southern China, the modeling analyses suggest that the Cl· produced from ClNO2 photolysis may substantially enhance the atmospheric oxidative capacity, VOC oxidation, and O3 formation, particularly in the early morning period. The results demonstrate the critical need for photochemical models to include more fully chlorine chemistry in order to better understand the atmospheric photochemistry in polluted environments subject to intense emissions of NOx, VOCs and chlorine-containing constituents.

Development of a chlorine chemistry module for the Master Chemical Mechanism

NASA Astrophysics Data System (ADS)

Xue, L. K.; Saunders, S. M.; Wang, T.; Gao, R.; Wang, X. F.; Zhang, Q. Z.; Wang, W. X.

2015-10-01

The chlorine atom (Cl·) has a high potential to perturb atmospheric photochemistry by oxidizing volatile organic compounds (VOCs), but the exact role it plays in the polluted troposphere remains unclear. The Master Chemical Mechanism (MCM) is a near-explicit mechanism that has been widely applied in the atmospheric chemistry research. While it addresses comprehensively the chemistry initiated by the OH, O3 and NO3 radicals, its representation of the Cl· chemistry is incomplete as it only considers the reactions for alkanes. In this paper, we develop a more comprehensive Cl· chemistry module that can be directly incorporated within the MCM framework. A suite of 205 chemical reactions describes the Cl·-initiated degradation of alkenes, aromatics, alkynes, aldehydes, ketones, alcohols, and some organic acids and nitrates, along with the inorganic chemistry involving Cl· and its precursors. To demonstrate the potential influence of the new chemistry module, it was incorporated into a MCM box model to evaluate the impacts of nitryl chloride (ClNO2), a product of nocturnal halogen activation by nitrogen oxides (NOX), on the following day's atmospheric photochemistry. With constraints of recent observations collected at a coastal site in Hong Kong, southern China, the modeling analyses suggest that the Cl· produced from ClNO2 photolysis may substantially enhance the atmospheric oxidative capacity, VOC oxidation and O3 formation, particularly in the early morning period. The results demonstrate the critical need for photochemical models to include more detailed chlorine chemistry in order to better understand the atmospheric photochemistry in polluted environments subject to intense emissions of NOX, VOCs and chlorine-containing constituents.

Investigation of low-cost ablative heat shield fabrication for space shuttles

NASA Technical Reports Server (NTRS)

Chandler, H. H.

1972-01-01

Improvements in the processes and design to reduce the manufacturing costs for low density ablative panels for the space shuttle are discussed. The areas that were studied included methods of loading honeycomb core, alternative reinforcement concepts, and the use of reusable subpanels. A review of previous studies on the fabrication of low-cost ablative panels and on permissible defects that do not affect thermal performance was conducted. Considerable differences in the quoted prices for ablative panels, even though the various contractors had reported similar fabrication times were discovered. How these cost differences arise from different estimating criteria and which estimating assumptions and other costs must be included in order to arrive at a realistic price are discussed.

Photochemistry on soft-glass hollow-core photonic crystal fibre

NASA Astrophysics Data System (ADS)

Cubillas, Ana M.; Jiang, Xin; Euser, Tijmen G.; Taccardi, Nicola; Etzold, Bastian J. M.; Wasserscheid, Peter; Russell, Philip St. J.

2014-05-01

Hollow-core photonic crystal fibre (HC-PCF) offers strong light confinement and long interaction lengths in an optofluidic channel. These unique advantages have motivated its recent use as a highly efficient and versatile microreactor for liquid-phase photochemistry and catalysis. In this work, we use a soft-glass HC-PCF to carry out photochemical experiments in a high-index solvent such as toluene. The high-intensity and strong confinement in the fibre is demonstrated to enhance the performance of a proof-of-principle photolysis reaction.

First detection of Mars atmospheric hydroxyl: CRISM Near-IR measurement versus LMD GCM simulation of OH Meinel band emission in the Mars polar winter atmosphere

NASA Astrophysics Data System (ADS)

Todd Clancy, R.; Sandor, Brad J.; García-Muñoz, Antonio; Lefèvre, Franck; Smith, Michael D.; Wolff, Michael J.; Montmessin, Franck; Murchie, Scott L.; Nair, Hari

2013-09-01

Visible and near-IR Meinel band emissions originate from excited OH in the terrestrial upper atmosphere (Meinel, I.A.B. [1950]. Astrophys. J. 111, 555. http://dx.doi.org/10.1086/145296), and have recently been detected in the Venus nightside upper mesosphere (Piccioni, G. et al. [2008]. Astron. Astrophys. 483, L29-L33. http://dx.doi.org/10.1051/0004-6361:200809761). Meinel band observations support key studies of transport and photochemistry in both of these atmospheres. In the case of Mars, OH regulates the basic stability of the CO2 atmosphere to photolytic decomposition (to CO and O2, e.g. Parkinson, T.D., Hunten, D.M. [1972]. J. Atmos. Sci. 29, 1380-1390. http://dx.doi.org/10.1175/1520-0469(1972)029<1380:SAAOOO>2.0.CO;2), and yet has never been measured. We present the first detection of Mars atmospheric OH, associated with CRISM near-IR spectral limb observations of polar night Meinel band emissions centered at 1.45 and 2.9 μm. Meinel band (1-0), (2-1), and (2-0) average limb intensities of 990 ± 280, 1060 ± 480, and 200 ± 100 kiloRayleighs (kR), respectively, are determined for 70-90 NS polar winter latitudes over altitudes of 40-56 km. Additional OH bands, such as (3-2), (3-1), and (4-2), present ⩽1σ measurements. Uncertainty in the (4-2) band emission rate contributes to increased uncertainty in the determination of the O2(1Δg) (0-0)/(0-1) band emission ratio A00/A01=47-12+26. An average profile retrieval for Mars OH polar nightglow indicates 45-55 km altitude levels for volume emission rates (VER) of 0.4 (2-0) to 2 (1-0, 2-1) × 104 photons/(cm3 s). Similar to polar night O2(1Δg) emission (e.g. Clancy, R.T. et al. [2012]. J. Geophys. Res. (Planets) 117, E00J10. http://dx.doi.org/10.1029/2011JE004018), Meinel OH band emission is supported by upper level, winter poleward transport of O and H in the deep Hadley solsticial circulations of Mars. The retrieved OH emission rates are compared to polar winter OH nightglow simulated by the LMD (Laboratoire de Météorologie Dynamique) photochemical GCM (global climate model), employing detailed photochemistry (e.g. Lefèvre, F., Lebonnois, S., Montmessin, F., Forget, F. [2004]. J. Geophys. Res. (Planets) 109, E07004. http://dx.doi.org/10.1029/2004JE002268) and energy transfer processes (excitation and quenching) developed for Mars Meinel OH band nightglow by García Muñoz et al. (García Muñoz, A., McConnell, J.C., McDade, I.C., Melo, S.M.L. [2005]. Icarus 176, 75-95). Modeled versus observed OH emission behavior agrees within measurement uncertainties with the assumptions of a Bates-Nicolet (H + O3) source for excited OH production, and ‘collisional-cascade’ quenching of the OH vibrational population by CO2. ‘Sudden-death’ quenching of excited OH by CO2 leads to 100× less OH emission than observed. The combined agreement between LMD GCM simulated and CRISM observed O2(1Δg) and Meinel OH polar nightglow behaviors represents a significant demonstration of the LMD model capability to couple odd oxygen and hydrogen photochemistry and transport by the Mars global circulation in a realistic fashion.

Matrix photochemistry of small molecules: Influencing reaction dynamics on electronically excited hypersurfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laursen, S.L.

Investigations of chemical reactions on electronically excited reaction surfaces are presented. The role of excited-surface multiplicity is of particular interest, as are chemical reactivity and energy transfer in systems in which photochemistry is initiated through a metal atom sensitizer.'' Two approaches are employed: A heavy-atom matrix affords access to forbidden triplet reaction surfaces, eliminating the need for a potentially reactive sensitizer. Later, the role of the metal atom in the photosensitization process is examined directly.

Photochemistry on ultrathin metal films: Strongly enhanced cross sections for NO2 on Ag /Si(100)

NASA Astrophysics Data System (ADS)

Wesenberg, Claudia; Autzen, Olaf; Hasselbrink, Eckart

2006-12-01

The surface photochemistry of NO2 on ultrathin Ag(111) films (5-60nm ) on Si(100) substrates has been studied. NO2, forming N2O4 on the surface, dissociates to release NO and NO2 into the gas phase with translational energies exceeding the equivalent of the sample temperature. An increase of the photodesorption cross section is observed for 266nm light when the film thickness is decreased below 30nm despite the fact that the optical absorptivity decreases. For 4.4nm film thickness this increase is about threefold. The data are consistent with a similar effect for 355nm light. The reduced film thickness has no significant influence on the average translation energy of the desorbing molecules or the branching into the different channels. The increased photodesorption cross section is interpreted to result from photon absorption in the Si substrate producing electrons with no or little momenta parallel to the surface at energies where this is not allowed in Ag. It is suggested that these electrons penetrate through the Ag film despite the gap in the surface projected band structure.

Improving emissions inventories in Mexico through systematic analysis of model performance along C-130 and DC-8 flight tracks during MILAGRO

NASA Astrophysics Data System (ADS)

Mena-Carrasco, M.; Carmichael, G. R.; Campbell, J. E.; Tang, Y.; Chai, T.

2007-05-01

During the MILAGRO campaign in March 2006 the University of Iowa provided regional air quality forecasting for scientific flight planning for the C-130 and DC-8. Model performance showed positive bias of ozone prediction (~15ppbv), associated to overpredictions in precursor concentrations (~2.15 ppbv NOy and ~1ppmv ARO1). Model bias showed a distinct geographical pattern in which the higher values were in and near Mexico City. Newer runs in which NOx and VOC emissions were decreased improved ozone prediction, decreasing bias and increasing model correlation, at the same time reducing regional bias over Mexico. This work will evaluate model performance using the newly published Mexico National Emissions Inventory, and the introduction of data assimilation to recover emissions scaling factors to optimize model performance. Finally the results of sensitivity runs showing the regional impact of Mexico City emissions on ozone concentrations will be shown, along with the influence of Mexico City aerosol concentrations on regional photochemistry.

Impacts of brown carbon from biomass burning on surface UV and ozone photochemistry in the Amazon Basin

PubMed Central

Mok, Jungbin; Krotkov, Nickolay A.; Arola, Antti; Torres, Omar; Jethva, Hiren; Andrade, Marcos; Labow, Gordon; Eck, Thomas F.; Li, Zhanqing; Dickerson, Russell R.; Stenchikov, Georgiy L.; Osipov, Sergey; Ren, Xinrong

2016-01-01

The spectral dependence of light absorption by atmospheric particulate matter has major implications for air quality and climate forcing, but remains uncertain especially in tropical areas with extensive biomass burning. In the September-October 2007 biomass-burning season in Santa Cruz, Bolivia, we studied light absorbing (chromophoric) organic or “brown” carbon (BrC) with surface and space-based remote sensing. We found that BrC has negligible absorption at visible wavelengths, but significant absorption and strong spectral dependence at UV wavelengths. Using the ground-based inversion of column effective imaginary refractive index in the range 305–368 nm, we quantified a strong spectral dependence of absorption by BrC in the UV and diminished ultraviolet B (UV-B) radiation reaching the surface. Reduced UV-B means less erythema, plant damage, and slower photolysis rates. We use a photochemical box model to show that relative to black carbon (BC) alone, the combined optical properties of BrC and BC slow the net rate of production of ozone by up to 18% and lead to reduced concentrations of radicals OH, HO2, and RO2 by up to 17%, 15%, and 14%, respectively. The optical properties of BrC aerosol change in subtle ways the generally adverse effects of smoke from biomass burning. PMID:27833145

Photochemistry of polycyclic aromatic hydrocarbons in cosmic water ice. II. Near UV/VIS spectroscopy and ionization rates

NASA Astrophysics Data System (ADS)

Bouwman, J.; Cuppen, H. M.; Steglich, M.; Allamandola, L. J.; Linnartz, H.

2011-05-01

Context. Mid-infrared emission features originating from polycyclic aromatic hydrocarbons (PAHs) are observed towards photon dominated regions in space. Towards dense clouds, however, these emission features are quenched. Observations of dense clouds show that many simple volatile molecules are frozen out on interstellar grains, forming thin layers of ice. Recently, observations have shown that more complex non-volatile species, presumably including PAHs, also freeze out and contribute to the ongoing solid-state chemistry. Aims: The study presented here aims at obtaining reaction rate data that characterize PAH photochemistry upon vacuum ultraviolet (VUV) irradiation in an interstellar H2O ice analogue to explore the potential impact of PAH:H2O ice reactions on overall interstellar ice chemistry. To this end, the experimental results are implemented in a chemical model under simple interstellar cloud conditions. Methods: Time-dependent near-UV/VIS spectroscopy on the VUV photochemistry of anthracene, pyrene, benzo[ghi]perylene and coronene containing interstellar H2O ice analogs is performed at 25 and 125 K, using an optical absorption setup. Results: Near-UV/VIS absorption spectra are presented for these four PAHs and their photoproducts including cationic species trapped in H2O ice. Oscillator strengths of the cation absorption bands are derived relative to the oscillator strength of the neutral parent PAH. The loss of the parent and growth of PAH photoproducts are measured as a function of VUV dose, yielding solid state reaction constants. The rate constants are used in an exploratory astrochemical model, to assess the importance of PAH:H2O ice photoprocessing in UV exposed interstellar environments, compared with the timescales in which PAH molecules are incorporated in interstellar ices. Conclusions: All four PAHs studied here are found to be readily ionized upon VUV photolysis when trapped in H2O ice and exhibit similar rates for ionization at astronomically relevant temperatures. Depending on the relative efficiency of H2O photodesorption and PAH photoionization in H2O ice, the latter may trigger a charge induced aromatic solid state chemistry, in which PAH cations play a central role.

Photochemical transformations accelerated in continuous-flow reactors: basic concepts and applications.

PubMed

Su, Yuanhai; Straathof, Natan J W; Hessel, Volker; Noël, Timothy

2014-08-18

Continuous-flow photochemistry is used increasingly by researchers in academia and industry to facilitate photochemical processes and their subsequent scale-up. However, without detailed knowledge concerning the engineering aspects of photochemistry, it can be quite challenging to develop a suitable photochemical microreactor for a given reaction. In this review, we provide an up-to-date overview of both technological and chemical aspects associated with photochemical processes in microreactors. Important design considerations, such as light sources, material selection, and solvent constraints are discussed. In addition, a detailed description of photon and mass-transfer phenomena in microreactors is made and fundamental principles are deduced for making a judicious choice for a suitable photomicroreactor. The advantages of microreactor technology for photochemistry are described for UV and visible-light driven photochemical processes and are compared with their batch counterparts. In addition, different scale-up strategies and limitations of continuous-flow microreactors are discussed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermally and vibrationally induced conformational isomerizations, infrared spectra, and photochemistry of gallic acid in low-temperature matrices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Justino, Licínia L. G., E-mail: liciniaj@ci.uc.pt; Reva, Igor; Fausto, Rui

2016-07-07

Near-infrared (near-IR) narrowband selective vibrational excitation and annealing of gallic acid (3,4,5-trihydroxybenzoic acid) isolated in cryogenic matrices were used to induce interconversions between its most stable conformers. The isomerizations were probed by infrared spectroscopy. An extensive set of quantum chemical calculations, carried out at the DFT(B3LYP)/6-311++G(d,p) level of approximation, was used to undertake a detailed analysis of the ground state potential energy surface of the molecule. This investigation of the molecule conformational space allowed extracting mechanistic insights into the observed annealing- or near-IR-induced isomerization processes. The infrared spectra of the two most stable conformers of gallic acid in N{sub 2},more » Xe, and Ar matrices were fully assigned. Finally, the UV-induced photochemistry of the matrix isolated compound was investigated.« less

The importance of charge-transfer interactions in determining chromophoric dissolved organic matter (CDOM) optical and photochemical properties.

PubMed

Sharpless, Charles M; Blough, Neil V

2014-04-01

Absorption of sunlight by chromophoric dissolved natural organic matter (CDOM) is environmentally significant because it controls photic zone depth and causes photochemistry that affects elemental cycling and contaminant fate. Both the optics (absorbance and fluorescence) and photochemistry of CDOM display unusual properties that cannot easily be ascribed to a superposition of individual chromophores. These include (i) broad, unstructured absorbance that decreases monotonically well into the visible and near IR, (ii) fluorescence emission spectra that all fall into a single envelope regardless of the excitation wavelength, and (iii) photobleaching and photochemical quantum yields that decrease monotonically with increasing wavelength. In contrast to a simple superposition model, these phenomena and others can be reasonably well explained by a physical model in which charge-transfer interactions between electron donating and accepting chromophores within the CDOM control the optical and photophysical properties. This review summarizes current understanding of the processes underlying CDOM photophysics and photochemistry as well as their physical basis.

Lysozyme Photochemistry as a Function of Temperature. The Protective Effect of Nanoparticles on Lysozyme Photostability

PubMed Central

Oliveira Silva, Catarina; Petersen, Steffen B.; Pinto Reis, Catarina; Rijo, Patrícia; Molpeceres, Jesús; Vorum, Henrik; Neves-Petersen, Maria Teresa

2015-01-01

The presence of aromatic residues and their close spatial proximity to disulphide bridges makes hen egg white lysozyme labile to UV excitation. UVB induced photo-oxidation of tryptophan and tyrosine residues leads to photochemical products, such as, kynurenine, N–formylkynurenine and dityrosine and to the disruption of disulphide bridges in proteins. We here report that lysozyme UV induced photochemistry is modulated by temperature, excitation power, illumination time, excitation wavelength and by the presence of plasmonic quencher surfaces, such as gold, and by the presence of natural fluorescence quenchers, such as hyaluronic acid and oleic acid. We show evidence that the photo-oxidation effects triggered by 295 nm at 20°C are reversible and non-reversible at 10°C, 25°C and 30°C. This paper provides evidence that the 295 nm damage threshold of lysozyme lies between 0.1 μW and 0.3 μW. Protein conformational changes induced by temperature and UV light have been detected upon monitoring changes in the fluorescence emission spectra of lysozyme tryptophan residues and SYPRO® Orange. Lysozyme has been conjugated onto gold nanoparticles, coated with hyaluronic acid and oleic acid (HAOA). Steady state and time resolved fluorescence studies of free and conjugated lysozyme onto HAOA gold nanoparticles reveals that the presence of the polymer decreased the rate of the observed photochemical reactions and induced a preference for short fluorescence decay lifetimes. Size and surface charge of the HAOA gold nanoparticles have been determined by dynamic light scattering and zeta potential measurements. TEM analysis of the particles confirms the presence of a gold core surrounded by a HAOA matrix. We conclude that HAOA gold nanoparticles may efficiently protect lysozyme from the photochemical effects of UVB light and this nanocarrier could be potentially applied to other proteins with clinical relevance. In addition, this study confirms that the temperature plays a critical role in the photochemical pathways a protein enters upon UV excitation. PMID:26656259

Lysozyme Photochemistry as a Function of Temperature. The Protective Effect of Nanoparticles on Lysozyme Photostability.

PubMed

Oliveira Silva, Catarina; Petersen, Steffen B; Pinto Reis, Catarina; Rijo, Patrícia; Molpeceres, Jesús; Vorum, Henrik; Neves-Petersen, Maria Teresa

2015-01-01

The presence of aromatic residues and their close spatial proximity to disulphide bridges makes hen egg white lysozyme labile to UV excitation. UVB induced photo-oxidation of tryptophan and tyrosine residues leads to photochemical products, such as, kynurenine, N-formylkynurenine and dityrosine and to the disruption of disulphide bridges in proteins. We here report that lysozyme UV induced photochemistry is modulated by temperature, excitation power, illumination time, excitation wavelength and by the presence of plasmonic quencher surfaces, such as gold, and by the presence of natural fluorescence quenchers, such as hyaluronic acid and oleic acid. We show evidence that the photo-oxidation effects triggered by 295 nm at 20°C are reversible and non-reversible at 10°C, 25°C and 30°C. This paper provides evidence that the 295 nm damage threshold of lysozyme lies between 0.1 μW and 0.3 μW. Protein conformational changes induced by temperature and UV light have been detected upon monitoring changes in the fluorescence emission spectra of lysozyme tryptophan residues and SYPRO® Orange. Lysozyme has been conjugated onto gold nanoparticles, coated with hyaluronic acid and oleic acid (HAOA). Steady state and time resolved fluorescence studies of free and conjugated lysozyme onto HAOA gold nanoparticles reveals that the presence of the polymer decreased the rate of the observed photochemical reactions and induced a preference for short fluorescence decay lifetimes. Size and surface charge of the HAOA gold nanoparticles have been determined by dynamic light scattering and zeta potential measurements. TEM analysis of the particles confirms the presence of a gold core surrounded by a HAOA matrix. We conclude that HAOA gold nanoparticles may efficiently protect lysozyme from the photochemical effects of UVB light and this nanocarrier could be potentially applied to other proteins with clinical relevance. In addition, this study confirms that the temperature plays a critical role in the photochemical pathways a protein enters upon UV excitation.

2013 Chemical reactions at surfaces. Surfaces in Energy and the Environment. Gordon Research Conference and Gordon Research Seminar (April 28 - May 3, 2013 - Les Diablerets, Switzerland)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stair, Peter C.

presentations on chemistry at solid and liquid surfaces of relevance to catalysis, synthesis, photochemistry, environmental science, and tribology. Topics include: Fundamental Surface Chemistry; Catalysis; Solid Liquid and Aerosol Interfaces; Surface Photochemistry; Synthesis of Surfaces; Environmental Interfaces; Hot Topics in Surface Chemical Reactions; Tribology; Gas-Surface Scattering and Reactions; Novel Materials and Environments.

Dehydrophenylnitrenes: matrix isolation and photochemical rearrangements.

PubMed

Sander, Wolfram; Winkler, Michael; Cakir, Bayram; Grote, Dirk; Bettinger, Holger F

2007-02-02

The photochemistry of 3-iodo-2,4,5,6-tetrafluorophenyl azide 8 and 3,5-diiodo-2,4,6-trifluorophenyl azide 9 was studied by IR and EPR spectroscopy in cryogenic argon and neon matrices. Both compounds form the corresponding nitrenes as primary photoproducts in photostationary equilibria with their azirine and ketenimine isomers. In contrast to fluorinated phenylnitrenes, ring-opened products are obtained upon short-wavelength irradiation of the iodine-containing systems, indicative of C-I bond cleavage in the nitrenes or didehydroazepines under these conditions. Neither 3-dehydrophenylnitrene 6 nor 3,5-didehydrophenylnitrene 7 could be detected directly. The structures of the acyclic photoproducts were identified by extensive comparison with DFT calculated spectra. Mechanistic aspects of the rearrangements leading to the observed products and the electronic properties of the title intermediates are discussed on the basis of DFT as well as high-level ab initio calculations. The computations indicate strong through-bond coupling of the exocyclic orbital in the meta position with the singly occupied in-plane nitrene orbital in the monoradical nitrenes. In contrast to the ortho or para isomers, this interaction results in low-spin ground states for meta nitrene radicals and a weakening of the C1-C2 bond causing the kinetic instability of these species even under low-temperature conditions. 3,5-Didehydrophenylnitrenes, on the other hand, in which a strong C3-C5 interaction reduces coupling of the radical sites with the nitrene unit, might be accessible synthetic targets if the intermediate formation of labile monoradicals could be circumvented.

Ozone photochemistry in an oil and natural gas extraction region during winter: simulations of a snow-free season in the Uintah Basin, Utah

NASA Astrophysics Data System (ADS)

Edwards, P. M.; Young, C. J.; Aikin, K.; deGouw, J.; Dubé, W. P.; Geiger, F.; Gilman, J.; Helmig, D.; Holloway, J. S.; Kercher, J.; Lerner, B.; Martin, R.; McLaren, R.; Parrish, D. D.; Peischl, J.; Roberts, J. M.; Ryerson, T. B.; Thornton, J.; Warneke, C.; Williams, E. J.; Brown, S. S.

2013-09-01

The Uintah Basin in northeastern Utah, a region of intense oil and gas extraction, experienced ozone (O3) concentrations above levels harmful to human health for multiple days during the winters of 2009-2010 and 2010-2011. These wintertime O3 pollution episodes occur during cold, stable periods when the ground is snow-covered, and have been linked to emissions from the oil and gas extraction process. The Uintah Basin Winter Ozone Study (UBWOS) was a field intensive in early 2012, whose goal was to address current uncertainties in the chemical and physical processes that drive wintertime O3 production in regions of oil and gas development. Although elevated O3 concentrations were not observed during the winter of 2011-2012, the comprehensive set of observations tests our understanding of O3 photochemistry in this unusual emissions environment. A box model, constrained to the observations and using the near-explicit Master Chemical Mechanism (MCM) v3.2 chemistry scheme, has been used to investigate the sensitivities of O3 production during UBWOS 2012. Simulations identify the O3 production photochemistry to be highly radical limited (with a radical production rate significantly smaller than the NOx emission rate). Production of OH from O3 photolysis (through reaction of O(1D) with water vapor) contributed only 170 pptv day-1, 8% of the total primary radical source on average (primary radicals being those produced from non-radical precursors). Other radical sources, including the photolysis of formaldehyde (HCHO, 52%), nitrous acid (HONO, 26%), and nitryl chloride (ClNO2, 13%) were larger. O3 production was also found to be highly sensitive to aromatic volatile organic compound (VOC) concentrations, due to radical amplification reactions in the oxidation scheme of these species. Radical production was shown to be small in comparison to the emissions of nitrogen oxides (NOx), such that NOx acted as the primary radical sink. Consequently, the system was highly VOC sensitive, despite the much larger mixing ratio of total non-methane hydrocarbons (230 ppbv (2080 ppbC), 6 week average) relative to NOx (5.6 ppbv average). However, the importance of radical sources which are themselves derived from NOx emissions and chemistry, such as ClNO2 and HONO, make the response of the system to changes in NOx emissions uncertain. Model simulations attempting to reproduce conditions expected during snow-covered cold-pool conditions show a significant increase in O3 production, although calculated concentrations do not achieve the highest seen during the 2010-2011 O3 pollution events in the Uintah Basin. These box model simulations provide useful insight into the chemistry controlling winter O3 production in regions of oil and gas extraction.

Studies on Cation-induced Thylakoid Membrane Stacking, Fluorescence Yield, and Photochemical Efficiency 1

PubMed Central

Jennings, Robert Charles; Forti, Giorgio; Gerola, Paolo Domenico; Garlaschi, Flavio Massimo

1978-01-01

Trypsin digestion of photosynthetic membranes isolated from spinach (Spinacia oleracea L.) leaves eliminates the cation stimulation of chlorophyll fluorescence. High concentrations of cations protect the fluorescence yield against trypsin digestion, and the cation specificity for this protection closely resembles that required for the stimulation of fluorescence by cations. Trypsin digestion reverses cation-induced thylakoid stacking, and the time course of this effect seems to parallel that of the reversal of cation fluorescence. High concentrations of cations protect thylakoid stacking and cation-stimulated fluorescence alike. The cation stimulation of photosytem II photochemistry remains intact after trypsinization has reversed both cation-induced thylakoid stacking and fluorescence yield. It is concluded that cation-stimulated fluorescence yield, and not the cation stimulation of photosystem II photochemistry, is associated with thylakoid membrane stacking. ImagesFig. 2Fig. 3 PMID:16660630

Studies in organic and physical photochemistry - an interdisciplinary approach.

PubMed

Oelgemöller, Michael; Hoffmann, Norbert

2016-08-21

Traditionally, organic photochemistry when applied to synthesis strongly interacts with physical chemistry. The aim of this review is to illustrate this very fruitful interdisciplinary approach and cooperation. A profound understanding of the photochemical reactivity and reaction mechanisms is particularly helpful for optimization and application of these reactions. Some typical reactions and particular aspects are reported such as the Norrish-Type II reaction and the Yang cyclization and related transformations, the [2 + 2] photocycloadditions, particularly the Paternò-Büchi reaction, photochemical electron transfer induced transformations, different kinds of catalytic reactions such as photoredox catalysis for organic synthesis and photooxygenation are discussed. Particular aspects such as the structure and reactivity of aryl cations, photochemical reactions in the crystalline state, chiral memory, different mechanisms of hydrogen transfer in photochemical reactions or fundamental aspects of stereoselectivity are discussed. Photochemical reactions are also investigated in the context of chemical engineering. Particularly, continuous flow reactors are of interest. Novel reactor systems are developed and modeling of photochemical transformations and different reactors play a key role in such studies. This research domain builds a bridge between fundamental studies of organic photochemical reactions and their industrial application.

Iron deficiency cause changes in photochemistry, thylakoid organization, and accumulation of photosystem II proteins in Chlamydomonas reinhardtii.

PubMed

Devadasu, Elsin Raju; Madireddi, Sai Kiran; Nama, Srilatha; Subramanyam, Rajagopal

2016-12-01

A trace element, iron (Fe) plays a pivotal role in photosynthesis process which in turn mediates the plant growth and productivity. Here, we have focused majorly on the photochemistry of photosystem (PS) II, abundance of proteins, and organization of supercomplexes of thylakoids from Fe-depleted cells in Chlamydomonas reinhardtii. Confocal pictures show that the cell's size has been reduced and formed rosette-shaped palmelloids; however, there is no cell death. Further, the PSII photochemistry was reduced remarkably. Further, the photosynthetic efficiency analyzer data revealed that both donor and acceptor side of PSII were equally damaged. Additionally, the room-temperature emission spectra showed the fluorescence emission maxima increased due to impaired energy transfer from PSII to PSI. Furthermore, the protein data reveal that most of the proteins of reaction center and light-harvesting antenna were reduced in Fe-depleted cells. Additionally, the supercomplexes of PSI and PSII were destabilized from thylakoids under Fe-deficient condition showing that Fe is an important element in photosynthesis mechanism.

Mapping Vinyl Cyanide and Other Nitriles in Titan’s Atmosphere Using ALMA

NASA Astrophysics Data System (ADS)

Lai, J. C.-Y.; Cordiner, M. A.; Nixon, C. A.; Achterberg, R. K.; Molter, E. M.; Teanby, N. A.; Palmer, M. Y.; Charnley, S. B.; Lindberg, J. E.; Kisiel, Z.; Mumma, M. J.; Irwin, P. G. J.

2017-11-01

Vinyl cyanide (C2H3CN) is theorized to form in Titan’s atmosphere via high-altitude photochemistry and is of interest regarding the astrobiology of cold planetary surfaces due to its predicted ability to form cell membrane-like structures (azotosomes) in liquid methane. In this work, we follow up on the initial spectroscopic detection of C2H3CN on Titan by Palmer et al. with the detection of three new C2H3CN rotational emission lines at submillimeter frequencies. These new, high-resolution detections have allowed for the first spatial distribution mapping of C2H3CN on Titan. We present simultaneous observations of C2H5CN, HC3N, and CH3CN emission, and obtain the first (tentative) detection of C3H8 (propane) at radio wavelengths. We present disk-averaged vertical abundance profiles, two-dimensional spatial maps, and latitudinal flux profiles for the observed nitriles. Similarly to HC3N and C2H5CN, which are theorized to be short-lived in Titan’s atmosphere, C2H3CN is most abundant over the southern (winter) pole, whereas the longer-lived CH3CN is more concentrated in the north. This abundance pattern is consistent with the combined effects of high-altitude photochemical production, poleward advection, and the subsequent reversal of Titan’s atmospheric circulation system following the recent transition from northern to southern winter. We confirm that C2H3CN and C2H5CN are most abundant at altitudes above 200 km. Using a 300 km step model, the average abundance of C2H3CN is found to be 3.03 ± 0.29 ppb, with a C2H5CN/C2H3CN abundance ratio of 2.43 ± 0.26. Our HC3N and CH3CN spectra can be accurately modeled using abundance gradients above the tropopause, with fractional scale-heights of 2.05 ± 0.16 and 1.63 ± 0.02, respectively.

Laboratory studies of low temperature rate coefficients: The atmospheric chemistry of the outer planets

NASA Technical Reports Server (NTRS)

Leone, Stephen R.

1993-01-01

The objectives are to measure laboratory rate coefficients for key reactions of hydrocarbon molecules and radicals at low temperatures, which are relevant to the atmospheric photochemistry of Saturn, Jupiter, and Titan. Upcoming NASA planetary missions, such as Cassini, will probe the atmosphere of Titan in more detail, offering an excellent opportunity to test kinetic models and to establish fiducial standards for using kinetic models to interpret various parameters of the outer planets. Accurate low temperature kinetic data, which are presently lacking, may require crucial revisions to the rates of formation and destruction and are of utmost importance to the success of these efforts. In this program, several key reactions of ethynyl radicals (C2H) with acetylene (C2H2), methane (CH4), and oxygen (O2), down to temperatures of 170 K were successfully investigated. The experimental apparatus developed in our laboratory for measuring reaction kinetics at low temperatures consists of a laser photolysis/infrared probe laser setup. The rate measurements are carried out as a function of (low) temperature with a transverse flow cell designed specifically for these studies. A 193 nm argon fluoride pulsed excimer laser is used to photolyze a suitable precursor molecule, such as acetylene to produce C2H, and a high resolution, tunable infrared F-center laser (2.3-3.35 mu m) probes the transient concentrations of the radical species directly in absorption to extract the kinetic rate coefficients.

Spectroscopic detection and mapping of vinyl cyanide on Titan

NASA Astrophysics Data System (ADS)

Cordiner, Martin; Yukiko Palmer, Maureen; Lai, James; Nixon, Conor A.; Teanby, Nicholas; Charnley, Steven B.; Vuitton, Veronique; Kisiel, Zbigniew; Irwin, Patrick; Molter, Ned; Mumma, Michael J.

2017-10-01

The first spectroscopic detection of vinyl cyanide (otherwise known as acrylonitrile; C2H3CN) on Titan was obtained by Palmer et al. (2017), based on three rotational emission lines observed with ALMA at millimeter wavelengths (in receiver band 6). The astrobiological significance of this detection was highlighted due to the theorized ability of C2H3CN molecules to combine into cell membrane-like structures under the cold conditions found in Titan's hydrocarbon lakes. Here we report the detection of three additional C2H3CN transitions at higher frequencies (from ALMA band 7 flux calibration data). We present the first emission maps for this gas on Titan, and compare the molecular distribution with that of other nitriles observed with ALMA including HC3N, CH3CN, C2H5CN and HNC. The molecular abundance patterns are interpreted based on our understanding of Titan's high-altitude photochemistry and time-variable global circulation. Similar to the short-lived HC3N molecule, vinyl cyanide is found to be most abundant in the vicinity of the southern (winter) pole, whereas the longer-lived CH3CN is more concentrated in the north. The vertical abundance profile of C2H3CN (from radiative transfer modeling), as well as its latitudinal distribution, are consistent with a short photochemical lifetime for this species. Complementary results from our more recent (2017) nitrile mapping studies at higher spatial resolution will also be discussed.REFERENCES:Palmer, M. Y., Cordiner, M. A., Nixon, C. A. et al. "ALMA detection and astrobiological potential of vinyl cyanide on Titan", Sci. Adv. 2017, 3, e1700022

Rate constants for the reacion C4H radical with various hydrocarbons at very low temperatures relevant to the atmospheric chemistry of Titan and other astronomical sources

NASA Astrophysics Data System (ADS)

Berteloite, Coralie; Le Picard, Sébastien D.; Canosa, André; Sims, Ian R.

There is a huge interest on the satellite of Saturn, Titan, because its atmosphere is probably comparable to our primitive atmosphere. This particular attention has been enhanced by the recent Cassini-Huygens mission that should significantly increase our knowledge about the atmospheres composition (especially for the minority species) and the complex chemistry that takes place. The atmosphere of Titan is mainly composed of molecular nitrogen with a notable fraction of methane (1.5 - 5 %). Many organic compounds have been detected and the active photochemistry taking place in the upper atmosphere is supposed to be responsible for the haze that hides Titan's surface. According to photochemical models, diacetylene C4H2 production is initiated by the photodissociation of acetylene C2H2 (a product of methane photolysis) with the following mechanism: C2H2 + hν → C2H + H(hν < 217nm) C2H + C2H2 → C4H2 + H Diacetylene (also called butadiyne) is the first of the polyynes series proposed as a route of formation of the haze particles present in the upper atmosphere. Photolysis of diacetylene can leads to a large amount of radicals including C4H that can react to form longer carbonated chain. Up to now, in photochemical models, the kinetics of C4H is assumed to be the same than C2H. This is however a highly speculative assumption. It is crucial, therefore to determine the rate constants of the reactions involving C4H at low temperatures, especially as this radical has been detected in many important astronomical sources (diffuse gas, dark molecular clouds and circumstellar envelopes). The CRESU technique (Cinétique de Réaction en Ecoulement Supersonique Uniforme) based on a gas expansion through a Laval nozzle has been used to generate a cold supersonic flow. Kinetics measurements were achieved using PLP (Pulsed Laser Photolysis) LIF (Laser Induced Fluorescence) technique.We present the first results on the kinetics of C4H reactions with several hydrocarbons such as C2H2, C2H4, C2H6 and C4H2.

Photoionization of oxidized coenzyme Q in microemulsion: laser flash photolysis study in biomembrane-like system.

PubMed

Li, Kun; Wang, Mei; Wang, Jin; Zhu, Rongrong; Sun, Dongmei; Sun, Xiaoyu; Wang, Shi-Long

2013-01-01

Photoexcitation to generate triplet state has been proved to be the main photoreaction in homogeneous system for many benzoquinone derivatives, including oxidized coenzyme Q (CoQ) and its analogs. In the present study, microemulsion of CoQ, a heterogeneous system, is employed to mimic the distribution of CoQ in biomembrane. The photochemistry of CoQ(10) in microemulsion and cyclohexane is investigated and compared using laser flash photolysis and results show that CoQ(10) undergoes photoionization via a monophotonic process to generate radical cation of CoQ(10) in microemulsion and photoexcitation to generate excited triplet state in cyclohexane. Meanwhile, photoreactions of duroquinone (DQ) and CoQ(0) in microemulsion are also investigated to analyze the influence of molecular structure on the photochemistry of benzoquinone derivatives in microemulsion. Results suggest that photoexcitation, which is followed by excited state-involved hydrogen-abstraction reaction, is the main photoreaction for DQ and CoQ(0) in microemulsion. However, photoexcited CoQ(0) also leads to the formation of hydrated electrons. The isoprenoid side chain-involved high resonance stabilization is proposed to explain the difference in photoreactions of CoQ(0) and CoQ(10) in microemulsion. Considering that microemulsion is close to biomembrane system, its photoionization in microemulsion may be helpful to understand the real photochemistry of biological quinones in biomembrane system. © 2012 Tongji University. Photochemistry and Photobiology © 2012 The American Society of Photobiology.

Interactive Photochemistry in Earth System Models to Assess Uncertainty in Ozone and Greenhouse Gases. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prather, Michael J.; Hsu, Juno; Nicolau, Alex

Atmospheric chemistry controls the abundances and hence climate forcing of important greenhouse gases including N 2O, CH 4, HFCs, CFCs, and O 3. Attributing climate change to human activities requires, at a minimum, accurate models of the chemistry and circulation of the atmosphere that relate emissions to abundances. This DOE-funded research provided realistic, yet computationally optimized and affordable, photochemical modules to the Community Earth System Model (CESM) that augment the CESM capability to explore the uncertainty in future stratospheric-tropospheric ozone, stratospheric circulation, and thus the lifetimes of chemically controlled greenhouse gases from climate simulations. To this end, we have successfullymore » implemented Fast-J (radiation algorithm determining key chemical photolysis rates) and Linoz v3.0 (linearized photochemistry for interactive O 3, N 2O, NO y and CH 4) packages in LLNL-CESM and for the first time demonstrated how change in O2 photolysis rate within its uncertainty range can significantly impact on the stratospheric climate and ozone abundances. From the UCI side, this proposal also helped LLNL develop a CAM-Superfast Chemistry model that was implemented for the IPCC AR5 and contributed chemical-climate simulations to CMIP5.« less

Molecular beam studies of stratospheric photochemistry

NASA Astrophysics Data System (ADS)

Moore, Teresa Anne

1998-12-01

Photochemistry of chlorine oxide containing species plays a major role in stratospheric ozone depletion. This thesis discusses two photodissociation studies of the key molecules ClONO2 and ClOOCl which were previously thought to only produce Cl-atom (ozone depleting) products at wavelengths relevant to the stratosphere. The development of a molecular beam source of ClOOCl and the photodissociation dynamics of the model system Cl2O are also discussed. In the first chapter, the photochemistry of ClONO2 is examined at 308 nm using the technique of photofragment translational spectroscopy. Two primary decomposition pathways, leading to Cl + NO3 and ClO + NO2, were observed, with a lower limit of 0.33 for the relative yield of ClO. The angular distributions for both channels were anisotropic, indicating that the dissociation occurs within a rotational period. Chapter two revisits the photodissociation dynamics of Cl2O at 248 and 308 nm, on which we had previously reported preliminary findings. At 248 nm, three distinct dissociation pathways leading to Cl + ClO products were resolved. At 308 nm, the angular distribution was slightly more isotropic that previously reported, leaving open the possibility that Cl2O excited at 308 nm lives longer than a rotational period. Chapter three describes the development and optimization of a molecular beam source of ClOOCl. We utilized pulsed laser photolysis of ClA2O to generate ClO radicals, and cooled the cell to promote three body recombination to form ClOOCl. The principal components in the beam were Cl2, Cl2O, and ClOOCl. In the fourth chapter, the photodissociation dynamics of ClOOCl are investigated at 248 and 308 nm. We observed multiple dissociation pathways which produced ClO + ClO and 2Cl + O2 products. The relative Cl:ClO product yields are 1.0:0.13 and 1.0:0.20 for ClOOCl photolysis at 248 and 308 nm, respectively. The upper limit for the relative yield of the ClO + ClO channel was 0.19 at 248 nm and 0.31 at 308 nm. These results substantially confirm the current assumption but decrease somewhat the efficiency of the ClOOCl ozone-depleting catalytic cycle. At 248 nm, ClOOCl photolysis exhibited novel dissociation dynamics which appeared to depend on the symmetry of the excited state.

Triple oxygen isotope analysis of tropospheric CO2 on the two sides of the Pacific Ocean

NASA Astrophysics Data System (ADS)

Liang, M. C.; Newman, S.; Laskar, A. H.

2017-12-01

The abundance variations of near surface atmospheric CO2 isotopologues (primarily 16O12C16O, 16O13C16O, 17O12C16O, and 18O12C16O) represent an integrated signal from anthropogenic/biogeochemical processes, including fossil fuel burning, biospheric photosynthesis and respiration, hydrospheric isotope exchange with water, stratospheric photochemistry, cross-tropopause exchange, and subsequent vertical mixing between the free troposphere and planetary boundary. Oxygen isotopes, in particular, are affected by both the carbon and water cycles. Being a useful tracer that directly probes governing processes in CO2 biogeochemical cycles, D17O (= ln(1+d17O) - 0.516 ln(1+d18O)) provides a powerful constraint on the strengths of the associated cycles involving CO2. Here, we report and compare summer to winter seasons CO2 isotopic composition from Taiwan (Taipei) and USA (Palos Verdes, CA). On average, the D17O values from Taiwan are significantly higher than those in USA. Analysis shows that the impact of 2014-2016 El Nino event on the observed D17O values is not visible, in contrast to what was reported for the 1997-1998 El Nino from the CO2 data collected from La Jolla, CA. Attempts are made to understand the elevated D17O values in the eastern Pacific compared to those in the western Pacific. Implications for utilizing the new tracer D17O along with the conventional d18O for carbon cycling studies are also discussed.

Photochemical approaches to ordered polymers

NASA Technical Reports Server (NTRS)

Meador, Michael A.; Abdulaziz, Mahmoud; Meador, Mary Ann B.

1990-01-01

The photocyclization of o-benzyloxyphenyl ketone chromophores provides an efficient, high yield route to the synthesis of 2,3-diphenylbenzofurans. The synthesis and solution of photochemistry of a series of polymers containing this chromophore is described. The photocuring of these polymers is a potential new approach to the synthesis of highly conjugated polymers based upon a p-phenylene bisbenzofuran repeat unit.

Ancillary Ligand Effects upon the Photochemistry of Mn(bpy)(CO)3X Complexes (X = Br-, PhCC-).

PubMed

Yempally, Veeranna; Moncho, Salvador; Hasanayn, Faraj; Fan, Wai Yip; Brothers, Edward N; Bengali, Ashfaq A

2017-09-18

The photochemistry of two Mn(bpy)(CO) 3 X complexes (X = PhCC - , Br - ) has been studied in the coordinating solvents THF (terahydrofuran) and MeCN (acetonitrile) employing time-resolved infrared spectroscopy. The two complexes are found to exhibit strikingly different photoreactivities and solvent dependencies. In MeCN, photolysis of 1-(CO)(Br) [1 = Mn(bpy)(CO) 2 ] affords the ionic complex [1-(MeCN) 2 ]Br as a final product. In contrast, photolysis of 1-(CO)(CCPh) in MeCN results in facial to meridional isomerization of the parent complex. When THF is used as solvent, photolysis results in facial to meridional isomerization in both complexes, though the isomerization rate is larger for X = Br - . Pronounced differences are also observed in the photosubstitution chemistry of the two complexes where both the rate of MeCN exchange from 1-(MeCN)(X) by THFA (tetrahydrofurfurylamine) and the nature of the intermediates generated in the reaction are dependent upon X. DFT calculations are used to support analysis of some of the experiments.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elicio, Andy U.

My ERM 593 applied project will provide guidance for the Los Alamos National Laboratory Waste Stream Profile reviewer (i.e. RCRA reviewer) in regards to Reviewing and Approving a Waste Stream Profile in the Waste Compliance and Tracking System. The Waste Compliance and Tracking system is called WCATS. WCATS is a web-based application that “supports the generation, characterization, processing and shipment of LANL radioactive, hazardous, and industrial waste.” The LANL generator must characterize their waste via electronically by filling out a waste stream profile (WSP) in WCATS. Once this process is completed, the designated waste management coordinator (WMC) will perform amore » review of the waste stream profile to ensure the generator has completed their waste stream characterization in accordance with applicable state, federal and LANL directives particularly P930-1, “LANL Waste Acceptance Criteria,” and the “Waste Compliance and Tracking System User's Manual, MAN-5004, R2,” as applicable. My guidance/applied project will describe the purpose, scope, acronyms, definitions, responsibilities, assumptions and guidance for the WSP reviewer as it pertains to each panel and subpanel of a waste stream profile.« less

Characterization of Industrial Emission Sources and Photochemistry in Houston, Texas

NASA Astrophysics Data System (ADS)

Washenfelder, R. A.; Atlas, E. L.; Degouw, J.; Flocke, F. M.; Fried, A.; Frost, G. J.; Holloway, J.; Richter, D.; Ryerson, T. B.; Schauffler, S.; Trainer, M.; Walega, J.; Warneke, C.; Weibring, P.; Zheng, W.

2009-12-01

The Houston-Galveston urban area contains a number of large industrial petrochemical emission sources that produce volatile organic compounds and nitrogen oxides. These co-located emissions result in rapid and efficient ozone production downwind. Unlike a single large power plant, the industrial complexes consist of numerous sources that can be difficult to quantify in emission inventories. During September - October 2006, the NOAA WP-3 aircraft conducted research flights as part of the second Texas Air Quality Study (TexAQS II). We examine measurements of NOx, SO2, and speciated hydrocarbons from the Houston Ship Channel, which contains a dense concentration of industrial petrochemical sources, and isolated petrochemical facilities. These measurements are used to derive source emission estimates, which are then compared to available emission inventories. We find that high hydrocarbon emissions are typical for the Houston Ship Channel and isolated petrochemical facilities. Ethene and propene are found to be major contributors to ozone formation. Ratios of C2H4 / NOx and C3H6 / NOx exceed emission inventory values by factors of 10 - 50. These findings are consistent with the first TexAQS study in 2000. We examine trends in C2H4 / NOx and C3H6 / NOx ratios between 2000 and 2006, and determine that day-to-day variability and within-plume variability exceeds any long-term reduction in ethene and propene emissions for the isolated petrochemical sources. We additionally examine downwind photochemical products formed by these alkenes.

Solar photochemistry - twenty years of progress, what`s been accomplished, and where does it lead?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blake, D M

1995-01-01

It has been more than 20 years since the first oil embargo. That event created an awareness of the need for alternative sources of energy and renewed interest in combining sunlight and chemistry to produce the chemicals and materials required by industry. This paper will review approaches that have been taken, progress that has been made, and give some projections for the near and longer term prospects for commercialization of solar photochemistry.

Photochemistry of Fe2(CO)8(Mu-CH2)

DTIC Science & Technology

2000-01-04

REPORT DOCUMENTATION PAGE Form Approved OMB No. 0704-0188 Public reporting burden for this collection of information is estimated to average 1...State University PUBLICATIONS 1. Branan, D. M.; Hoffman, N. W.; McElroy, E. A.; Prokopuk, N.; Salazar, A. B.; Robbins, M. J.; Hill, W. E.; Webb, T...17), 2915, (1987) FIELDS OF STUDY Major Field: Chemistiy TABLE OF CONTENTS ABSTRACT jj DEDICATION jjj ACKNOWLEDGMENTS iv VITA v PUBLICATIONS

Photoactive high explosives: linear and nonlinear photochemistry of petrin tetrazine chloride.

PubMed

Greenfield, Margo T; McGrane, Shawn D; Bolme, Cindy A; Bjorgaard, Josiah A; Nelson, Tammie R; Tretiak, Sergei; Scharff, R Jason

2015-05-21

Pentaerythritol tetranitrate (PETN), a high explosive, initiates with traditional shock and thermal mechanisms. In this study, the tetrazine-substituted derivative of PETN, pentaerythritol trinitrate chlorotetrazine (PetrinTzCl), is being investigated for a photochemical initiation mechanism that could allow control over the chemistry contributing to decomposition leading to initiation. PetrinTzCl exhibits a photochemical quantum yield (QYPC) at 532 nm not evident with PETN. Using static spectroscopic methods, we observe energy absorption on the tetrazine (Tz) ring that results in photodissociation yielding N2, Cl-CN, and Petrin-CN as the major photoproducts. The QYPC was enhanced with increasing irradiation intensity. Experiment and theoretical calculations imply this excitation mechanism follows sequential photon absorption. Dynamic simulations demonstrate that the relaxation mechanism leading to the observed photochemistry in PetrinTzCl is due to vibrational excitation during internal conversion. PetrinTzCl's single photon stability and intensity dependence suggest this material could be stable in ambient lighting, yet possible to initiate with short-pulsed lasers.

Future directions for H sub x O sub y detection, executive summary

NASA Technical Reports Server (NTRS)

1986-01-01

New methods for the measurement of OH radicals were assessed as were currently available and possible future methods for the other H sub x O sub y species, HO2 and H2O2. The workshop participants were invited from different groups: modelers of atmospheric photochemistry, experimentalists measuring H sub x O y species with laser and nonlaser methods, and chemists and physicists familiar with such experiments but not involved in atmospheric monitoring. There were three major conclusions from the workshop concerning the OH radical. First, it was felt that local measurements made by laser techniques would be ready within 2 or 3 years to furnish reliable measurements at the level of 1,000,000 cu. cm. Second, measurements at this level of sensitivity and with attainable levels of precision could indeed be used to make useful and interesting tests of the fast photochemistry of the troposphere. It is important, however, that the measurements be carefully designed, with respect to spatial and temporal averaging, if there is to be a meaningful comparison between results from two experimental methods or a measurement and a model. Third, nonlocal measurements using released reactants and tracers would also be very useful. These could be made on a regional or global basis, although they still require experimental design including choice of compounds.

Response of Atmospheric Biomarkers to NOx-Induced Photochemistry Generated by Stellar Cosmic Rays for Earth-like Planets in the Habitable Zone of M Dwarf Stars

PubMed Central

Grießmeier, Jean-Mathias; von Paris, Philip; Patzer, A. Beate C.; Lammer, Helmut; Stracke, Barbara; Gebauer, Stefanie; Schreier, Franz; Rauer, Heike

2012-01-01

Abstract Understanding whether M dwarf stars may host habitable planets with Earth-like atmospheres and biospheres is a major goal in exoplanet research. If such planets exist, the question remains as to whether they could be identified via spectral signatures of biomarkers. Such planets may be exposed to extreme intensities of cosmic rays that could perturb their atmospheric photochemistry. Here, we consider stellar activity of M dwarfs ranging from quiet up to strong flaring conditions and investigate one particular effect upon biomarkers, namely, the ability of secondary electrons caused by stellar cosmic rays to break up atmospheric molecular nitrogen (N2), which leads to production of nitrogen oxides (NOx) in the planetary atmosphere, hence affecting biomarkers such as ozone (O3). We apply a stationary model, that is, without a time dependence; hence we are calculating the limiting case where the atmospheric chemistry response time of the biomarkers is assumed to be slow and remains constant compared with rapid forcing by the impinging stellar flares. This point should be further explored in future work with time-dependent models. We estimate the NOx production using an air shower approach and evaluate the implications using a climate-chemical model of the planetary atmosphere. O3 formation proceeds via the reaction O+O2+M→O3+M. At high NOx abundances, the O atoms arise mainly from NO2 photolysis, whereas on Earth this occurs via the photolysis of molecular oxygen (O2). For the flaring case, O3 is mainly destroyed via direct titration, NO+O3→NO2+O2, and not via the familiar catalytic cycle photochemistry, which occurs on Earth. For scenarios with low O3, Rayleigh scattering by the main atmospheric gases (O2, N2, and CO2) became more important for shielding the planetary surface from UV radiation. A major result of this work is that the biomarker O3 survived all the stellar-activity scenarios considered except for the strong case, whereas the biomarker nitrous oxide (N2O) could survive in the planetary atmosphere under all conditions of stellar activity considered here, which clearly has important implications for missions that aim to detect spectroscopic biomarkers. Key Words: M dwarf—Atmosphere—Earth-like—Biomarkers—Stellar cosmic rays. Astrobiology 12, 1109–1122. PMID:23215581

Response of atmospheric biomarkers to NO(x)-induced photochemistry generated by stellar cosmic rays for earth-like planets in the habitable zone of M dwarf stars.

PubMed

Grenfell, John Lee; Grießmeier, Jean-Mathias; von Paris, Philip; Patzer, A Beate C; Lammer, Helmut; Stracke, Barbara; Gebauer, Stefanie; Schreier, Franz; Rauer, Heike

2012-12-01

Understanding whether M dwarf stars may host habitable planets with Earth-like atmospheres and biospheres is a major goal in exoplanet research. If such planets exist, the question remains as to whether they could be identified via spectral signatures of biomarkers. Such planets may be exposed to extreme intensities of cosmic rays that could perturb their atmospheric photochemistry. Here, we consider stellar activity of M dwarfs ranging from quiet up to strong flaring conditions and investigate one particular effect upon biomarkers, namely, the ability of secondary electrons caused by stellar cosmic rays to break up atmospheric molecular nitrogen (N(2)), which leads to production of nitrogen oxides (NO(x)) in the planetary atmosphere, hence affecting biomarkers such as ozone (O(3)). We apply a stationary model, that is, without a time dependence; hence we are calculating the limiting case where the atmospheric chemistry response time of the biomarkers is assumed to be slow and remains constant compared with rapid forcing by the impinging stellar flares. This point should be further explored in future work with time-dependent models. We estimate the NO(x) production using an air shower approach and evaluate the implications using a climate-chemical model of the planetary atmosphere. O(3) formation proceeds via the reaction O+O(2)+M→O(3)+M. At high NO(x) abundances, the O atoms arise mainly from NO(2) photolysis, whereas on Earth this occurs via the photolysis of molecular oxygen (O(2)). For the flaring case, O(3) is mainly destroyed via direct titration, NO+O(3)→NO(2)+O(2), and not via the familiar catalytic cycle photochemistry, which occurs on Earth. For scenarios with low O(3), Rayleigh scattering by the main atmospheric gases (O(2), N(2), and CO(2)) became more important for shielding the planetary surface from UV radiation. A major result of this work is that the biomarker O(3) survived all the stellar-activity scenarios considered except for the strong case, whereas the biomarker nitrous oxide (N(2)O) could survive in the planetary atmosphere under all conditions of stellar activity considered here, which clearly has important implications for missions that aim to detect spectroscopic biomarkers.

Proceedings of the Scientific Data Compression Workshop

NASA Technical Reports Server (NTRS)

Ramapriyan, H. K. (Editor)

1989-01-01

Continuing advances in space and Earth science requires increasing amounts of data to be gathered from spaceborne sensors. NASA expects to launch sensors during the next two decades which will be capable of producing an aggregate of 1500 Megabits per second if operated simultaneously. Such high data rates cause stresses in all aspects of end-to-end data systems. Technologies and techniques are needed to relieve such stresses. Potential solutions to the massive data rate problems are: data editing, greater transmission bandwidths, higher density and faster media, and data compression. Through four subpanels on Science Payload Operations, Multispectral Imaging, Microwave Remote Sensing and Science Data Management, recommendations were made for research in data compression and scientific data applications to space platforms.

Model study of the organic photochemistry in the atmosphere of Mars in the context of the upcoming NOMAD/ExoMars mission

NASA Astrophysics Data System (ADS)

Viscardy, Sébastien; Daerden, Frank; Neary, Lori; García Muñoz, Antonio; Carine Vandaele, Ann

2017-04-01

Several detections of atmospheric methane on Mars have been reported over the last years (Krasnopolsky et al., Icarus, 2004, Formisano et al., Science, 2004, Mumma et al., Science, 2009, Fonti and Marzo, A&A, 2010 , Webster et al., Science, 2015). However those results have been disputed (Zahnle et al., Icarus, 2011) given that the observed lifetime of methane is apparently several orders of magnitude shorter than expected by the known photochemistry (Lefèvre and Forget, Nature, 2009). Until now it remains unclear whether a sink process has still to be discovered or the photochemistry itself is not fully well described. The NOMAD instrument onboard the ExoMars Trace Gas Orbiter (Vandaele et al., PSS, 2015, Robert et al., PSS, 2016) is thus expected to provide key information and make one able to better understand the fate of methane on Mars. Furthermore it has been recently shown that, instead of spreading uniformly in the atmosphere, the methane may form transient layers at 40-50 km in height during the first weeks after surface release (Viscardy et al., GRL, 2016). In this context, we aim to reinvestigate the organic photochemistry using a 3D Global Circulation Model (GCM) in the light of this result. In addition, it has been suggested that there could be a simultaneous release of methane and water vapor (Mumma et al., Science, 2009), e.g. resulting from the destabilization of methane clathrate hydrates. We will thus study how much this can affect the evolution of the atmospheric methane.

An Overview of Snow Photochemistry: Evidence, Mechanisms and Impacts

NASA Technical Reports Server (NTRS)

Grannas, A. M.; Jones, A. E.; Dibb, J.; Ammann, M.; Anastasio, C.; Beine, H. J.; Bergin, M.; Bottenheim, J.; Boxe, C. S.; Carver, G.;

Nitrogen Starvation Induced Oxidative Stress in an Oil-Producing Green Alga Chlorella sorokiniana C3

PubMed Central

He, Chen-Liu; Wang, Qiang

2013-01-01

Microalgal lipid is one of the most promising feedstocks for biodiesel production. Chlorella appears to be a particularly good option, and nitrogen (N) starvation is an efficient environmental pressure used to increase lipid accumulation in Chlorella cells. The effects of N starvation of an oil-producing wild microalga, Chlorella sorokiniana C3, on lipid accumulation were investigated using thin layer chromatography (TLC), confocal laser scanning microscopy (CLSM) and flow cytometry (FCM). The results showed that N starvation resulted in lipid accumulation in C. sorokiniana C3 cells, oil droplet (OD) formation and significant lipid accumulation in cells were detected after 2 d and 8 d of N starvation, respectively. During OD formation, reduced photosynthetic rate, respiration rate and photochemistry efficiency accompanied by increased damage to PSII were observed, demonstrated by chlorophyll (Chl) fluorescence, 77K fluorescence and oxygen evolution tests. In the mean time the rate of cyclic electron transportation increased correspondingly to produce more ATP for triacylglycerols (TAGs) synthesis. And 0.5 d was found to be the turning point for the early stress response and acclimation of cells to N starvation. Increased level of membrane peroxidation was also observed during OD formation, and superoxide dismutase (SOD), peroxide dismutase (POD) and catalase (CAT) enzyme activity assays suggested impaired reactive oxygen species (ROS) scavenging ability. Significant neutral lipid accumulation was also observed by artificial oxidative stress induced by H2O2 treatment. These results suggested coupled neutral lipid accumulation and oxidative stress during N starvation in C. sorokiniana C3. PMID:23874918

Probing Titan's Complex Atmospheric Chemistry Using the Atacama Large Millimeter/Submillimeter Array

NASA Technical Reports Server (NTRS)

Cordiner, Martin A.; Nixon, Conor; Charnley, Steven B.; Teanby, Nick; Irwin, Pat; Serigano, Joseph; Palmer, Maureen; Kisiel, Zbigniew

2015-01-01

Titan is Saturn's largest moon, with a thick (1.45 bar) atmosphere composed primarily of molecular nitrogen and methane. Atmospheric photochemistry results in the production of a wide range of complex organic molecules, including hydrocarbons, nitriles, aromatics and other species of possible pre-biotic relevance. Titan's carbon-rich atmosphere may be analogous to that of primitive terrestrial planets throughout the universe, yet its origin, evolution and complete chemical inventory are not well understood. Here we present spatially-resolved maps of emission from C2H5CN, HNC, HC3N, CH3CN and CH3CCH in Titan's atmosphere, observed using the Atacama Large Millimeter/submillimeter Array (ALMA) in 2012-2013. These data show previously-undetected spatial structures for the observed species and provide the first spectroscopic detection of C2H5CN on Titan. Our maps show spatially resolved peaks in Titan's northern and southern hemispheres, consistent with photochemical production and transport in the upper atmosphere followed by subsidence over the poles. The HNC emission peaks are offset from the polar axis, indicating that Titan's mesosphere may be more longitudinally variable than previously thought.

Ultraviolet photochemistry of cyanoacetylene: Application to Titan. [Abstract only

NASA Technical Reports Server (NTRS)

Clarke, D. W.; Ferris, J. P.

1994-01-01

Cyanoacetylene is believed to have had a central role in the formation of the pyrimidines essential for RNA synthesis leading to the origin of life on Earth. Cyanoacetylene has also been detected on Titan, Saturn's largest moon, and the only moon in the solar system that possesses a dense atmosphere. It is generally accepted that photochemistry plays a major role in the formation of the complex organic molecules and aerosols found in Titan's atmosphere. Because of its long wavelength absorption and low dissociation threshold it is expected that cyanoacetylene is an important part of these photochemical processes. Since cyanoacetylene would also have been subject to ultraviolet light in the atmosphere of early Earth, an investigation of cyanoacetylene photochemistry on Titan might lead to a better understanding of both the photochemical reactions occurring on primitive earth and the processes of chemical evolution as they occur in planetary atmospheres. The effects of irradiation wavelength, mixing with Titan's atmospheric gases, reducing the temperature and lowering cyanoacetylene partial pressures on product formation and polymer composition have been determined with the ultimate goal of understanding the chemical transformations taking place in Titan's atmosphere.

Contribution of nitrated phenols to wood burning brown carbon light absorption in Detling, United Kingdom during winter time.

PubMed

Mohr, Claudia; Lopez-Hilfiker, Felipe D; Zotter, Peter; Prévôt, André S H; Xu, Lu; Ng, Nga L; Herndon, Scott C; Williams, Leah R; Franklin, Jonathan P; Zahniser, Mark S; Worsnop, Douglas R; Knighton, W Berk; Aiken, Allison C; Gorkowski, Kyle J; Dubey, Manvendra K; Allan, James D; Thornton, Joel A

2013-06-18

We show for the first time quantitative online measurements of five nitrated phenol (NP) compounds in ambient air (nitrophenol C6H5NO3, methylnitrophenol C7H7NO3, nitrocatechol C6H5NO4, methylnitrocatechol C7H7NO4, and dinitrophenol C6H4N2O5) measured with a micro-orifice volatilization impactor (MOVI) high-resolution chemical ionization mass spectrometer in Detling, United Kingdom during January-February, 2012. NPs absorb radiation in the near-ultraviolet (UV) range of the electromagnetic spectrum and thus are potential components of poorly characterized light-absorbing organic matter ("brown carbon") which can affect the climate and air quality. Total NP concentrations varied between less than 1 and 98 ng m(-3), with a mean value of 20 ng m(-3). We conclude that NPs measured in Detling have a significant contribution from biomass burning with an estimated emission factor of 0.2 ng (ppb CO)(-1). Particle light absorption measurements by a seven-wavelength aethalometer in the near-UV (370 nm) and literature values of molecular absorption cross sections are used to estimate the contribution of NP to wood burning brown carbon UV light absorption. We show that these five NPs are potentially important contributors to absorption at 370 nm measured by an aethalometer and account for 4 ± 2% of UV light absorption by brown carbon. They can thus affect atmospheric radiative transfer and photochemistry and with that climate and air quality.

Photochemistry of Fe:H2O Adducts in Argon Matrixes: A Combined Experimental and Theoretical Study in the Mid-IR and UV-Visible Regions.

PubMed

Deguin, Vincent; Mascetti, Joëlle; Simon, Aude; Ben Amor, Nadia; Aupetit, Christian; Latournerie, Sandra; Noble, Jennifer A

2018-01-18

The photochemistry of Fe:H 2 O adducts is of interest in fields as diverse as catalysis and astrochemistry. Industrially, iron can be used as a catalyst to convert H 2 O to H 2 , whereas in the interstellar medium it may be an important component of dust grains, influencing the chemistry on their icy surfaces. This study consisted of the deposition and spectral characterization of binary systems of atomic iron with H 2 O in cryogenic argon matrixes. In this way, we were able to obtain information about the interaction of the two species; we observed the formation of adducts of iron monomers and dimers with water molecules in the mid-IR and UV-visible spectral domains. Upon irradiation with a UV radiation source, the iron species were inserted into the water molecules to form HFeOH and HFe 2 OH, leading in some cases to the formation of FeO possibly accompanied by the production of H 2 . DFT and correlated multireference wave function calculations confirmed our attributions. This combination of IR and UV-visible spectroscopy with theoretical calculations allowed us to determine, for the first time, the spectral characteristics of iron adducts and their photoproducts in the UV-visible and in the OH stretching region of the mid-IR domain.

A Surface Science Perspective on TiO2 Photocatalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Henderson, Michael A.

2011-06-15

The field of surface science provides a unique approach to understanding bulk, surface and interfacial phenomena occurring during TiO2 photochemistry and photocatalysis. This review highlights, from a surface science perspective, recent literature providing molecular-level insights into phonon-initiated events on TiO2 surfaces obtained in seven key scientific issues: (1) photon absorption, (2) charge transport and trapping, (3) electron transfer dynamics, (4) the adsorbed state, (5) mechanisms, (6) poisons and promoters, and (7) phase and form.

Uranium azide photolysis results in C-H bond activation and provides evidence for a terminal uranium nitride

NASA Astrophysics Data System (ADS)

Thomson, Robert K.; Cantat, Thibault; Scott, Brian L.; Morris, David E.; Batista, Enrique R.; Kiplinger, Jaqueline L.

2010-09-01

Uranium nitride [U≡N]x is an alternative nuclear fuel that has great potential in the expanding future of nuclear power; however, very little is known about the U≡N functionality. We show, for the first time, that a terminal uranium nitride complex can be generated by photolysis of an azide (U-N=N=N) precursor. The transient U≡N fragment is reactive and undergoes insertion into a ligand C-H bond to generate new N-H and N-C bonds. The mechanism of this unprecedented reaction has been evaluated through computational and spectroscopic studies, which reveal that the photochemical azide activation pathway can be shut down through coordination of the terminal azide ligand to the Lewis acid B(C6F5)3. These studies demonstrate that photochemistry can be a powerful tool for inducing redox transformations for organometallic actinide complexes, and that the terminal uranium nitride fragment is reactive, cleaving strong C-H bonds.

Meridional Variations of C2H2 and C2H6 in Jupiter's Atmosphere from Cassini CIRS Infrared Spectra

NASA Technical Reports Server (NTRS)

Nixon, C. A.; Achterberg, R. K.; Conrath, B. J.; Irwin, P. G. J.; Fouchet, T.; Parrish, P. D.; Romani, P. N.; Abbas, M.; LeClair, A.; Strobel, D.

2004-01-01

Hydrocarbons such as acetylene (C2H2) and ethane (C2H6) are important tracers in Jupiter's atmosphere, constraining our models of the chemical and dynamical processes. However, our knowledge of the vertical and meridional variations of their abundances has remained sparse. During the flyby of the Cassini spacecraft in December 2000, the Composite Infrared Spectrometer (CIRS) instrument was used to map the spatial variation of emissions from 10-1400 cm(sup -1) (1000-7 microns). In this paper we analyze a zonally-averaged set of CIRS spectra taken at the highest (0.5 cm(sup -1)) resolution, to infer atmospheric temperatures in the stratosphere at 0.5-20 mbar via the v4 band of CH4, and in the troposphere at 150-400 mbar, via the H2 absorption at 600-800 cm(sup -1). Simultaneously, we retrieve the abundances of C2H2 and C2H6 via the v5 and vg bands respectively. Tropospheric absorption and stratospheric emission are highly anti-correlated at the CIRS resolution, introducing a non-uniqueness into the retrievals, such that vertical gradient and column abundance cannot both be found without additional constraints. Assuming profile gradients from photochemical calculations, we show that the column abundance of C2H2 decreases sharply towards the poles by a factor approximately 4, while C2H6 is unchanged in the north and increasing in the south, by a factor approximately 1.8. An explanation for the meridional trends is proposed in terms of a combination of photochemistry and dynamics. Poleward, the decreasing UV flux is predicted to decrease the abundances of C2H2 and C2H6 by factors 2.7 and 3.5 respectively at a latitude 70 deg. However, the lifetime of C2H6 in the stratosphere (5 x 10(exp 9)) is much longer than the dynamical timescale for meridional motions inferred from SL-9 debris (5 x 10(exp 8 s)), and therefore the constant or rising abundance towards high latitudes likely indicates that meridional mixing dominates over photochemical effects. For C2H2, the opposite occurs, with the relatively short photochemical lifetime (3 x 10(exp 7 s)), compared to meridional mixing times, ensuring that the expected photochemical trends are visible.

Isotopic Ratios in Titan's Methane: Measurements and Modeling

NASA Technical Reports Server (NTRS)

Nixon, C. A.; Temelso, B.; Vinatier, S.; Teanby, N. A.; Bezard, B.; Achterberg, R. K.; Mandt, K. E.; Sherrill, C. D.; Irwin, P. G.; Jennings, D. E.;

Collaborative Research: Atmospheric Pressure Microplasma Chemistry-Photon Synergies Final Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Graves, David

Combining the effects of low temperature, atmospheric pressure microplasmas and microplasma photon sources shows greatly expanded range of applications of each of them. The plasma sources create active chemical species and these can be activated further by addition of photons and associated photochemistry. There are many ways to combine the effects of plasma chemistry and photochemistry, especially if there are multiple phases present. The project combines construction of appropriate test experimental systems, various spectroscopic diagnostics and mathematical modeling.

Role of pigmentation in protecting Aspergillus niger conidiospores against pulsed light radiation.

PubMed

Esbelin, Julia; Mallea, Sabine; Ram, Arthur F; Carlin, Frédéric

2013-01-01

The photoprotective potential of fungus pigments was investigated by irradiating conidiospores of three Aspergillus niger strains possessing the same genetic background, but differing in their degree of pigmentation with pulsed light (PL) and monochromatic (254 nm) UV-C radiation. Spores of A. niger MA93.1 and JHP1.1 presenting, respectively, a fawn and a white pigmentation were more sensitive to PL and continuous UV-C radiation than the wild-type A. niger strain N402 possessing a dark pigment. Both spores of the dark A. niger N402 and the fawn-color mutant were equally resistant to moist heat at 56°C while spores of the white-color mutant were highly sensitive. These results indicate that melanin protects pigmented spores of A. niger from PL. © 2013 Wiley Periodicals, Inc. Photochemistry and Photobiology © 2013 The American Society of Photobiology.

Effects of multiple scattering and surface albedo on the photochemistry of the troposphere

NASA Technical Reports Server (NTRS)

Augustsson, T. R.; Tiwari, S. N.

1981-01-01

The effect of treatment of incoming solar radiation on the photochemistry of the troposphere is discussed. A one dimensional photochemical model of the troposphere containing the species of the nitrogen, oxygen, carbon, hydrogen, and sulfur families was developed. The vertical flux is simulated by use of the parameterized eddy diffusion coefficients. The photochemical model is coupled to a radiative transfer model that calculates the radiation field due to the incoming solar radiation which initiates much of the photochemistry of the troposphere. Vertical profiles of tropospheric species were compared with the Leighton approximation, radiative transfer, matrix inversion model. The radiative transfer code includes the effects of multiple scattering due to molecules and aerosols, pure absorption, and surface albedo on the transfer of incoming solar radiation. It is indicated that significant differences exist for several key photolysis frequencies and species number density profiles between the Leighton approximation and the profiles generated with, radiative transfer, matrix inversion technique. Most species show enhanced vertical profiles when the more realistic treatment of the incoming solar radiation field is included

Effects of multiple scattering and surface albedo on the photochemistry of the troposphere. Final report, period ending 30 Nov 1981

DOE Office of Scientific and Technical Information (OSTI.GOV)

Augustsson, T.R.; Tiwari, S.N.

The effect of treatment of incoming solar radiation on the photochemistry of the troposphere is discussed. A one dimensional photochemical model of the troposphere containing the species of the nitrogen, oxygen, carbon, hydrogen, and sulfur families was developed. The vertical flux is simulated by use of the parameterized eddy diffusion coefficients. The photochemical model is coupled to a radiative transfer model that calculates the radiation field due to the incoming solar radiation which initiates much of the photochemistry of the troposphere. Vertical profiles of tropospheric species were compared with the Leighton approximation, radiative transfer, matrix inversion model. The radiative transfermore » code includes the effects of multiple scattering due to molecules and aerosols, pure absorption, and surface albedo on the transfer of incoming solar radiation. It is indicated that significant differences exist for several key photolysis frequencies and species number density profiles between the Leighton approximation and the profiles generated with, radiative transfer, matrix inversion technique. Most species show enhanced vertical profiles when the more realistic treatment of the incoming solar radiation field is included« less

On the relationship between the greenhouse effect, atmospheric photochemistry, and species distribution

NASA Technical Reports Server (NTRS)

Callis, L. B.; Boughner, R. E.; Natarajan, M.

1983-01-01

The coupling that exists between infrared opacity changes and tropospheric (and to a lesser extent stratospheric) chemistry is explored in considerable detail, and the effects arising from various perturbations are examined. The studies are carried out with a fully coupled one-dimensional radiative-convective-photochemical model (RCP) that extends from the surface to 53.5 km and has the capability of calculating surface temperature changes due to both chemical and radiative perturbations. The model encompasses contemporary atmospheric chemistry and photochemistry involving the O(x), HO(x), NO(x), and Cl(x) species.

Lightning chemistry on Earth-like exoplanets

NASA Astrophysics Data System (ADS)

Ardaseva, Aleksandra; Rimmer, Paul B.; Waldmann, Ingo; Rocchetto, Marco; Yurchenko, Sergey N.; Helling, Christiane; Tennyson, Jonathan

2017-09-01

We present a model for lightning shock-induced chemistry that can be applied to atmospheres of arbitrary H/C/N/O chemistry, hence for extrasolar planets and brown dwarfs. The model couples hydrodynamics and the STAND2015 kinetic gas-phase chemistry. For an exoplanet analogue to the contemporary Earth, our model predicts NO and NO2 yields in agreement with observation. We predict height-dependent mixing ratios during a storm soon after a lightning shock of NO ≈10-3 at 40 km and NO2 ≈10-4 below 40 km, with O3 reduced to trace quantities (≪10-10). For an Earth-like exoplanet with a CO2/N2 dominated atmosphere and with an extremely intense lightning storm over its entire surface, we predict significant changes in the amount of NO, NO2, O3, H2O, H2 and predict a significant abundance of C2N. We find that, for the Early Earth, O2 is formed in large quantities by lightning but is rapidly processed by the photochemistry, consistent with previous work on lightning. The chemical effect of persistent global lightning storms are predicted to be significant, primarily due to NO2, with the largest spectral features present at ˜3.4 and ˜6.2 μm. The features within the transmission spectrum are on the order of 1 ppm and therefore are not likely detectable with the James Webb Space Telescope. Depending on its spectral properties, C2N could be a key tracer for lightning on Earth-like exoplanets with a N2/CO2 bulk atmosphere, unless destroyed by yet unknown chemical reactions.

Photosynthetic Photovoltaic Cells

DTIC Science & Technology

2007-06-21

OFF (T). B. SPR detection of the binding of Ni2+, RC, and cytochrome to NTA surface. The arrows indicate the periods of time ON (t) and OFF (1) when...photosynthesis. Structure and spectroscopy of reaction centers of purple bacteria . Physics Reports-Review Section of Physics Letters, 1997. 287(1-2): p. 2-247. 7...photosynthetic bacteria reaction centers. Journal of Photochemistry and Photobiology a-Chemistry, 1997. 111(1-3): p. 111-138. 27. Beratan, D.N., J.N. Betts, and

What can meteorites tell us about comets?

NASA Technical Reports Server (NTRS)

Anders, Edward

1986-01-01

Cometary silicates, carbon, and volatiles are reviewed using data from the Halley probes, interplanetary dust particles, and cometary spectra. The origins of anhydrous Fe(2+)-bearing silicates; whether hydrated silicates, if present, were made by gaseous or liquid H2O3; sources of organic compounds: ion-molecule reactions, photochemistry, grain catalysis; sources of CO2 and of organic polymers; and interstellar molecules and grains in comets are discussed.

Formic acid interaction with the uranyl(VI) ion: structural and photochemical characterization.

PubMed

Lucks, Christian; Rossberg, André; Tsushima, Satoru; Foerstendorf, Harald; Fahmy, Karim; Bernhard, Gert

2013-10-07

Complex formation between the uranyl(VI) ion and formic acid was studied by infrared absorption (IR) and X-ray absorption (EXAFS) spectroscopy as well as density functional theory (DFT) calculations. In contrast to the acetate ion which forms exclusively a bidentate complex with uranyl(VI), the formate ion binds to uranyl(VI) in a unidentate fashion. The photochemistry of the uranyl(VI)-formic acid system was explored by DFT calculations and photoreduction of uranyl(VI) in the presence of formic acid was found to occur via an intermolecular process, that is, hydrogen abstraction from hydrogenformate by the photo-excited uranyl(VI). There is no photo-induced decarboxylation of uranyl(VI) formate via an intramolecular process, presumably due to lack of a C=C double bond.

Modeling C1-C4 Alkyl Nitrate Photochemistry and Their Impacts on O3 Production in Urban and Suburban Environments of Hong Kong

NASA Astrophysics Data System (ADS)

Lyu, X. P.; Guo, H.; Wang, N.; Simpson, I. J.; Cheng, H. R.; Zeng, L. W.; Saunders, S. M.; Lam, S. H. M.; Meinardi, S.; Blake, D. R.

2017-10-01

As intermediate products of photochemical reactions, alkyl nitrates (RONO2) regulate ozone (O3) formation. In this study, a photochemical box model incorporating master chemical mechanism well reproduced the observed RONO2 at an urban and a mountainous site, with index of agreement in the range of 0.66-0.73. The value 0.0003 was identified to be the most appropriate branching ratio for C1 RONO2, with the error less than 50%. Although levels of the parent hydrocarbons and nitric oxide (NO) were significantly higher at the urban site than the mountainous site, the production of C2-C3 RONO2 was comparable to or even lower than at the mountainous site, due to the lower concentrations of oxidative radicals in the urban environment. Based on the profiles of air pollutants at the mountainous site, the formation of C2-C4 RONO2 was limited by NOx (volatile organic compounds (VOCs)) when total volatile organic compounds (TVOCs)/NOx was higher (lower) than 10.0 ± 0.4 parts per billion by volume (ppbv)/ppbv. This dividing ratio decreased (p < 0.05) to 8.7 ± 0.4 ppbv/ppbv at the urban site, mainly due to the different air pollutant profiles at the two sites. For the formation of C1 RONO2, the NOx-limited regime extended the ratio of TVOCs/NOx to as low as 2.4 ± 0.2 and 3.1 ± 0.1 ppbv/ppbv at the mountainous and urban site, respectively. RONO2 formation led to a decrease of simulated O3, with reduction efficiencies (O3 reduction/RONO2 production) of 4-5 parts per trillion by volume (pptv)/pptv at the mountainous site and 3-4 pptv/pptv at the urban site. On the other hand, the variations of simulated O3 induced by RONO2 degradation depended upon the regimes controlling O3 formation and the relative abundances of TVOCs and NOx.

Synthesis of monodisperse silica microspheres and modification with diazoresin for mixed-mode ultra high performance liquid chromatography separations.

PubMed

Cong, Hailin; Yu, Bing; Tian, Chao; Zhang, Shuai; Yuan, Hua

2017-11-01

Monodisperse silica particles with average diameters of 1.9-2.9 μm were synthesized by a modified Stöber method, in which tetraethyl orthosilicate was continuously supplied to the reaction mixture containing KCl electrolyte, water, ethanol, and ammonia. The obtained silica particles were modified by self-assembly with positively charged photosensitive diazoresin on the surface. After treatment with ultraviolet light, the ionic bonding between silica and diazoresin was converted into covalent bonding through a unique photochemistry reaction of diazoresin. Depending on the chemical structure of diazoresin and mobile phase composition, the diazoresin-modified silica stationary phase showed different separation mechanisms, including reversed phase and hydrophilic interactions. Therefore, a variety of baseline separation of benzene analogues and organic acids was achieved by using the diazoresin-modified silica particles as packing materials in ultra high performance liquid chromatography. According to the π-π interactional difference between carbon rings of fullerenes and benzene rings of diazoresin, C 60 and C 70 were also well separated by ultra-high performance liquid chromatography. Because it has a small size, the ∼2.5 μm monodisperse diazoresin-modified silica stationary phase shows ultra-high efficiency compared with the commercial C 18 -silica high-performance liquid chromatography stationary phase with average diameters of ∼5 μm. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct Aqueous Photochemistry of Isoprene High-NOx Secondary Organic Aerosol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, Tran B.; Laskin, Alexander; Laskin, Julia

2012-05-17

Secondary organic aerosol (SOA) generated from the high-NOx photooxidation of isoprene was dissolved in water and irradiated with {lambda} > 290 nm light to simulate direct photolytic processing of organics in atmospheric water droplets. High-resolution mass spectrometry was used to characterize the composition at four time intervals (0, 1, 2, and 4 h). Photolysis resulted in the decomposition of high molecular weight (MW) oligomers, reducing the average length of organics by 2 carbon units. Approximately 65% by count of SOA molecules decomposed during photolysis, accompanied by the formation of new products. An average of 30 % of the organic massmore » was modified after 4 h of direct photolysis. In contrast, only a small fraction of the mass (<2 %), belonging primarily to organic nitrates, decomposed in the absence of irradiation by hydrolysis. We observed a statistically-significant increase in average O/C, decrease in H/C, and increase in N/C ratios resulting from photolysis. Furthermore, the concentration of aromatic compounds increased significantly during photolysis. Approximately 10 % of photodegraded compounds and 50 % of the photoproducts contain nitrogen. Organic nitrates and multifunctional oligomers were identified as compounds degraded by photolysis. Low-MW 0N (compounds with 0 nitrogen atoms in their structure) and 2N compounds were the dominant photoproducts. Fragmentation experiments using tandem mass spectrometry (MSn, n = 2-3) indicate that the 2N products are likely heterocyclic/aromatic and are tentatively identified as furoxans. Although the exact mechanism is unclear, these 2N heterocyclic compounds are produced by reactions between photochemically-formed aqueous NOx species and SOA organics.« less

[Effects of water stress and temperature on gas exchange and chlorophyll fluorescence of Sinocalycanthus chinensis leaves].

PubMed

Ke, Shi-sheng; Jin, Ze-xin

2008-01-01

Sinocalycanthus chinensis is an endangered species in Sinocalycanthus, and only distributed in Zhejiang Province of China. This paper studied the photosynthetic responses of 2-year-old pot-cultured S. chinensis to different levels of water stress and temperature. The results indicated that under mild and moderate water stress, the net photosynthetic rate (Pn) of S. chinensis leaves was decreased to 92.3% and 74.3% of the control, respectively, which was mainly attributed to stomatal limitation; and under severe water stress, the Pn was decreased to 44.4% of the control, which might be mainly linked to non-stomatal limitation. The appropriate temperature for S. chinensis photosynthesis was from 20 degrees C to 28 degrees C. At 39 degrees C, the Pn, water use efficiency (WUE), and maximal photochemistry efficiency (Fv/Fm) were decreased significantly, while the dark respiration rate (Rd) and transpiration rate (Tr) were enhanced significantly. With increasing water stress and temperature, some photosynthetic parameters including light saturation point (LSP), apparent quantum yield (AQY) and maximal CO2 assimilation rate (Pmax) decreased to certain extents, while light compensation point (LCP) increased, suggesting that both severe water stress and higher temperature were the important environmental factors affecting the survival of S. chinensis.

Using the Flipchem Photochemistry Model When Fitting Incoherent Scatter Radar Data

NASA Astrophysics Data System (ADS)

Reimer, A. S.; Varney, R. H.

2017-12-01

The North face Resolute Bay Incoherent Scatter Radar (RISR-N) routinely images the dynamics of the polar ionosphere, providing measurements of the plasma density, electron temperature, ion temperature, and line of sight velocity with seconds to minutes time resolution. RISR-N does not directly measure ionospheric parameters, but backscattered signals, recording them as voltage samples. Using signal processing techniques, radar autocorrelation functions (ACF) are estimated from the voltage samples. A model of the signal ACF is then fitted to the ACF using non-linear least-squares techniques to obtain the best-fit ionospheric parameters. The signal model, and therefore the fitted parameters, depend on the ionospheric ion composition that is used [e.g. Zettergren et. al. (2010), Zou et. al. (2017)].The software used to process RISR-N ACF data includes the "flipchem" model, which is an ion photochemistry model developed by Richards [2011] that was adapted from the Field LineInterhemispheric Plasma (FLIP) model. Flipchem requires neutral densities, neutral temperatures, electron density, ion temperature, electron temperature, solar zenith angle, and F10.7 as inputs to compute ion densities, which are input to the signal model. A description of how the flipchem model is used in RISR-N fitting software will be presented. Additionally, a statistical comparison of the fitted electron density, ion temperature, electron temperature, and velocity obtained using a flipchem ionosphere, a pure O+ ionosphere, and a Chapman O+ ionosphere will be presented. The comparison covers nearly two years of RISR-N data (April 2015 - December 2016). Richards, P. G. (2011), Reexamination of ionospheric photochemistry, J. Geophys. Res., 116, A08307, doi:10.1029/2011JA016613.Zettergren, M., Semeter, J., Burnett, B., Oliver, W., Heinselman, C., Blelly, P.-L., and Diaz, M.: Dynamic variability in F-region ionospheric composition at auroral arc boundaries, Ann. Geophys., 28, 651-664, https://doi.org/10.5194/angeo-28-651-2010, 2010.Zou, S., D. Ozturk, R. Varney, and A. Reimer (2017), Effects of sudden commencement on the ionosphere: PFISR observations and global MHD simulation, Geophys. Res. Lett., 44, 3047-3058, doi:10.1002/2017GL072678.

Photochemistry of Pluto's Atmosphere

NASA Technical Reports Server (NTRS)

Krasnopolsky, Vladimir A.

1999-01-01

This work include studies of two problems: (1) Modeling thermal balance, structure. and escape processes in Pluto's upper atmosphere. This study has been completed in full. A new method, of analytic solution for the equation of hydrodynamic flow from in atmosphere been developed. It was found that the ultraviolet absorption by methane which was previously ignored is even more important in Pluto's thermal balance than the extreme ultraviolet absorption by nitrogen. Two basic models of the lower atmosphere have been suggested, with a tropopause and a planetary surface at the bottom of the stellar occultation lightcurve, respectively, Vertical profiles, of temperature, density, gas velocity, and the CH4 mixing ratio have been calculated for these two models at low, mean, and high solar activity (six models). We prove that Pluto' " s atmosphere is restricted to 3060-4500 km, which makes possible a close flyby of future spacecraft. Implication for Pluto's evolution have also been discussed. and (2) Modeling of Pluto's photochemistry. Based on the results of (1), we have made some changes in the basic continuity equation and in the boundary conditions which reflect a unique can of hydrodynamic escape and therefore have not been used in modeling of other planetary atmospheres. We model photochemistry of 44 neutral and 23 ion species. This work required solution of a set of 67 second-order nonlinear ordinary differential equations. Two models have been developed. Each model consists of the vertical profiles for 67 species, their escape and precipitation rates. These models predict the chemical structure and basic chemical processes in the current atmosphere and possible implication of these processes for evolution. This study has also been completed in full.

Seasonal/Latitudinal Models of Stratospheric Photochemistry on Saturn

NASA Astrophysics Data System (ADS)

Moses, J. I.; Greathouse, T. K.

2004-11-01

To date, most investigations of stratospheric photochemistry on the outer planets have involved one-dimensional (1-D) ``global-average'' or single-latitude models for a single season. With Cassini CIRS poised to map hydrocarbon distributions across Saturn, and with advances in detector technology and telescope size for Earth-based observations allowing composition and temperatures to be derived as a function of latitude, we are now in a position to evaluate the effectiveness of 1-D models in describing the stratospheric composition. Are 2-D models that include meridional transport necessary to reproduce the observed hydrocarbon latitudinal distributions, or can 1-D seasonal models provide an accurate description? In order to evaluate these questions, we have developed a realistic, time-variable, 1-D seasonal model for stratospheric photochemistry on Saturn. The model accounts for variations in orbital position and in ultraviolet flux due to solar-cycle variations and ring-shadow effects. The results for one Saturnian year, starting at Ls = 0o in 1980 and running until the next vernal equinox in 2009, are presented for numerous latitudes. Due to the long vertical diffusion time scale at pressures greater than ˜1 mbar, we find that seasonal effects are more pronounced at high altitudes. In addition, a phase lag between insolation and chemical response increases with increasing pressure. In the summer hemisphere, hydrocarbon abundances do not exhibit much variation with latitude because the increase in the length of the day with increasing latitude counterbalances the increasing solar zenith angle, causing the daily-averaged insolation to remain nearly constant over a wide range of latitudes. Latitudinal variations are more pronounced during other seasons. We compare our model results with various observations.

Dissociation energy and photochemistry of NO[sub 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Davis, H.F.; Kim, Bongsoo; Johnston, H.S.

1993-03-11

The photodissociation of NO[sub 3] was studied using the method of molecular beam photofragmentation translational spectroscopy. The existence of two photodissociation channels was confirmed under collision-free conditions. At excitation energies below D[sub 0](O-NO[sub 2]) for internally cold NO[sub 3], the authors observe a large quantum yield (0.70 [+-] 0.10 at 588 nm) for a concerted three-center rearrangement resulting in NO([sup 2][Pi]) + O[sub 2]([sup 3][Sigma][sub g][sup [minus

Allelochemical stress inhibits growth, leaf water relations, PSII photochemistry, non-photochemical fluorescence quenching, and heat energy dissipation in three C3 perennial species

PubMed Central

Hussain, M. Iftikhar; Reigosa, Manuel J.

2011-01-01

In this study, the effect of two allelochemicals, benzoxazolin-2(3H)-one (BOA) and cinnamic acid (CA), on different physiological and morphological characteristics of 1-month-old C3 plant species (Dactylis glomerata, Lolium perenne, and Rumex acetosa) was analysed. BOA inhibited the shoot length of D. glomerata, L. perenne, and R. acetosa by 49%, 19%, and 19% of the control. The root length of D. glomerata, L. perenne, and R. acetosa growing in the presence of 1.5 mM BOA and CA was decreased compared with the control. Both allelochemicals (BOA, CA) inhibited leaf osmotic potential (LOP) in L. perenne and D. glomerata. In L. perenne, Fv/Fm decreased after treatment with BOA (1.5 mM) while CA (1.5 mM) also significantly reduced Fv/Fm in L. perenne. Both allelochemicals decreased ΦPSII in D. glomerata and L. perenne within 24 h of treatment, while in R. acetosa, ΦPSII levels decreased by 72 h following treatment with BOA and CA. There was a decrease in qP and NPQ on the first, fourth, fifth, and sixth days after treatment with BOA in D. glomerata, while both allelochemicals reduced the qP level in R. acetosa. There was a gradual decrease in the fraction of light absorbed by PSII allocated to PSII photochemistry (P) in R. acetosa treated with BOA and CA. The P values in D. glomerata were reduced by both allelochemicals and the portion of absorbed photon energy that was thermally dissipated (D) in D. glomerata and L. perenne was decreased by BOA and CA. Photon energy absorbed by PSII antennae and trapped by ‘closed’ PSII reaction centres (E) was decreased after CA exposure in D. glomerata. BOA and CA (1.5 mM concentration) decreased the leaf protein contents in all three perennial species. This study provides new understanding of the physiological and biochemical mechanisms of action of BOA and CA in one perennial dicotyledon and two perennial grasses. The acquisition of such knowledge may ultimately provide a rational and scientific basis for the design of safe and effective herbicides. PMID:21659663

Regulation of energy partitioning and alternative electron transport pathways during cold acclimation of lodgepole pine is oxygen dependent.

PubMed

Savitch, Leonid V; Ivanov, Alexander G; Krol, Marianna; Sprott, David P; Oquist, Gunnar; Huner, Norman P A

2010-09-01

Second year needles of Lodgepole pine (Pinus contorta L.) were exposed for 6 weeks to either simulated control summer ['summer'; 25 °C/250 photon flux denisty (PFD)], autumn ('autumn'; 15°C/250 PFD) or winter conditions ('winter'; 5 °C/250 PFD). We report that the proportion of linear electron transport utilized in carbon assimilation (ETR(CO2)) was 40% lower in both 'autumn' and 'winter' pine when compared with the 'summer' pine. In contrast, the proportion of excess photosynthetic linear electron transport (ETR(excess)) not used for carbon assimilation within the total ETR(Jf) increased by 30% in both 'autumn' and 'winter' pine. In 'autumn' pine acclimated to 15°C, the increased amounts of 'excess' electrons were directed equally to 21  kPa O2-dependent and 2  kPa O2-dependent alternative electron transport pathways and the fractions of excitation light energy utilized by PSII photochemistry (Φ(PSII)), thermally dissipated through Φ(NPQ) and dissipated by additional quenching mechanism(s) (Φ(f,D)) were similar to those in 'summer' pine. In contrast, in 'winter' needles acclimated to 5 °C, 60% of photosynthetically generated 'excess' electrons were utilized through the 2  kPa O2-dependent electron sink and only 15% by the photorespiratory (21  kPa O2) electron pathway. Needles exposed to 'winter' conditions led to a 3-fold lower Φ(PSII), only a marginal increase in Φ(NPQ) and a 2-fold higher Φ(f,D), which was O2 dependent compared with the 'summer' and 'autumn' pine. Our results demonstrate that the employment of a variety of alternative pathways for utilization of photosynthetically generated electrons by Lodgepole pine depends on the acclimation temperature. Furthermore, dissipation of excess light energy through constitutive non-photochemical quenching mechanisms is O2 dependent.

Detection and mapping of organic molecules in Titan's atmosphere using ALMA

NASA Astrophysics Data System (ADS)

Cordiner, Martin

2016-06-01

Titan's atmospheric photochemistry results in the production of a wide range of organic molecules, including hydrocarbons, nitriles, aromatics and other complex species of possible pre-biotic relevance. Studies of Titan's atmospheric chemistry thus provide a unique opportunity to explore the origin and evolution of organic matter in primitive (terrestrial) planetary atmospheres. The Atacama Large Millimeter/submillimeter Array (ALMA) is a powerful new facility, well suited to the study of molecular emission from Titan's upper and middle-atmosphere. Results will be presented from our ongoing studies of Titan using ALMA data obtained during the period 2012-2014 [1,2], including detection and mapping of emission from C2H5CN, HNC, HC3N, CH3CN and CH3CCH. In addition, combining data from multiple ALMA Band 6 observations, we obtained high-resolution spectra with unprecedented sensitivity, enabling the first detection of C2H3CN (vinyl cyanide) on Titan, and derived a mean C2H3CN C2H5CN abundance ratio above 300 km of 0.3. Vinyl cyanide has recently been investigated as a possible constituent of (pre-biotic) vesicle membranes in Titan's liquid CH4 oceans [3]. Radiative transfer models and possible chemical formation pathways for the detected molecules will be discussed. ALMA observations provide instantaneous snapshot mapping of Titan's entire Earth-facing hemisphere for gases inaccessible to previous studies, and therefore provide new insights into photochemical production and transport, particularly at higher altitudes. Our maps show spatially resolved peaks in Titan's northern and southern hemispheres, consistent with the molecular distributions found in previous studies at infrared wavelengths by Voyager and Cassini, but high-altitude longitudinal asymmetries in our nitrile data indicate that the mesosphere may be more spatially variable than previously thought.

Destruction of PAHs by X-Rays in circumnuclear regions of AGNs

NASA Astrophysics Data System (ADS)

Monfredini, T.; Wolff, W.; Boechat-Roberty, H. M.; Sales, D. A.; Pastoriza, M. G.

2017-07-01

Emission bands associated with PAH molecules are observed in the direction of some classes of AGNs like Seyfert 2, LINERs and obscured quasars (e.g. Kaneda et al., 2008, Sansigre et al., 2008 and Sales et al. 2013). The molecular stability in these environments suggest the presence of very dense gas (˜ 1023-24 cm-2) to shield the cloud of PAHs against X-ray radiation (Voit, 1992, Tielens, 2011, Sales et al., 2013). We examined the photochemistry of simple PAHs: naphtalene (C10H8), anthracene (C14H10), methyl-anthracene (C15H12) and pyrene (C16H10) at the photon energies of 275 eV, 310 eV, 1900 eV and 2500 eV in order to apply the findings at the AGN scenario. The absolute single and double photoionization and photodissociation cross sections were determined for each molecule at each energy. Their ionization and destruction induced by X-rays were examined in the conditions of the circumnuclear region of NGC 1808, a Seyfert 2 galaxy, where PAH emission was detected at 26 pc from the central object (Sales et al., 2013). It was verified the higher photostability of PAHs without functional groups attached. At higher photon energies, the results suggest a higher production yield of double charged PAHs in comparision with the single charged ones (e.g., 2 × higher for double ionized naphtalene at 2500 eV). The production of double charged molecules increase with the size of the molecules. We also discuss a minimum formation rate of PAH to balance the photodestruction rate and maintain a minimum density for their detection (e.g. 4,0× 10-7 M⊙ year-1 for a column density NH of 1023 cm-2 at 26 pc).

Mapping Vinyl Cyanide and Other Nitriles in Titan’s Atmosphere Using ALMA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lai, J. C.-Y.; Cordiner, M. A.; Nixon, C. A.

Vinyl cyanide (C{sub 2}H{sub 3}CN) is theorized to form in Titan’s atmosphere via high-altitude photochemistry and is of interest regarding the astrobiology of cold planetary surfaces due to its predicted ability to form cell membrane-like structures (azotosomes) in liquid methane. In this work, we follow up on the initial spectroscopic detection of C{sub 2}H{sub 3}CN on Titan by Palmer et al. with the detection of three new C{sub 2}H{sub 3}CN rotational emission lines at submillimeter frequencies. These new, high-resolution detections have allowed for the first spatial distribution mapping of C{sub 2}H{sub 3}CN on Titan. We present simultaneous observations of C{submore » 2}H{sub 5}CN, HC{sub 3}N, and CH{sub 3}CN emission, and obtain the first (tentative) detection of C{sub 3}H{sub 8} (propane) at radio wavelengths. We present disk-averaged vertical abundance profiles, two-dimensional spatial maps, and latitudinal flux profiles for the observed nitriles. Similarly to HC{sub 3}N and C{sub 2}H{sub 5}CN, which are theorized to be short-lived in Titan’s atmosphere, C{sub 2}H{sub 3}CN is most abundant over the southern (winter) pole, whereas the longer-lived CH{sub 3}CN is more concentrated in the north. This abundance pattern is consistent with the combined effects of high-altitude photochemical production, poleward advection, and the subsequent reversal of Titan’s atmospheric circulation system following the recent transition from northern to southern winter. We confirm that C{sub 2}H{sub 3}CN and C{sub 2}H{sub 5}CN are most abundant at altitudes above 200 km. Using a 300 km step model, the average abundance of C{sub 2}H{sub 3}CN is found to be 3.03 ± 0.29 ppb, with a C{sub 2}H{sub 5}CN/C{sub 2}H{sub 3}CN abundance ratio of 2.43 ± 0.26. Our HC{sub 3}N and CH{sub 3}CN spectra can be accurately modeled using abundance gradients above the tropopause, with fractional scale-heights of 2.05 ± 0.16 and 1.63 ± 0.02, respectively.« less

Structure of Full-length Drosophila Cryptochrome

PubMed Central

Zoltowski, Brian D.; Vaidya, Anand T.; Top, Deniz; Widom, Joanne; Young, Michael W.; Crane, Brian R.

2011-01-01

The Cryptochrome/Photolyase (CRY/PL) family of photoreceptors mediates adaptive responses to UV and blue light exposure in all kingdoms of life 1; 2; 3; 4; 5. Whereas PLs function predominantly in DNA repair of cyclobutane pyrimidine dimers (CPDs)and 6-4 photolesions caused by UV radiation, CRYs transduce signals important for growth, development, magnetosensitivity and circadian clocks1; 2; 3; 4; 5. Despite these diverse functions, PLs/CRYs preserve a common structural fold, a dependence on flavin adenine dinucleotide (FAD) and an internal photoactivation mechanism3; 6. However, members of the CRY/PL family differ in the substrates recognized (protein or DNA), photochemical reactions catalyzed and involvement of an antenna cofactor. It is largely unknown how the animal CRYs that regulate circadian rhythms act on their substrates. CRYs contain a variable C-terminal tail that appends the conserved PL homology domain (PHD) and is important for function 7; 8; 9; 10; 11; 12. Herein, we report a 2.3 Å resolution crystal structure of Drosophila CRY with an intact C-terminus. The C-terminal helix docks in the analogous groove that binds DNA substrates in PLs. Conserved Trp536 juts into the CRY catalytic center to mimic PL recognition of DNA photolesions. The FAD anionic semiquinone found in the crystals assumes a conformation to facilitate restructuring of the tail helix. These results help reconcile the diverse functions of the CRY/PL family by demonstrating how conserved protein architecture, and photochemistry can be elaborated into a range of light-driven functions. PMID:22080955

Numerical experiments with a general circulation model concerning the distribution of ozone in the stratosphere

NASA Technical Reports Server (NTRS)

Kurzeja, R. J.; Haggard, K. V.; Grose, W. L.

1984-01-01

The distribution of ozone below 60 km altitude has been simulated in two experiments employing a nine-layer quasi-geostrophic spectral model and linear parameterization of ozone photochemistry, the first of which included thermal and orographic forcing of the planetary scale waves, while the second omitted it. The first experiment exhibited a high latitude winter ozone buildup which was due to a Brewer-Dodson circulation forced by large amplitude (planetary scale) waves in the winter lower stratosphere. Photochemistry was also found to be important down to lower altitudes (20 km) in the summer stratosphere than had previously been supposed.

The molecular physics of photolytic fractionation of sulfur and oxygen isotopes in planetary atmospheres (Invited)

NASA Astrophysics Data System (ADS)

Johnson, M. S.; Schmidt, J. A.; Hattori, S.; Danielache, S.; Meusinger, C.; Schinke, R.; Ueno, Y.; Nanbu, S.; Kjaergaard, H. G.; Yoshida, N.

2013-12-01

Atmospheric photochemistry is able to produce large mass independent anomalies in atmospheric trace gases that can be found in geological and cryospheric records. This talk will present theoretical and experimental investigations of the molecular mechanisms producing photolytic fractionation of isotopes with special attention to sulfur and oxygen. The zero point vibrational energy (ZPE) shift and reflection principle theories are starting points for estimating isotopic fractionation, but these models ignore effects arising from isotope-dependent changes in couplings between surfaces, excited state dynamics, line densities and hot band populations. The isotope-dependent absorption spectra of the isotopologues of HCl, N2O, OCS, CO2 and SO2 have been examined in a series of papers and these results are compared with experiment and ZPE/reflection principle models. Isotopic fractionation in planetary atmospheres has many interesting applications. The UV absorption of CO2 is the basis of photochemistry in the CO2-rich atmospheres of the ancient Earth, and of Mars and Venus. For the first time we present accurate temperature and isotope dependent CO2 absorption cross sections with important implications for photolysis rates of SO2 and H2O, and the production of a mass independent anomaly in the Ox reservoir. Experimental and theoretical results for OCS have implications for the modern stratospheric sulfur budget. The absorption bands of SO2 are complex with rich structure producing isotopic fractionation in photolysis and photoexcitation.

Extraterrestrial cold chemistry. A need for a specific database.

NASA Astrophysics Data System (ADS)

Pernot, P.; Carrasco, N.; Dobrijevic, M.; Hébrard, E.; Plessis, S.; Wakelam, V.

2008-09-01

The major resource databases for building chemical models for photochemistry in cold environments are mainly based on those designed for Earth atmospheric chemistry or combustion, in which reaction rates are reported for temperatures typically above 300 K [1,2]. Kinetic data measured at low temperatures are very sparse; for instance, in stateoftheart photochemical models of Titan atmosphere, less than 10% of the rates have been measured in the relevant temperature range (100200 K) [35]. In consequence, photochemical models rely mostly on lowT extrapolations by Arrheniustype laws. There is more and more evidence that this is often inappropriate [6], and low T extrapolations are hindered by very high uncertainty [3] (Fig.1). The predictions of models based on those extrapolations are expected to be very inaccurate [4,7]. We argue that there is not much sense in increasing the complexity of the present models as long as this predictivity issue has not been resolved. Fig. 1 Uncertainty of low temperature extrapolation for the N(2D) +C2H4 reaction rate, from measurements in the range 225 292 K [10], assuming an Arrhenius law (blue line). The sample of rate laws is generated by Monte Carlo uncertainty propagation after a Bayesian Data reAnalysis (BDA) of experimental data. A dialogue between modellers and experimentalists is necessary to improve this situation. Considering the heavy costs of low temperature reaction kinetics experiments, the identification of key reactions has to be based on an optimal strategy to improve the predictivity of photochemical models. This can be achieved by global sensitivity analysis, as illustrated on Titan atmospheric chemistry [8]. The main difficulty of this scheme is that it requires a lot of inputs, mainly the evaluation of uncertainty for extrapolated reaction rates. Although a large part has already been achieved by Hébrard et al. [3], extension and validation requires a group of experts. A new generation of collaborative kinetic database is needed to implement efficiently this scheme. The KIDA project [9], initiated by V. Wakelam for astrochemistry, has been joined by planetologists with similar prospects. EuroPlaNet will contribute to this effort through the organization of comities of experts on specific processes in atmospheric photochemistry.

A Lagrangian View of Stratospheric Trace Gas Distributions

NASA Technical Reports Server (NTRS)

Schoeberl, M. R.; Sparling, L.; Dessler, A.; Jackman, C. H.; Fleming, E. L.

1998-01-01

As a result of photochemistry, some relationship between the stratospheric age-of-air and the amount of tracer contained within an air sample is expected. The existence of such a relationship allows inferences about transport history to be made from observations of chemical tracers. This paper lays down the conceptual foundations for the relationship between age and tracer amount, developed within a Lagrangian framework. In general, the photochemical loss depends not only on the age of the parcel but also on its path. We show that under the "average path approximation" that the path variations are less important than parcel age. The average path approximation then allows us to develop a formal relationship between the age spectrum and the tracer spectrum. Using the relation between the tracer and age spectra, tracer-tracer correlations can be interpreted as resulting from mixing which connects parts of the single path photochemistry curve, which is formed purely from the action of photochemistry on an irreducible parcel. This geometric interpretation of mixing gives rise to constraints on trace gas correlations, and explains why some observations are do not fall on rapid mixing curves. This effect is seen in the ATMOS observations.

Chemical transitions for interstellar C2 and CN in cloud envelopes

NASA Technical Reports Server (NTRS)

Federman, S. R.; Strom, C. J.; Lambert, D. L.; Cardelli, Jason A.; Smith, V. V.; Joseph, C. L.

1994-01-01

Observations were made of absorption from CH, C2, and CN toward moderately reddened stars in Sco, OB2, Ceo OB3, and Taurus/Auriga. For these directions, most of the reddening is associated with a single cloud complex, for example, the rho Ophiuchus molecular cloud, and as a result, the observations probe moderately dense material. When combined with avaliable data for nearby directions, the survey provides the basis for a comprehensive analysis of the chemistry for these species. The chemical transitions affecting C2 and CN in cloud envelopes were analyzed. The depth into a cloud at which a transition takes place was characterized by tau(sub uv), the grain optical depth at 1000 A. One transition at tau(sub uv) approx. = 2, which arises from, the conversion of C(+) into CO, affects the chemistries for both molecules because of the key role this ion plays. A second one involving production terms in the CN chemistry occurs at tau(sub uv) of approx. = 3; neutral reactions which C2 and CH is more important at larger values for tau(sub uv). The transition from photodissociation to chemical destruction takes place at tau(sub uv) approx. = 4.5 for C2 and CN. The observational data for stars in Sco OB2, Cep OB3, and Taurus/Auriga were studied with chemical rate equations containing the most important production and destruction mechanisms. Because the sample of stars in Sco OB2 includes sight lines with A(sub v) ranging from 1-4 mag, sight lines dominated by photochemistry could be analyzed separately from those controlled by gas-phase destruction. The analysis yielded values for two poorly known rate constants for reactions involved in the production of CN; the reactions are C2 + N yields CN + C and C(+) + NH yields all products. The other directions were analyzed with the inferred values. The predicted column densities for C2 and CN agree with the observed values to better than 50%, and in most instances 20%. When combining the estimates for density and temperature derived from chemical modeling and molecular excitation for a specific cloud, such as the rho Ophiuchus molecular cloud, the portion of the cloud envelope probed by C2 and CN absorption was found to be in pressure equilibrium.

Ground based Mid-IR Observations of Temporally Varying Ethylene Emission on Jupiter

NASA Astrophysics Data System (ADS)

Romani, P. N.; Jennings, D. E.; Bjoraker, G. L.; Sada, P. V.; Boyle, R.; McCabe, G.

2003-05-01

Ethylene (C2H4)is an important species in our understanding of hydrocarbon photochemistry in the atmospheres of the giant planets. It also provides a sensitive probe of conditions at the 10-microbar level in Jupiter's atmosphere, a region that is strongly influenced by aurora. We performed high-resolution spectral observations of C2H4 at 10.53 microns (949.5 cm-1) on Jupiter with Celeste, a Goddard-developed cryogenic echelle spectrometer, during October-November 1998 at the McMath-Pierce telescope of the National Solar Observatory at Kitt Peak and during June 2000 at the IRTF at Mt. Kea in Hawai'i. We observed C2H4 line emission in the equatorial region and enhanced emission in the auroral latitudes. We modeled the emission using photochemical model profiles and either multiplied the model profile by a constant factor, adjusted the temperature in the isothermal region of the atmosphere, or adjusted the pressure level where the large thermal gradient starts. Analysis of the southern and northern auroral region emission yielded similar results with the exception of one day (21 June 2000) in the northern hemisphere "hot spot: (LIII 180 degrees). On this day the C2H4 emission was exceptionally bright. To match the emission required either multiplying the photochemical model profile by 25, or increasing the isothermal region temperature from 168K to 261K, or lowering the start of the temperature gradient region to 0.055 mbar. Of these three possibilities the increase in C2H4 abundance profile provided the poorest fit. Since the C2H4 emission on either side of this day was lower, and similar to each other, whatever mechanism that caused the increase in emission had to "turn on and off" within 48 hours. Similar short term behavior has been seen with Cassini-CIRS (see abstract by Sada et al.) This work is supported by the NASA Planetary Astronomy Program.

Surveys of research in the Chemistry Division, Argonne National Laboratory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grazis, B.M.

1992-01-01

Research reports are presented on reactive intermediates in condensed phase (radiation chemistry, photochemistry), electron transfer and energy conversion, photosynthesis and solar energy conversion, metal cluster chemistry, chemical dynamics in gas phase, photoionization-photoelectrons, characterization and reactivity of coal and coal macerals, premium coal sample program, chemical separations, heavy elements coordination chemistry, heavy elements photophysics/photochemistry, f-electron interactions, radiation chemistry of high-level wastes (gas generation in waste tanks), ultrafast molecular electronic devices, and nuclear medicine. Separate abstracts have been prepared. Accelerator activites and computer system/network services are also reported.

Surveys of research in the Chemistry Division, Argonne National Laboratory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grazis, B.M.

1992-11-01

Research reports are presented on reactive intermediates in condensed phase (radiation chemistry, photochemistry), electron transfer and energy conversion, photosynthesis and solar energy conversion, metal cluster chemistry, chemical dynamics in gas phase, photoionization-photoelectrons, characterization and reactivity of coal and coal macerals, premium coal sample program, chemical separations, heavy elements coordination chemistry, heavy elements photophysics/photochemistry, f-electron interactions, radiation chemistry of high-level wastes (gas generation in waste tanks), ultrafast molecular electronic devices, and nuclear medicine. Separate abstracts have been prepared. Accelerator activites and computer system/network services are also reported.

The intriguing near-ultraviolet photochemistry of H 2Te

NASA Astrophysics Data System (ADS)

Underwood, J.; Chastaing, D.; Lee, S.; Boothe, P.; Flood, T. C.; Wittig, C.

2002-08-01

The ultraviolet absorption spectrum of H 2Te has a long wavelength tail that extends to 400 nm. Photodissociation at 355 nm yields TeH( 2Π 1/2) selectively relative to the 2Π 3/2 ground state; the transition moments for these channels lie in, and perpendicular to, the molecular plane, respectively. Vibrational structure in the region 380-400 nm is consistent with a shallow well in the adiabat leading to 2Π 1/2, akin to the one in HI leading to I( 2P 1/2). These effects have no counterparts with the light Group 6A dihydrides.

Observation of novel photochemistry in the multiphoton ionization of Mo(CO) sub 6 van der Waals clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peifer, W.R.; Garvey, J.F.

1989-07-27

van der Waals clusters of Mo(CO){sub 6} generated in the free-jet expansion of a pulsed beam of seeded helium are subjected to multiphoton ionization and the product ions analyzed by quadrupole mass spectrometry. Oxomolybdenum and dioxomolybdenum ions are observed to be produced with high efficiency. This behavior is in striking contrast to that of metal carbonyl monomers and covalently bound cluster carbonyls, which under complete ligand loss prior to ionization. The observed photochemistry is ascribed to reactions between a photoproduced molybdenum atom and the ligands of neighboring Mo(CO){sub 6} solvent molecules within the van der Waals cluster.

Continuous flow photochemistry.

PubMed

Gilmore, Kerry; Seeberger, Peter H

2014-06-01

Due to the narrow width of tubing/reactors used, photochemistry performed in micro- and mesoflow systems is significantly more efficient than when performed in batch due to the Beer-Lambert Law. Owing to the constant removal of product and facility of flow chemical scalability, the degree of degradation observed is generally decreased and the productivity of photochemical processes is increased. In this Personal Account, we describe a wide range of photochemical transformations we have examined using both visible and UV light, covering cyclizations, intermolecular couplings, radical polymerizations, as well as singlet oxygen oxygenations. Copyright © 2014 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Understanding the Atmosphere of 51 Eri b: Do Photochemical Hazes Cloud the Planets Spectrum?

NASA Technical Reports Server (NTRS)

Marley, Mark Scott; Zahnle, Kevin; Moses, J.; Morley, C.

2015-01-01

The first young giant planet to be discovered by the Gemini Planet Imager was the (is) approximately 2MJ planet 51 Eri b. This approximately 20 Myr old young Jupiter is the first directly imaged planet to show unmistakable methane in H band. To constrain the planet's mass, atmospheric temperature, and composition, the GPI J and H band spectra as well as some limited photometric points were compared to the predictions of substellar atmosphere models. The best fitting models reported in the discovery paper (Macintosh et al. 2015) relied upon a combination of clear and cloudy atmospheric columns to reproduce the data. However for an object as cool as 700 K, the origin of the cloud coverage is somewhat puzzling, as the global silicate and iron clouds would be expected to have sunk well below the photosphere by this effective temperature. While strong vertical mixing in these low gravity atmospheres remains a plausible explanation, we have explored whether atmospheric photochemistry, driven by the UV flux from the primary star, may yield hazes that also influence the observed spectrum of the planet. To explore this possibility we have modeled the atmospheric photochemistry of 51 Eri b using two state-of-the-art photochemical models, both capable of predicting yields of complex hydrocarbons under various atmospheric conditions. In our presentation we will summarize the modeling approach employed to characterize 51 Eri b, explaining constraints on the planet's effective temperature, gravity, and atmospheric composition and also present results of our studies of atmospheric photochemistry. We will discuss whether photochemical hazes could indeed be responsible for the particulate opacity that apparently sculpts the spectrum of the planet.

Transient repetitive exposure to low level light therapy enhances collateral blood vessel growth in the ischemic hindlimb of the tight skin mouse.

PubMed

Zaidi, Maria; Krolikowki, John G; Jones, Deron W; Pritchard, Kirkwood A; Struve, Janine; Nandedkar, Sandhya D; Lohr, Nicole L; Pagel, Paul S; Weihrauch, Dorothée

2013-01-01

The tight skin mouse (Tsk(-/+)) is a model of scleroderma characterized by impaired vasoreactivity, increased oxidative stress, attenuated angiogenic response to VEGF and production of the angiogenesis inhibitor angiostatin. Low-level light therapy (LLLT) stimulates angiogenesis in myocardial infarction and chemotherapy-induced mucositis. We hypothesize that repetitive LLLT restores vessel growth in the ischemic hindlimb of Tsk(-/+) mice by attenuating angiostatin and enhancing angiomotin effects in vivo. C57Bl/6J and Tsk(-/+) mice underwent ligation of the femoral artery. Relative blood flow to the foot was measured using a laser Doppler imager. Tsk(-/+) mice received LLLT (670 nm, 50 mW cm(-2), 30 J cm(-2)) for 10 min per day for 14 days. Vascular density was determined using lycopersicom lectin staining. Immunofluorescent labeling, Western blot analysis and immunoprecipitation were used to determine angiostatin and angiomotin expression. Recovery of blood flow to the ischemic limb was reduced in Tsk(-/+) compared with C57Bl/6 mice 2 weeks after surgery. LLLT treatment of Tsk(-/+) mice restored blood flow to levels observed in C57Bl/6 mice. Vascular density was decreased, angiostatin expression was enhanced and angiomotin depressed in the ischemic hindlimb of Tsk(-/+) mice. LLLT treatment reversed these abnormalities. LLLT stimulates angiogenesis by increasing angiomotin and decreasing angiostatin expression in the ischemic hindlimb of Tsk(-/+) mice. © 2012 Wiley Periodicals, Inc. Photochemistry and Photobiology © 2012 The American Society of Photobiology.

Role of surface crossings in the photochemistry of nitromethane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arenas, Juan F.; Otero, Juan C.; Pelaez, Daniel

2005-02-22

The photodissociation dynamics of nitromethane (CH{sub 3}NO{sub 2}) starting at the S{sub 3} excited state has been studied at the complete active space self-consistent field level of theory in conjunction with atomic natural orbital type basis sets. In addition, the energies of all the critical points and the energy profiles connecting them have been recomputed with the multiconfigurational second-order perturbation method. It is found that the key step in the reaction mechanism is a radiationless decay through an S{sub 3}/S{sub 2} conical intersection. The branching space spanned by the gradient difference and nonadiabatic coupling vectors of this crossing point comprisesmore » dissociation into excited nitromethane plus singlet atomic oxygen [CH{sub 3}NO(1A{sup ''})+O({sup 1}D)] and S{sub 3}{yields}S{sub 2} deactivation, respectively. Furthermore, deactivated nitromethane S{sub n(nlt3)} can decompose in subsequent steps into CH{sub 3}+NO{sub 2}, where NO{sub 2} is generated at least in two different electronic states (1 {sup 2}B{sub 2} and 1 {sup 2}A{sub 1}). It is shown that formation of excited nitric oxide NO(A {sup 2}{sigma}) arises from CH{sub 3}NO(1A{sup ''}) generated in the previous step. In addition, four crossings between singlet and triplet states are localized; however, no evidence is found for a relevant role of such crossings in the photochemistry of CH{sub 3}NO{sub 2} initiated at S{sub 3} state in the gas phase.« less

Ultrafast photochemistry of polyatomic molecules containing labile halogen atoms in solution

NASA Astrophysics Data System (ADS)

Mereshchenko, Andrey S.

Because breaking and making of chemical bonds lies at the heart of chemistry, this thesis focuses on dynamic studies of labile molecules in solutions using ultrafast transient absorption spectroscopy. Specifically, my interest is two-fold: (i) novel reaction intermediates of polyhalogenated carbon, boron and phosphorus compounds; (ii) photophysics and photochemistry of labile copper(II) halide complexes. Excitation of CH2Br2, CHBr3, BBr 3, and PBr3 into n(Br)sigma*(X-Br) states, where X=C, B, or P, leads to direct photoisomerization with formation of isomers having Br-Br bonds as well as rupture of one of X-Br bonds with the formation of a Br atom and a polyatomic radical fragment, which subsequently recombine to form similar isomer products. Nonpolar solvation stabilizes the isomers, consistent with intrinsic reaction coordinate calculations of the isomer ground state potential energy surfaces at the density functional level of theory, and consequently, the involvement of these highly energetic species on chemically-relevant time scales needs to be taken into account. Monochlorocomplexes in methanol solutions promoted to the ligand-to-metal charge transfer (LMCT) excited state predominantly undergo internal conversion via back electron transfer, giving rise to vibrationally hot ground-state parent complexes. Copper-chloride homolitical bond dissociation yielding the solvated copper(I) and Cl- atom/solvent CT complexes constitutes a minor pathway. Insights into ligand substitution mechanisms were acquired by monitoring the recovery of monochloro complexes at the expense of two unexcited dichloro- and unsubstituted forms of Cu(II) complexes also present in the solution. Detailed description of ultrafast excited-state dynamics of CuCl 42- complexes in acetonitrile upon excitation into all possible Ligand Field (LF) excited states and two most intense LMCT transitions is reported. The LF states were found to be nonreactive with lifetimes remarkably longer than those for copper(II) complexes studied so far, in particular, copper blue proteins. The highest 2A1 and lowest 2E LF states relax directly to the ground electronic state whereas the intermediate 2B1 LF state relaxes stepwise through the 2E state. The LMCT excited states are short-lived undergoing either ionic dissociation (CuCl3- + Cl-) or cascading relaxation through the manifold of vibrationally hot LF states to the ground state.

Reactivity of biogenic manganese oxide for metal sequestration and photochemistry: Computational solid state physics study (in Korean)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kwon, K.D.; Sposito, G.

2010-02-01

Many microbes, including both bacteria and fungi, produce manganese (Mn) oxides by oxidizing soluble Mn(II) to form insoluble Mn(IV) oxide minerals, a kinetically much faster process than abiotic oxidation. These biogenic Mn oxides drive the Mn cycle, coupling it with diverse biogeochemical cycles and determining the bioavailability of environmental contaminants, mainly through strong adsorption and redox reactions. This mini review introduces recent findings based on quantum mechanical density functional theory that reveal the detailed mechanisms of toxic metal adsorption at Mn oxide surfaces and the remarkable role of Mn vacancies in the photochemistry of these minerals.

Naval Research Laboratory Ecological -- Photochemical -- Bio-optical--Numerical Experiment (Neptune) Version 1: A Portable, Flexible Modeling Environment Designed to Resolve Time-dependent Feedbacks Between Upper Ocean Ecology, Photochemistry, and Optics

DTIC Science & Technology

2007-02-21

dependent upon the carbon gross growth efficiency ( GGE ) and the C:N:P ratio of the organic substrate. This calculation and its structural...product of the temperature adjusted maximum gross carbon assimilation rate, the carbon gross growth efficiency ( GGE ), and the uptake kinetics for DOC...substrate: max T 4 [ ]( ) [ ]Cb b DOCg g GGE n DOC ⎛ ⎞ = ⎜ ⎟+⎝ ⎠ (21) and ( )( 30)max T m30 m30min[ , ]Kt Tb b bg g g e −= (22) To

A Chemical Model of the Coma of Comet C/2009 P1 (Garradd)

NASA Astrophysics Data System (ADS)

Boice, Daniel C.; Kawakita, H.; Kobayashi, H.; Naka, C.; Phelps, L.

2012-10-01

Modeling is essential to understand the important physical and chemical processes that occur in cometary comae. Photochemistry is a major source of ions and electrons that further initiate key gas-phase reactions, leading to the plethora of molecules and atoms observed in comets. The effects of photoelectrons that react via impacts are important to the overall ionization. We identify the relevant processes within a global modeling framework to understand simultaneous observations in the visible and near-IR of Comet C/2009 (Garradd) and to provide valuable insights into the intrinsic properties of its nucleus. Details of these processes are presented in the collision-dominated, inner coma of the comet to evaluate the relative chemical pathways and the relationship between parent and sibling molecules. Acknowledgements: We appreciate support from the NSF Planetary Astronomy Program.

An Evaluation of Evidence for the Carcinogenic Activity of Bisphenol A

PubMed Central

Keri, Ruth A.; Ho, Shuk-Mei; Hunt, Patricia A.; Knudsen, Karen E.; Soto, Ana M.; Prins, Gail S.

2008-01-01

The National Institutes of Health (NIEHS, NIDCR) and the United States Environmental Protection Agency convened an expert panel of scientists with experience in the field of environmental endocrine disruptors, particularly with knowledge and research on Bisphenol A (BPA). Five subpanels were charged to review the published literature and previous reports in five specific areas and to compile a consensus report with recommendations. These were presented and discussed at an open forum entitled “Bisphenol A: An Expert Panel Examination of the Relevance of Ecological, In Vitro and Laboratory Animal Studies for Assessing Risks to Human Health” in Chapel Hill, NC on November 28-30, 2006. The present review consists of the consensus report on the evidence for a role of BPA in carcinogenesis, examining the available evidence in humans and animal models with recommendations for future areas of research. PMID:17706921

Conformational landscape, photochemistry, and infrared spectra of sulfanilamide.

PubMed

Borba, Ana; Gómez-Zavaglia, Andrea; Fausto, Rui

2013-01-31

A combined matrix isolation FTIR and theoretical DFT(B3LYP)/6-311++G(3df,3pd) study of sulfanilamide (SA) was performed. The full conformational search on the potential energy surface of the compound allowed the identification of four different minima, all of them bearing the sulfamide nitrogen atom placed in the perpendicular orientation relatively to the aromatic ring and differing from each other in the orientation of the hydrogen atoms connected to the two nitrogen atoms of the molecule. All conformers were predicted to be significantly populated in the gas phase (at 100 °C, their relative populations were estimated as being 1:0.9:0.3:0.2). However, in agreement with the theoretically calculated low-energy barriers for conformational isomerization, in the low-temperature matrices, only the most stable conformer could be observed, with the remaining forms being converted into this form during matrix deposition (conformational cooling). The unimolecular photochemistry of matrix-isolated SA (in both argon and xenon) was also investigated. Upon broadband UV irradiation (λ > 215 nm), two photofragmentation pathways were observed: the prevalent pathway (A), leading to extrusion of sulfur dioxide and simultaneous formation of benzene-1,4-diamine, which then converts to 2,5-cyclohexadiene-1,4-diimine, and the minor pathway (B), conducting an γ-cleavage plus [1,3] H-atom migration from the sulfamide group to the aromatic ring, which leads to formation of iminosulfane dioxide and aniline, the latter undergoing subsequent phototransformation into cyclohexa-2,5-dien-1-imine. Finally, the crystalline polymorph of SA resulting from warming (265 K) the amorphous solid obtained from fast cooling of the vapor of the compound onto the cold (13 K) substrate of the cryostat was identified spectroscopically, and found to be the γ-crystalline phase, the one exhibiting in average longer H-bonds and an infrared spectrum resembling more that of the low temperature SA glass. Full assignment of the infrared spectra of this crystalline variety as well as of those of the β-polymorph room temperature crystalline sample and low temperature amorphous state was undertaken with help of theoretical results obtained for the crystallographically relevant dimer of SA.

Blue and red light-induced germination of resting spores in the red-tide diatom Leptocylindrus danicus.

PubMed

Shikata, Tomoyuki; Iseki, Mineo; Matsunaga, Shigeru; Higashi, Sho-ichi; Kamei, Yasuhiro; Watanabe, Masakatsu

2011-01-01

Photophysiological and pharmacological approaches were used to examine light-induced germination of resting spores in the red-tide diatom Leptocylindrus danicus. The equal-quantum action spectrum for photogermination had peaks at about 440 nm (blue light) and 680 nm (red light), which matched the absorption spectrum of the resting spore chloroplast, as well as photosynthetic action spectra reported for other diatoms. DCMU, an inhibitor of photosynthetic electron flow near photosystem II, completely blocked photogermination. These results suggest that the photosynthetic system is involved in the photoreception process of light-induced germination. Results of pharmacological studies of the downstream signal transduction pathway suggested that Ca(2+) influx is the closest downstream neighbor, followed by steps involving calmodulin, nitric oxide synthase, guanylyl cyclase, protein-tyrosine-phosphatase, protein kinase C and actin polymerization and translation. © 2011 The Authors. Photochemistry and Photobiology © 2011 The American Society of Photobiology.

A Leaf-Inspired Luminescent Solar Concentrator for Energy-Efficient Continuous-Flow Photochemistry.

PubMed

Cambié, Dario; Zhao, Fang; Hessel, Volker; Debije, Michael G; Noël, Timothy

2017-01-19

The use of solar light to promote chemical reactions holds significant potential with regard to sustainable energy solutions. While the number of visible light-induced transformations has increased significantly, the use of abundant solar light has been extremely limited. We report a leaf-inspired photomicroreactor that constitutes a merger between luminescent solar concentrators (LSCs) and flow photochemistry to enable green and efficient reactions powered by solar irradiation. This device based on fluorescent dye-doped polydimethylsiloxane collects sunlight, focuses the energy to a narrow wavelength region, and then transports that energy to embedded microchannels where the flowing reactants are converted. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of the isoprene chemistry observed during the New England Air Quality Study (NEAQS) 2002 intensive experiment

NASA Astrophysics Data System (ADS)

Roberts, James M.; Marchewka, Mathew; Bertman, Steven B.; Goldan, Paul; Kuster, William; de Gouw, Joost; Warneke, Carsten; Williams, Eric; Lerner, Brian; Murphy, Paul; Apel, Eric; Fehsenfeld, Fred C.

2006-12-01

Isoprene and its first and second generation photochemical products, methyl vinyl ketone (MVK), methacrolein (MACR), and peroxymethacrylic nitric anhydride (MPAN), were measured off the coast of New England during the 2002 New England Air Quality Study (NEAQS) on board the NOAA Research Vessel Ronald H. Brown. The results of these measurements were analyzed using a simple sequential reaction model that has been used previously to examine regional oxidant chemistry. The highest isoprene impact was observed in air masses that had passed over an area of high isoprene emission WSW of Boston. The relative concentrations of isoprene and its first generation products show that the photochemistry is consistently "older" than the isoprene photochemistry observed at continental sites. The sequential reaction model was also applied to the aldehyde-PANs (Peroxycarboxylic nitric anhydride) system, and the resulting PPN (peroxypropionic nitric anhydride)/propanal and PAN (peroxyacetic nitric anhydride)/acetaldehyde relationships were consistent with additional sources of PAN in this environment, e.g., isoprene photochemistry. This isoprene source was estimated to result in approximately 1.6 to 4 times more PAN in this environment relative to that produced from anthropogenic VOCs (volatile organic compounds) alone.

The catalytic role of water in the photochemistry of ammonia ice: from diluted to concentrated phase

NASA Astrophysics Data System (ADS)

Jonusas, Mindaugas; Krim, Lahouari

2017-10-01

Using infrared spectroscopy as an in situ probe for reactions occurring in the solid phase, we investigated the influence of water molecules on the photochemistry of ammonia ices. Experiments were carried out in diluted and concentrated phases and between 3 and 130 K. We showed that the photolysis of NH3-H2O (2 per cent of H2O) ices using continuous radiation from 115 to 400 nm produces NH2OH as the main photoproduct, but also that such a photoinduced reaction strongly depends on both the initial ice temperature and the environment where the primary reactants NH3 and H2O are trapped. Our experimental results highlight the catalytic role played by H2O molecules in enhancing the formation yield of NH2 during the photolysis process through the NH3 + OH → NH2 + H2O hydrogen abstraction reaction, which is only favored at low temperatures in the range of 3-60 K. During heating of such irradiated ammonia-water ices, the amount of NH2OH keeps rising while that of NH2, is greatly reduced only from 70 K onwards. These behaviours are attributed to the competition that occurs between NH2 formation from the NH3 + OH reaction and its consumption from the NH2 + OH radical recombination. These results might explain the variable abundances of NH2 and NH3 provided by previous astronomical observations, where the NH2/NH3 ratio ranges from 0.02 to 0.5 depending on the regions of the interstellar medium that were analysed.

Photochemistry of fac-[Re(CO)3(dcbH2)( trans-stpy)]+: New Insights on the Isomerization Mechanism of Coordinated Stilbene-like Ligands.

PubMed

Faustino, Leandro A; Hora Machado, Antonio Eduardo; Patrocinio, Antonio Otavio T

2018-03-05

In this work, a novel complex fac-[Re(CO) 3 (dcbH 2 )( trans-stpy)] + , (dcbH 2 = 4,4'-dicarboxylic acid-2,2'-bipyridine; trans-stpy = trans-4-styrylpyridine) was synthesized and characterized toward its spectroscopic, photochemical, and photophysical properties. The experimental data provide new insights on the mechanism of photochemical trans-to- cis isomerization of the stilbene-like ligand coordinated to Re(I) polypyridyl complexes. The new complex exhibits an unusual and strong dependence of the isomerization quantum yield (Φ t →c ) on the irradiation wavelength. Φ t →c was 0.81 ± 0.08 for irradiation at 365 nm and continuously decreased as the irradiation wavelength is shifted to the visible. At 405 nm irradiation Φ t →c is almost 2 orders of magnitude lower (0.010 ± 0.005) than that observed at 365 nm excitation. This behavior can be explained by the low-lying triplet metal-to-ligand charge-transfer excited state ( 3 MLCT) that hinders the triplet photoreaction mechanism under visible light absorption. Under UV irradiation, direct population of styrylpyridine-centered excited state ( 1 IL) leads to the occurrence of the photoisomerization via a singlet mechanism. Further experiments were performed with the complex immobilized on the surface of TiO 2 and Al 2 O 3 films. The nonoccurrence of isomerization at the oxide surfaces even under UV excitation evidences the role of energy gap between the 1 IL/ 1 MLCT states on the photochemical/photophysical processes. The results establish important relationships between the molecular structure and the photoelectrochemical behavior, which can further contribute to the development of solid-state molecular switches based on Re(I) polypyridyl complexes.

Adaptation of an In Situ Ground-Based Tropospheric OH/HO2 Instrument for Aircraft Use

NASA Technical Reports Server (NTRS)

Brune, William H.

1997-01-01

In-situ HO(x) (OH and HO2) measurements are an essential part of understanding the photochemistry of aircraft exhaust in the atmosphere. HO(x) affects the partitioning of nitrogen species in the NO(y) family. Its reactions are important sources and sinks for tropospheric ozone, thus providing a link between the NO(x) in aircraft exhaust and tropospheric ozone. OH mixing ratios are enhanced in aircraft wakes due to the photolysis of the HONO that is made close to the engine. Measurements of HO(x) in aircraft wakes, along with NO(x) measurements, thus provides a constraint on chemical models of the engine combustion and exhaust. The development of the Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS) is reported. We designed, developed, and successfully flew this instrument. It was part of the instrument complement on board the NASA DC-8 during SUCCESS, which took place in Kansas in April and May, 1996. ATHOS has a limit-of-detection for OH (S/N = 2) of 10(exp 5) OH molecules cm(exp -3) in less than 150 seconds. While this sensitivity is about 2-3 times less than the initial projections in the proposal, it is more than adequate for good measurements of OH and HO2 from the planetary boundary layer to the stratosphere. Our participation in SUCCESS was to be engineering test flights for ATHOS; however, the high-quality measurements we obtained are being used to study HO(x) photochemistry in contrails, clouds, and the clear air.

Photosystem II Photochemistry and Phycobiliprotein of the Red Algae Kappaphycus alvarezii and Their Implications for Light Adaptation

PubMed Central

Wang, Jinfeng; Zhu, Jianyi; Yao, Chunyan; Liu, Jianguo; Qin, Song; Jiang, Peng

2013-01-01

Photosystem II photochemistry and phycobiliprotein (PBP) genes of red algae Kappaphycus alvarezii, raw material of κ-carrageenan used in food and pharmaceutical industries, were analyzed in this study. Minimum saturating irradiance (I k) of this algal species was less than 115 μmol m−2 s−1. Its actual PSII efficiency (yield II) increased when light intensity enhanced and decreased when light intensity reached 200 μmol m−2 s−1. Under dim light, yield II declined at first and then increased on the fourth day. Under high light, yield II retained a stable value. These results indicate that K. alvarezii is a low-light-adapted species but possesses regulative mechanisms in response to both excessive and deficient light. Based on the PBP gene sequences, K. alvarezii, together with other red algae, assembled faster and showed a closer relationship with LL-Prochlorococcus compared to HL-Prochlorococcus. Many amino acid loci in PBP sequences of K. alvarezii were conserved with those of LL-Prochlorococcus. However, loci conserved with HL-Prochlorococcus but divergent with LL-Prochlorococcus were also found. The diversities of PE and PC are proposed to have played some roles during the algal evolution and divergence of light adaption. PMID:24380080

Photosystem II photochemistry and phycobiliprotein of the red algae Kappaphycus alvarezii and their implications for light adaptation.

PubMed

Guan, Xiangyu; Wang, Jinfeng; Zhu, Jianyi; Yao, Chunyan; Liu, Jianguo; Qin, Song; Jiang, Peng

2013-01-01

Photosystem II photochemistry and phycobiliprotein (PBP) genes of red algae Kappaphycus alvarezii, raw material of κ -carrageenan used in food and pharmaceutical industries, were analyzed in this study. Minimum saturating irradiance (I k) of this algal species was less than 115 μmol m(-2) s(-1). Its actual PSII efficiency (yield II) increased when light intensity enhanced and decreased when light intensity reached 200 μmol m(-2) s(-1). Under dim light, yield II declined at first and then increased on the fourth day. Under high light, yield II retained a stable value. These results indicate that K. alvarezii is a low-light-adapted species but possesses regulative mechanisms in response to both excessive and deficient light. Based on the PBP gene sequences, K. alvarezii, together with other red algae, assembled faster and showed a closer relationship with LL-Prochlorococcus compared to HL-Prochlorococcus. Many amino acid loci in PBP sequences of K. alvarezii were conserved with those of LL-Prochlorococcus. However, loci conserved with HL-Prochlorococcus but divergent with LL-Prochlorococcus were also found. The diversities of PE and PC are proposed to have played some roles during the algal evolution and divergence of light adaption.

Solar Rejection Filter for Large Telescopes

NASA Technical Reports Server (NTRS)

Hemmati, Hamid; Lesh, James

2009-01-01

To reject solar radiation photons at the front aperture for large telescopes, a mosaic of large transmission mode filters is placed in front of the telescope or at the aperture of the dome. Filtering options for effective rejection of sunlight include a smaller filter down-path near the focus of the telescope, and a large-diameter filter located in the front of the main aperture. Two types of large filters are viable: reflectance mode and transmittance mode. In the case of reflectance mode, a dielectric coating on a suitable substrate (e.g. a low-thermal-expansion glass) is arranged to reflect only a single, narrow wavelength and to efficiently transmit all other wavelengths. These coatings are commonly referred to as notch filter. In this case, the large mirror located in front of the telescope aperture reflects the received (signal and background) light into the telescope. In the case of transmittance mode, a dielectric coating on a suitable substrate (glass, sapphire, clear plastic, membrane, and the like) is arranged to transmit only a single wavelength and to reject all other wavelengths (visible and near IR) of light. The substrate of the large filter will determine its mass. At first glance, a large optical filter with a diameter of up to 10 m, located in front of the main aperture, would require a significant thickness to avoid sagging. However, a segmented filter supported by a structurally rugged grid can support smaller filters. The obscuration introduced by the grid is minimal because the total area can be made insignificant. This configuration can be detrimental to a diffraction- limited telescope due to diffraction effects at the edges of each sub-panel. However, no discernable degradation would result for a 20 diffraction-limit telescope (a photon bucket). Even the small amount of sagging in each subpanel should have minimal effect in the performance of a non-diffraction limited telescope because the part has no appreciable optical power. If the front aperture filter is integrated with the telescope dome, it will reject heat from the dome and will significantly reduce dome temperature regulation requirements and costs. Also, the filter will protect the telescope optics from dust and other contaminants in the atmosphere. It will be simpler to clean or replace this filter than the telescope primary mirror. It may be necessary to paint the support grid with a highly reflective material to avoid overheating.

Photogeneration of reactive transient species upon irradiation of natural water samples: Formation quantum yields in different spectral intervals, and implications for the photochemistry of surface waters.

PubMed

Marchisio, Andrea; Minella, Marco; Maurino, Valter; Minero, Claudio; Vione, Davide

2015-04-15

Chromophoric dissolved organic matter (CDOM) in surface waters is a photochemical source of several transient species such as CDOM triplet states ((3)CDOM*), singlet oxygen ((1)O2) and the hydroxyl radical (OH). By irradiation of lake water samples, it is shown here that the quantum yields for the formation of these transients by CDOM vary depending on the irradiation wavelength range, in the order UVB > UVA > blue. A possible explanation is that radiation at longer wavelengths is preferentially absorbed by the larger CDOM fractions, which show lesser photoactivity compared to smaller CDOM moieties. The quantum yield variations in different spectral ranges were definitely more marked for (3)CDOM* and OH compared to (1)O2. The decrease of the quantum yields with increasing wavelength has important implications for the photochemistry of surface waters, because long-wavelength radiation penetrates deeper in water columns compared to short-wavelength radiation. The average steady-state concentrations of the transients ((3)CDOM*, (1)O2 and OH) were modelled in water columns of different depths, based on the experimentally determined wavelength trends of the formation quantum yields. Important differences were found between such modelling results and those obtained in a wavelength-independent quantum yield scenario. Copyright © 2015 Elsevier Ltd. All rights reserved.

Photochemistry and Photophysics of Aqueous Cr(NH3)5(CN)(2+) and Trans-Cr(NH3)4(CN)(2+).

DTIC Science & Technology

1983-06-01

molecular sieve., and distilled at reduced pressure, under nitrogen atmosphere, before use. -4- Equipment and procedures. - Emission lifetimes...either process could be assigned such an activation energy from the molecular point of view. Chemical reaction from Dl could certainly be activated. In...requiring both a change in molecular geometry and in spin. In the present case, incidentally, it is difficult to estimate the Ql0-D 0 energy gap because of

Photophysics and Photochemistry of 2-Aminobenzoic Acid Anion in Aqueous Solution

NASA Astrophysics Data System (ADS)

Pozdnyakov, Ivan P.; Plyusnin, Victor F.; Grivin, Vjacheslav P.

2009-11-01

Nanosecond laser flash photolysis and absorption and fluorescence spectroscopy were used to study photochemical processes of 2-aminobenzoic acid anion (ABA-) in aqueous solutions. Excitation of this species gives rise to the ABA- triplet state to the ABA• radical and to the hydrated electron (eaq-). The last two species result from two-photon processes. In a neutral medium, the main decay channels of ABA- triplet state, the ABA• radical, and eaq- are T-T annihilation, recombination, and capture by the ABA- anion, respectively.

Active molecular iodine photochemistry in the Arctic

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raso, Angela R. W.; Custard, Kyle D.; May, Nathaniel W.

During springtime, the Arctic atmospheric boundary layer undergoes frequent rapid depletions in ozone and gaseous elemental mercury due to reactions with halogen atoms, influencing atmospheric composition and pollutant fate. Although bromine chemistry has been shown to initiate ozone depletion events, and it has long been hypothesized that iodine chemistry may contribute, no previous measurements of molecular iodine (I 2) have been reported in the Arctic. Iodine chemistry also contributes to atmospheric new particle formation and therefore cloud properties and radiative forcing. Here we present Arctic atmospheric I2 and snowpack iodide (I-) measurements, which were conducted near Utqiagvik, AK, in Februarymore » 2014. Using chemical ionization mass spectrometry, I2 was observed in the atmosphere at mole ratios of 0.3–1.0 ppt, and in the snowpack interstitial air at mole ratios up to 22 ppt under natural sunlit conditions and up to 35 ppt when the snowpack surface was artificially irradiated, suggesting a photochemical production mechanism. Further, snow meltwater I-measurements showed enrichments of up to ~1,900 times above the seawater ratio of I-/Na+, consistent with iodine activation and recycling. Modeling shows that observed I 2 levels are able to significantly increase ozone depletion rates, while also producing iodine monoxide (IO) at levels recently observed in the Arctic. These results emphasize the significance of iodine chemistry and the role of snowpack photochemistry in Arctic atmospheric composition, and imply that I 2 is likely a dominant source of iodine atoms in the Arctic.« less

Active molecular iodine photochemistry in the Arctic

DOE PAGES

Raso, Angela R. W.; Custard, Kyle D.; May, Nathaniel W.; ...

2017-09-05

During springtime, the Arctic atmospheric boundary layer undergoes frequent rapid depletions in ozone and gaseous elemental mercury due to reactions with halogen atoms, influencing atmospheric composition and pollutant fate. Although bromine chemistry has been shown to initiate ozone depletion events, and it has long been hypothesized that iodine chemistry may contribute, no previous measurements of molecular iodine (I 2) have been reported in the Arctic. Iodine chemistry also contributes to atmospheric new particle formation and therefore cloud properties and radiative forcing. Here we present Arctic atmospheric I 2 and snowpack iodide (I -) measurements, which were conducted near Utqiagvik, AK,more » in February 2014. Using chemical ionization mass spectrometry, I 2 was observed in the atmosphere at mole ratios of 0.3–1.0 ppt, and in the snowpack interstitial air at mole ratios up to 22 ppt under natural sunlit conditions and up to 35 ppt when the snowpack surface was artificially irradiated, suggesting a photochemical production mechanism. Further, snow meltwater I-measurements showed enrichments of up to ~1,900 times above the seawater ratio of I-/Na +, consistent with iodine activation and recycling. Modeling shows that observed I 2 levels are able to significantly increase ozone depletion rates, while also producing iodine monoxide (IO) at levels recently observed in the Arctic. Furthermore, these results emphasize the significance of iodine chemistry and the role of snowpack photochemistry in Arctic atmospheric composition, and imply that I 2 is likely a dominant source of iodine atoms in the Arctic.« less

Active molecular iodine photochemistry in the Arctic

NASA Astrophysics Data System (ADS)

Raso, Angela R. W.; Custard, Kyle D.; May, Nathaniel W.; Tanner, David; Newburn, Matt K.; Walker, Lawrence; Moore, Ronald J.; Huey, L. G.; Alexander, Liz; Shepson, Paul B.; Pratt, Kerri A.

2017-09-01

During springtime, the Arctic atmospheric boundary layer undergoes frequent rapid depletions in ozone and gaseous elemental mercury due to reactions with halogen atoms, influencing atmospheric composition and pollutant fate. Although bromine chemistry has been shown to initiate ozone depletion events, and it has long been hypothesized that iodine chemistry may contribute, no previous measurements of molecular iodine (I2) have been reported in the Arctic. Iodine chemistry also contributes to atmospheric new particle formation and therefore cloud properties and radiative forcing. Here we present Arctic atmospheric I2 and snowpack iodide (I-) measurements, which were conducted near Utqiaġvik, AK, in February 2014. Using chemical ionization mass spectrometry, I2 was observed in the atmosphere at mole ratios of 0.3-1.0 ppt, and in the snowpack interstitial air at mole ratios up to 22 ppt under natural sunlit conditions and up to 35 ppt when the snowpack surface was artificially irradiated, suggesting a photochemical production mechanism. Further, snow meltwater I- measurements showed enrichments of up to ˜1,900 times above the seawater ratio of I-/Na+, consistent with iodine activation and recycling. Modeling shows that observed I2 levels are able to significantly increase ozone depletion rates, while also producing iodine monoxide (IO) at levels recently observed in the Arctic. These results emphasize the significance of iodine chemistry and the role of snowpack photochemistry in Arctic atmospheric composition, and imply that I2 is likely a dominant source of iodine atoms in the Arctic.

Active molecular iodine photochemistry in the Arctic.

PubMed

Raso, Angela R W; Custard, Kyle D; May, Nathaniel W; Tanner, David; Newburn, Matt K; Walker, Lawrence; Moore, Ronald J; Huey, L G; Alexander, Liz; Shepson, Paul B; Pratt, Kerri A

2017-09-19

During springtime, the Arctic atmospheric boundary layer undergoes frequent rapid depletions in ozone and gaseous elemental mercury due to reactions with halogen atoms, influencing atmospheric composition and pollutant fate. Although bromine chemistry has been shown to initiate ozone depletion events, and it has long been hypothesized that iodine chemistry may contribute, no previous measurements of molecular iodine (I 2 ) have been reported in the Arctic. Iodine chemistry also contributes to atmospheric new particle formation and therefore cloud properties and radiative forcing. Here we present Arctic atmospheric I 2 and snowpack iodide (I - ) measurements, which were conducted near Utqiaġvik, AK, in February 2014. Using chemical ionization mass spectrometry, I 2 was observed in the atmosphere at mole ratios of 0.3-1.0 ppt, and in the snowpack interstitial air at mole ratios up to 22 ppt under natural sunlit conditions and up to 35 ppt when the snowpack surface was artificially irradiated, suggesting a photochemical production mechanism. Further, snow meltwater I - measurements showed enrichments of up to ∼1,900 times above the seawater ratio of I - /Na + , consistent with iodine activation and recycling. Modeling shows that observed I 2 levels are able to significantly increase ozone depletion rates, while also producing iodine monoxide (IO) at levels recently observed in the Arctic. These results emphasize the significance of iodine chemistry and the role of snowpack photochemistry in Arctic atmospheric composition, and imply that I 2 is likely a dominant source of iodine atoms in the Arctic.

HOx Radical Behavior in Urban, Biogenic and Mixed Environments

NASA Astrophysics Data System (ADS)

Cantrell, C. A.; Mauldin, L.; Schardt, N.; Mukherjee, A. D.

2014-12-01

The importance of HOx radicals in tropospheric chemistry is well-recognized. These roles include control of the lifetimes of a wide variety of trace gases, and control of photochemical ozone formation. The continued advance in understanding comes from laboratory investigations and field observations especially as part of comprehensive measurement campaigns. We participated in two recent observational campaigns aboard the NSF/NCAR C-130 aircraft platform: NOMADSS (Nitrogen, Oxidants, Mercury and Aerosol Distributions, Sources and Sinks) and FRAPPE (Front Range Atmospheric Pollution and Photochemistry Experiment). During these studies, a wide varieties of air masses were sampled ranging from fresh urban to rural both without and without biogenic influence to marine, and including the impacts of emissions from oil and gas extraction and animal production. Among the wide variety of parameters and species related to tropospheric chemistry that were measured, our group made observations of HOx and related species: OH, HO2, HO2+RO2, H2SO4, and stabilized Criegee intermediates (sCIs) using selected ion chemical ionization mass spectrometry. The paper discusses the functional dependence of these species on other measures of the chemical environment (e.g. NO, VOCs, j-values) as well as comparison of model estimates with the observations.

An enhanced procedure for measuring organic acids and methyl esters in PM2.5

NASA Astrophysics Data System (ADS)

Liu, F.; Duan, F. K.; He, K. B.; Ma, Y. L.; Rahn, K. A.; Zhang, Q.

2015-11-01

A solid-phase extraction (SPE) pretreatment procedure allowing organic acids to be separated from methyl esters in fine aerosol has been developed. The procedure first separates the organic acids from fatty acid methyl esters (FAMEs) and other nonacid organic compounds by aminopropyl-based SPE cartridge and then quantifies them by gas chromatography/mass spectrometry. The procedure prevents the fatty acids and dimethyl phthalate from being overestimated, and so allows us to accurately quantify the C4-C11 dicarboxylic acids (DCAs) and the C8-C30 monocarboxylic acids (MCAs). Results for the extraction of DCAs, MCAs, and AMAs in eluate and FAMEs in effluate by SAX and NH2 SPE cartridges exhibited that the NH2 SPE cartridge gave higher extraction efficiency than the SAX cartridge. The recoveries of analytes ranged from 67.5 to 111.3 %, and the RSD ranged from 0.7 to 10.9 %. The resulting correlations between the aliphatic acids and FAMEs suggest that the FAMEs had sources similar to those of the carboxylic acids, or were formed by esterifying carboxylic acids, or that aliphatic acids were formed by hydrolyzing FAMEs. Through extraction and cleanup using this procedure, 17 aromatic acids in eluate were identified and quantified by gas chromatography/tandem mass spectrometry, including five polycyclic aromatic hydrocarbon (PAH): acids 2-naphthoic, biphenyl-4-carboxylic, 9-oxo-9H-fluorene-1-carboxylic, biphenyl-4,4´-dicarboxylic, and phenanthrene-1-carboxylic acid, plus 1,8-naphthalic anhydride. Correlations between the PAH acids and the dicarboxylic and aromatic acids suggested that the first three acids and 1,8-naphthalic anhydride were secondary atmospheric photochemistry products and the last two mainly primary.

Photochemical Production of Singlet Oxygen from Dissolved Organic Matter in Ice.

PubMed

Fede, Alexis; Grannas, Amanda M

2015-11-03

Dissolved natural organic matter (DOM) is a ubiquitous component of natural waters and an important photosensitizer. A variety of reactive oxygen species (ROS) are known to be produced from DOM photochemistry, including singlet oxygen, 1O2. Recently, it has been determined that humic-like substances and unknown organic chromophores are significant contributors to sunlight absorption in snowpack; however, DOM photochemistry in snow/ice has received little attention in the literature. We recently showed that DOM plays an important role in indirect photolysis processes in ice, producing ROS and leading to the efficient photodegradation of a probe hydrophobic organic pollutant, aldrin.1 ROS scavenger experiments indicated that 1O2 played a significant role in the indirect photodegradation of aldrin. Here we quantitatively examine 1O2 photochemically produced from DOM in frozen and liquid aqueous solutions. Steady-state 1O2 production is enhanced up to nearly 1000 times in frozen DOM samples compared to liquid samples. 1O2 production is dependent on the concentration of DOM, but the nature of the DOM source (terrestrial vs microbial) does not have a significant effect on 1O2 production in liquid or frozen samples, with different source types producing similar steady-state concentrations of 1O2. The temperature of frozen samples also has a significant effect on steady-state 1O2 production in the range of 228-262 K, with colder samples producing more steady-state 1O2. The large enhancement in 1O2 in frozen samples suggests that it may play a significant role in the photochemical processes that occur in snow and ice, and DOM could be a significant, but to date poorly understood, oxidant source in snow and ice.

Modification of porous silicon rugate filters through thiol-yne photochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Soeriyadi, Alexander H., E-mail: alexander.soeriyadi@unsw.edu.au; Zhu, Ying, E-mail: alexander.soeriyadi@unsw.edu.au; Gooding, J. Justin, E-mail: justin.gooding@unsw.edu.au

2014-02-24

Porous silicon (PSi) has a considerable potential as biosensor platform. In particular, the ability to modify the surface chemistry of porous silicon is of interest. Here we present a generic method to modify the surface of porous silicon through thiol-yne photochemistry initiated by a radical initiator. Firstly, a freshly etched porous silicon substrate is modified through thermal hydrosilylation with 1,8-nonadiyne to passivate the surface and introduce alkyne functionalities. The alkyne functional surface could then be further reacted with thiol species in the presence of a radical initiator and UV light. Functionalization of the PSi rugate filter is followed with opticalmore » reflectivity measurements as well as high resolution X-ray photoelectron spectroscopy (XPS)« less

Prebiotic significance of extraterrestrial ice photochemistry: detection of hydantoin in organic residues.

PubMed

de Marcellus, Pierre; Bertrand, Marylène; Nuevo, Michel; Westall, Frances; Le Sergeant d'Hendecourt, Louis

2011-11-01

The delivery of extraterrestrial organic materials to primitive Earth from meteorites or micrometeorites has long been postulated to be one of the origins of the prebiotic molecules involved in the subsequent apparition of life. Here, we report on experiments in which vacuum UV photo-irradiation of interstellar/circumstellar ice analogues containing H(2)O, CH(3)OH, and NH(3) led to the production of several molecules of prebiotic interest. These were recovered at room temperature in the semi-refractory, water-soluble residues after evaporation of the ice. In particular, we detected small quantities of hydantoin (2,4-imidazolidinedione), a species suspected to play an important role in the formation of poly- and oligopeptides. In addition, hydantoin is known to form under extraterrestrial, abiotic conditions, since it has been detected, along with various other derivatives, in the soluble part of organic matter of primitive carbonaceous meteorites. This result, together with other related experiments reported recently, points to the potential importance of the photochemistry of interstellar "dirty" ices in the formation of organics in Solar System materials. Such molecules could then have been delivered to the surface of primitive Earth, as well as other telluric (exo-) planets, to help trigger first prebiotic reactions with the capacity to lead to some form of primitive biomolecular activity.

3D printing of natural organic materials by photochemistry

NASA Astrophysics Data System (ADS)

Da Silva Gonçalves, Joyce Laura; Valandro, Silvano Rodrigo; Wu, Hsiu-Fen; Lee, Yi-Hsiung; Mettra, Bastien; Monnereau, Cyrille; Schmitt Cavalheiro, Carla Cristina; Pawlicka, Agnieszka; Focsan, Monica; Lin, Chih-Lang; Baldeck, Patrice L.

2016-03-01

In previous works, we have used two-photon induced photochemistry to fabricate 3D microstructures based on proteins, anti-bodies, and enzymes for different types of bio-applications. Among them, we can cite collagen lines to guide the movement of living cells, peptide modified GFP biosensing pads to detect Gram positive bacteria, anti-body pads to determine the type of red blood cells, and trypsin columns in a microfluidic channel to obtain a real time biochemical micro-reactor. In this paper, we report for the first time on two-photon 3D microfabrication of DNA material. We also present our preliminary results on using a commercial 3D printer based on a video projector to polymerize slicing layers of gelatine-objects.

Photochemistry, Ion Chemistry, and Haze Formation in Pluto’s Atmosphere

NASA Astrophysics Data System (ADS)

Summers, Michael E.; Stern, S. A.; Gladstone, G. Randal; Young, Leslie A.; Olkin, C. B.; Weaver, H. A.; Cheng, A. F.; Strobel, D. F.; Ennico, K. A.; Kammer, J. A.; Parker, A. H.; Retherford, K. D.; Schindhelm, E.; Singer, K. N.; Steffl, A. J.; Tsang, C. C.; Versteeg, M. H.; Greathouse, T. K.; Linscott, I. R.; Tyler, L. G.; Woods, W. W.; Hinson, D. P.; Parker, J. W.; Renaud, J. P.; Ewell, M.; Lisse, Cary M.

2015-11-01

The detection of ethylene (C2H4) and acetylene (C2H2) in Pluto’s atmosphere provides important ground-truth observations for validating photochemical models of Pluto’s atmosphere. Their detection also confirms the production of precursor chemical compounds involved in the formation of tholins, which are thought to give Pluto’s surface its reddish color. Photochemical models predict many other hydrocarbon and nitrile products, currently undetected, which may also be participants in tholin production on Pluto’s surface or on atmospheric haze particles. The observed atmospheric haze layer extending to altitudes of ~140 km above Pluto’s surface, suggests a global and very robust process of atmospheric particle nucleation, growth, and sedimentation onto Pluto’s surface. The high altitude extent of the haze layer suggests that the nucleation process begins above the expected altitude range where hydrocarbons become supersaturated (below ~30 km altitude). This situation may be analogous to that in Titan’s atmosphere, wherein nucleation and aerosol growth is directly related to large negative ion production. In the case of Pluto, this means that nucleation may occur at altitudes as high as 1200 km altitude where ionization in Pluto’s atmosphere peaks. In this paper we discuss these processes and their implications for haze formation in Pluto’s atmosphere and its deposition onto Pluto’s surface. This work was supported by NASA's New Horizons project.

Using Biogenic Sulfur Gases as Remotely Detectable Biosignatures on Anoxic Planets

PubMed Central

Meadows, Victoria S.; Claire, Mark W.; Kasting, James F.

2011-01-01

Abstract We used one-dimensional photochemical and radiative transfer models to study the potential of organic sulfur compounds (CS2, OCS, CH3SH, CH3SCH3, and CH3S2CH3) to act as remotely detectable biosignatures in anoxic exoplanetary atmospheres. Concentrations of organic sulfur gases were predicted for various biogenic sulfur fluxes into anoxic atmospheres and were found to increase with decreasing UV fluxes. Dimethyl sulfide (CH3SCH3, or DMS) and dimethyl disulfide (CH3S2CH3, or DMDS) concentrations could increase to remotely detectable levels, but only in cases of extremely low UV fluxes, which may occur in the habitable zone of an inactive M dwarf. The most detectable feature of organic sulfur gases is an indirect one that results from an increase in ethane (C2H6) over that which would be predicted based on the planet's methane (CH4) concentration. Thus, a characterization mission could detect these organic sulfur gases—and therefore the life that produces them—if it could sufficiently quantify the ethane and methane in the exoplanet's atmosphere. Key Words: Exoplanets—Biosignatures—Anoxic atmospheres—Planetary atmospheres—Remote life detection—Photochemistry. Astrobiology 11, 419–441. PMID:21663401

Evidence for a vibrational phase-dependent isotope effect on the photochemistry of vision.

PubMed

Schnedermann, C; Yang, X; Liebel, M; Spillane, K M; Lugtenburg, J; Fernández, I; Valentini, A; Schapiro, I; Olivucci, M; Kukura, P; Mathies, R A

2018-04-01

Vibronic coupling is key to efficient energy flow in molecular systems and a critical component of most mechanisms invoking quantum effects in biological processes. Despite increasing evidence for coherent coupling of electronic states being mediated by vibrational motion, it is not clear how and to what degree properties associated with vibrational coherence such as phase and coupling of atomic motion can impact the efficiency of light-induced processes under natural, incoherent illumination. Here, we show that deuteration of the H 11 -C 11 =C 12 -H 12 double-bond of the 11-cis retinal chromophore in the visual pigment rhodopsin significantly and unexpectedly alters the photoisomerization yield while inducing smaller changes in the ultrafast isomerization dynamics assignable to known isotope effects. Combination of these results with non-adiabatic molecular dynamics simulations reveals a vibrational phase-dependent isotope effect that we suggest is an intrinsic attribute of vibronically coherent photochemical processes.

Development and testing of meteorology and air dispersion models for Mexico City

NASA Astrophysics Data System (ADS)

Williams, M. D.; Brown, M. J.; Cruz, X.; Sosa, G.; Streit, G.

Los Alamos National Laboratory and Instituto Mexicano del Petróleo are completing a joint study of options for improving air quality in Mexico City. We have modified a three-dimensional, prognostic, higher-order turbulence model for atmospheric circulation (HOTMAC) and a Monte Carlo dispersion and transport model (RAPTAD) to treat domains that include an urbanized area. We used the meteorological model to drive models which describe the photochemistry and air transport and dispersion. The photochemistry modeling is described in a separate paper. We tested the model against routine measurements and those of a major field program. During the field program, measurements included: (1) lidar measurements of aerosol transport and dispersion, (2) aircraft measurements of winds, turbulence, and chemical species aloft, (3) aircraft measurements of skin temperatures, and (4) Tethersonde measurements of winds and ozone. We modified the meteorological model to include provisions for time-varying synoptic-scale winds, adjustments for local wind effects, and detailed surface-coverage descriptions. We developed a new method to define mixing-layer heights based on model outputs. The meteorology and dispersion models were able to provide reasonable representations of the measurements and to define the sources of some of the major uncertainties in the model-measurement comparisons.

Photoproduction of ammonium in the southeastern Beaufort Sea and its biogeochemical implications

NASA Astrophysics Data System (ADS)

Xie, H.; Bélanger, S.; Song, G.; Benner, R.; Taalba, A.; Blais, M.; Tremblay, J.-É.; Babin, M.

2012-08-01

Photochemistry of dissolved organic matter (DOM) plays an important role in marine biogeochemical cycles, including the regeneration of inorganic nutrients. DOM photochemistry affects nitrogen cycling by converting bio-refractory dissolved organic nitrogen to labile inorganic nitrogen, mainly ammonium (NH4+). During the August 2009 Mackenzie Light and Carbon (MALINA) Program, the absorbed photon-based efficiency spectra of NH4+ photoproduction (i.e. photoammonification) were determined using water samples from the SE Beaufort Sea, including the Mackenzie River estuary, shelf, and Canada Basin. The photoammonification efficiency decreased with increasing wavelength across the ultraviolet and visible regimes and was higher in offshore waters than in shelf and estuarine waters. The efficiency was positively correlated with the molar nitrogen:carbon ratio of DOM and negatively correlated with the absorption coefficient of chromophoric DOM (CDOM). Combined with collateral measurements of CO2 and CO photoproduction, this study revealed a stoichiometry of DOM photochemistry with a CO2 : CO : NH4+ molar ratio of 165 : 11 : 1 in the estuary, 60 : 3 : 1 on the shelf, and 18 : 2 : 1 in the Canada Basin. The NH4+ efficiency spectra, along with solar photon fluxes, CDOM absorption coefficients and sea ice concentrations, were used to model the monthly surface and depth-integrated photoammonification rates in 2009. The summertime (June-August) rates at the surface reached 6.6 nmol l-1 d-1 on the Mackenzie Shelf and 3.7 nmol l-1 d-1 further offshore; the depth-integrated rates were correspondingly 8.8 μmol m-2 d-1 and 11.3 μmol m-2 d-1. The offshore depth-integrated rate in August (8.0 μmol m-2 d-1) was comparable to the missing dissolved inorganic nitrogen (DIN) source required to support the observed primary production in the upper 10-m layer of that area. The yearly NH4+ photoproduction in the entire study area was estimated to be 1.4 × 108 moles, with 85% of it being generated in summer when riverine DIN input is low. Photoammonification could mineralize 4% of the annual dissolved organic nitrogen (DON) exported from the Mackenzie River and provide a DIN source corresponding to 7% of the riverine DIN discharge and 1400 times the riverine NH4+ flux. Under a climate warming-induced ice-free scenario, these quantities could increase correspondingly to 6%, 11%, and 2100 times. Photoammonification is thus a significant nitrogen cycling term and may fuel previously unrecognized autotrophic and heterotrophic production pathways in the surface SE Beaufort Sea.

Photoproduction of ammonium in the Southeastern Beaufort Sea and its biogeochemical implications

NASA Astrophysics Data System (ADS)

Xie, H.; Bélanger, S.; Song, G.; Benner, R.; Taalba, A.; Blais, M.; Lefouest, V.; Tremblay, J.-É.; Babin, M.

2012-04-01

Photochemistry of dissolved organic matter (DOM) plays an important role in marine biogeochemical cycles, including the regeneration of inorganic nutrients. DOM photochemistry affects nitrogen cycling by converting bio-refractory dissolved organic nitrogen to labile inorganic nitrogen, mainly ammonium (NH4+). During the August 2009 Mackenzie Light and Carbon (MALINA) Program, the absorbed photon-based efficiency spectra of NH4+ photoproduction (i.e. photoammonification) were determined using water samples from the SE Beaufort Sea, including the Mackenzie River estuary, shelf, and Canada Basin. The photoammonification efficiency decreased with increasing wavelength across the ultraviolet and visible regimes and was higher in offshore waters than in shelf and estuarine waters. The efficiency was positively correlated with the molar nitrogen : carbon ratio of DOM and negatively correlated with the absorption coefficient of chromophoric DOM (CDOM). Combined with collateral measurements of CO2 and CO photoproduction, this study revealed a stoichiometry of DOM photochemistry with a CO2:CO:NH4+ molar ratio of 165:11:1 in the estuary, 60:3:1 on the shelf, and 18:2:1 in the Canada Basin. The NH4+ efficiency spectra, along with solar photon fluxes, CDOM absorption coefficients and sea ice concentrations, were used to model the monthly surface and depth-integrated photoammonification rates in 2009. The summertime (June-August) rates at the surface reached 6.6 nmol l-1 d-1 on the Mackenzie Shelf and 3.7 nmol l-1 d-1 further offshore; the depth-integrated rates were correspondingly 8.8 μmol m-2 d-1 and 11.3 μmol m-2 d-1. The offshore depth-integrated rate in August (8.0 μmol m-2 d-1) was comparable to the missing dissolved inorganic nitrogen (DIN) source required to support the observed primary production in the upper 10-m layer of that area. The yearly NH4+ photoproduction in the entire study area was estimated to be 1.4 × 108 moles, with 85 % of it being generated in summer when riverine DIN input is low. Photoammonification could mineralize 4 % of the annual dissolved organic nitrogen (DON) exported from the Mackenzie River and provide a~DIN source corresponding to 7 % of the riverine DIN discharge and 1400 times the riverine NH4+ flux. Under a climate warming-induced ice-free scenario, these quantities would increase correspondingly to 6 %, 11 %, and 2100 times. Photoammonification is thus a significant nitrogen cycling term and may fuel previously unrecognized autotrophic and heterotrophic production pathways in the surface SE Beaufort Sea.

Atmospheric Transport and Photochemistry of Ozone Over Central Southern Africa During the Southern Africa Fire-Atmosphere Research Initiative

NASA Technical Reports Server (NTRS)

Tyson, P. D.; Garstang, M.; Thompson, A. M.; DAbreton, P.; Diab, R. D.; Browell, E. V.

1997-01-01

Vertically integrated back and forward trajectories for the 300-200, 700-500 and surface-800 hPa levels are calculated using Pretoria as point of origin for the Southern Africa Fire-Atmosphere Research Initiative (SAFARI) period September-October 1992. The transport fields are then combined to show both horizontal and vertical transport of air to and from Pretoria at the different levels. Air transport patterns in the vertical are linked to the occurrence of absolutely stable layers which are also evident in the 16 ozonesonde profiles recorded at Pretoria during SAFARI. The coherence of the stratification based on dynamical and ozone analysis permits the use of mean ozone profiles with air volume fluxes to interpret the ozone in terms of photochemistry and transport within stable layers. Extensive recirculation across the meridional plane at Pretoria implies that advection of ozone is slow and that photochemistry is responsible for the observed vertical structure over central southern Africa in September and October 1992. Requisite ozone formation rates are supported by model analysis of ozone and ozone precursors measured from SAFARI and Transport and Atmospheric Research Chemistry near the Equator-Atlantic aircraft.

Insights into Acetone Photochemistry on Rutile TiO2(110). 1. Off-Normal CH3 Ejection from Acetone Diolate.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrik, Nikolay G.; Henderson, Michael A.; Kimmel, Gregory A.

2015-06-04

Thermal- and photon-stimulated reactions of acetone co-adsorbed with oxygen on rutile TiO2(110) surface are studied with infrared reflection-adsorption spectroscopy (IRAS) combined with temperature programmed desorption and angle-resolved photon stimulated desorption. IRAS results show that n2-acetone diolate ((CH3)2COO) is produced via thermally-activated reactions between the chemisorbed oxygen with co-adsorbed acetone. Formation of acetone diolate is also consistent with 18O / 16O isotopic exchange experiments. During UV irradiation at 30 K, CH3 radicals are ejected from the acetone diolate with a distribution that is peaked at .-. +- 66 degrees from the surface normal along the azimuth (i.e. perpendicular to the rowsmore » of bridging oxygen and Ti5c ions). This distribution is also consistent with the orientation of the C–CH3 bonds in the n2-acetone diolate on TiO2(110). The acetone diolate peaks disappear from the IRAS spectra after UV irradiation and new peaks are observed and associated with n2-acetate. The data presented here demonstrate direct signatures of the proposed earlier 2-step mechanism for acetone photooxidation on TiO2(110)« less

Multistate photo-induced relaxation and photoisomerization ability of fumaramide threads: a computational and experimental study.

PubMed

Altoè, Piero; Haraszkiewicz, Natalia; Gatti, Francesco G; Wiering, Piet G; Frochot, Céline; Brouwer, Albert M; Balkowski, Grzegorz; Shaw, Daniel; Woutersen, Sander; Buma, Wybren Jan; Zerbetto, Francesco; Orlandi, Giorgio; Leigh, David A; Garavelli, Marco

2009-01-14

Fumaric and maleic amides are the photoactive units of an important and widely investigated class of photocontrollable rotaxanes as they trigger ring shuttling via a cis-trans photoisomerization. Here, ultrafast decay and photoinduced isomerization in isolated fumaramide and solvated nitrogen-substituted fumaramides (that are employed as threads in those rotaxanes) have been investigated by means of CASPT2//CASSCF computational and time-resolved spectroscopic techniques, respectively. A complex multistate network of competitive deactivation channels, involving both internal conversion and intersystem crossing (ISC) processes, has been detected and characterized that accounts for the picosecond decay and photochemical/photophysical properties observed in the singlet as well as triplet (photosensitized) photochemistry of fumaramides threads. Interestingly, singlet photochemistry appears to follow a non-Kasha rule model, where nonequilibrium dynamical factors control the outcome of the photochemical process: accessible high energy portions of extended crossing seams turn out to drive the deactivation process and ground-state recovery. Concurrently, extended singlet/triplet degenerate regions of twisted molecular structures with significant spin-orbit-coupling values account for ultrafast (picosecond time scale) ISC processes that lead to higher photoisomerization efficiencies. This model discloses the principles behind the intrinsic photochemical reactivity of fumaramide and its control.

Probing Cosmic Infrared Sources: A Computer Modeling Approach

DTIC Science & Technology

1992-06-01

developed to study various physical phenomena involving dust grains, e.g., molecule formation on grains, grain formation in expanding circumstellar...EVALUATION OF METHODS OF ANALYSIS IN INFRARED ASTR9?NOMY 16 4.0 THEORETICAL STUDIES INVOLVING DUST GRAINS., 16 4.1 Theory of Molecule Formation on Dust Grains...17 4.2 Modeling Grain Formation in Stellar Outflows 7 18 4.3 Infrared Emission from Fractal Grains * 19 4.4 Photochemistry in Circumstellar Envelopes

Novel Anthra[1,2-c][1,2,5]Thiadiazole-6,11-Diones as Promising Anticancer Lead Compounds: Biological Evaluation, Characterization & Molecular Targets Determination.

PubMed

Ali, Ahmed Atef Ahmed; Lee, Yu-Ru; Chen, Tsung-Chih; Chen, Chun-Liang; Lee, Chia-Chung; Shiau, Chia-Yang; Chiang, Chiao-Hsi; Huang, Hsu-Shan

2016-01-01

The novel compounds NSC745885 and NSC757963 developed at our laboratory were tested against a panel of 60 cancer cell lines at the National Cancer Institute, USA, and a panel of 39 cancer cell lines at the Japanese Foundation of Cancer Research. Both compounds demonstrated selective unique multi-log differential patterns of activity, with GI50 values in the sub-micro molar range against cancer cells rather than normal cardiac cells. NSC757963 showed high selectivity towards the leukemia subpanel. Activities of both compounds strongly correlated to expression of NFKB1 and CSNK2B genes, implying that they may inhibit the NF-κB pathway. Immunocytochemical microscopy of OVCAR-3 cells showed clear cytosolic accumulation of the NF-κB p65 subunit following treatment. Western blotting showed dose dependent inhibition of the nuclear expression of the NF-κB p65 subunit with subsequent accumulation in the cytosol following treatment. Docking experiments showed binding of both compounds to the NF-κB activator IKKβ subunit preventing its translocation to the nucleus. Collectively, these results confirm the ability of our compounds to inhibit the constitutively active NF-κB pathway of OVCAR-3 cells. Furthermore, COMPARE analysis indicated that the activity of NSC757963 is similar to the antituberculosis agent rifamycin SV, this was confirmed by testing the antimycobacterial activity of NSC757963 against Mycobacterium tuberculosis, results revealed potent activity suitable for use in clinical practice. Molecular properties and Lipinski's parameters predicted acceptable bioavailability properties with no indication of mutagenicity, tumorigenicity, irritability and reproductive effects. Oral absorption experiments using the human Caco-2 model showed high intestinal absorption of NSC745885 by passive transport mechanism with no intestinal efflux or active transport mechanisms. The unique molecular characterization as well as the illustrated anticancer spectra of activity and bioavailability properties warrant further development of our compounds and present a foundation brick in the pre-clinical investigations to implement such compounds in clinical practice.

Active Molecular Iodine Photochemistry in the Arctic

NASA Astrophysics Data System (ADS)

Raso, A. R. W.; Custard, K. D.; May, N.; Tanner, D.; Newburn, M. K.; Walker, L. R.; Moore, R.; Huey, L. G.; Alexander, M. L. L.; Shepson, P. B.; Pratt, K.

2017-12-01

During springtime, the Arctic atmospheric boundary layer undergoes frequent rapid depletions in ozone and gaseous elemental mercury due to reactions with halogen atoms, influencing atmospheric composition, and pollutant fate. While bromine chemistry has been shown to initiate ozone depletion events, and it has long been hypothesized that iodine chemistry may contribute, no previous measurements of molecular iodine (I2) have been reported in the Arctic. The presence of iodine chemistry is also expected to impact atmospheric new particle formation and therefore cloud properties and radiative forcing. Here we present the first Arctic I2 and snowpack iodide (I-) measurements, which were conducted near Utqiaġvik, AK in January and February 2014. Using chemical ionization mass spectrometry, I2 was observed in the boundary layer at molar ratios of 0.3 ppt and in the snowpack interstitial air at molar ratios up to 22 ppt under natural sunlit conditions and up to 35 ppt when the snowpack surface was artificially irradiated. I2 was not observed in the dark, suggesting a photochemical production mechanism. This is supported by our snowpack measurements of I-, which showed enrichment of up to 1900 times above the seawater ratio of I-/Na+. Simulations show even these low concentrations of I2 observed significantly increases ozone depletion rates, while also producing iodine monoxide at levels recently observed in the Arctic. These results emphasize the significance of iodine chemistry and the role of snowpack photochemistry in Arctic atmospheric composition, and imply that I2 is likely a dominant source of iodine atoms in the Arctic.

Photochemistry of formaldoxime−nitrous acid complexes in an argon matrix: identification of formaldoxime nitrite.

PubMed

Golec, Barbara; Bil, Andrzej; Mielke, Zofia

2009-08-27

We have studied the structure and photochemistry of the formaldoxime−nitrous acid system (CH2NOH−HONO) by help of FTIR matrix isolation spectroscopy and ab initio methods. The MP2/6-311++G(2d,2p) calculations show stability of six isomeric CH2NOH···HONO complexes. The FTIR spectra evidence formation of two hydrogen bonded complexes in an argon matrix whose structures are determined by comparison of the experimental spectra with the calculated ones for the six stable complexes. In the matrix there is present the most stable cyclic complex with two O−H···N bonds; a strong bond is formed between the OH group of HONO and the N atom of CH2NOH and the weaker one between the OH group of CH2NOH and the N atom of HONO. In the other complex present in the matrix the OH group of formaldoxime is attached to the OH group of HONO forming an O−H···O bond. The irradiation of the CH2NOH···HONO complexes with the filtered output of the mercury lamp (λ > 345 nm) leads to the formation of formaldoxime nitrite, CH2NONO, and its two isomeric complexes with water. The main product is the CH2NONO···H2O complex in which water is hydrogen bonded to the N atom of the C═N group. The identity of the photoproducts is confirmed by both FTIR spectroscopy and MP2 or QCISD(full) calculations with the 6-311++G(2d,2p) basis set. The intermediate in this reaction is iminoxyl radical that is formed by abstraction of hydrogen atom from formaldoxime OH group by an OH radical originating from HONO photolysis.

Evaluation of Anticancer Activity of Curcumin Analogues Bearing a Heterocyclic Nucleus.

PubMed

Ahsan, Mohamed Jawed; Ahsan, Mohamed Jawed

2016-01-01

We report herein an in vitro anticancer evaluation of a series of seven curcumin analogues (3a-g). The National Cancer Institute (NCI US) Protocol was followed and all the compounds were evaluated for their anticancer activity on nine different panels (leukemia, non small cell lung cancer, colon cancer, CNS cancer, melanoma, ovarian cancer, renal cancer, prostate cancer and breast cancer) represented by 60 NCI human cancer cell lines. All the compounds showed significant anticancer activity in one dose assay (drug concentration 10 μM) and hence were evaluated further in five dose assays (0.01, 0.1, 1, 10 and 100 μM) and three dose related parameters GI50, TGI and LC50 were calculated for each (3a-g) in micro molar drug concentrations (μM). The compound 3d (NSC 757927) showed maximum mean percent growth inhibition (PGI) of 112.2%, while compound 3g (NSC 763374) showed less mean PGI of 40.1% in the one dose assay. The maximum anticancer activity was observed with the SR (leukemia) cell line with a GI50 of 0.03 μM. The calculated average sensitivity of all cell lines of a particular subpanel toward the test agent showed that all the curcumin analogues showed maximum activity on leukemia cell lines with GI50 values between 0.23 and 2.67 μM.

THE {sup 12}C/{sup 13}C RATIO ON TITAN FROM CASSINI INMS MEASUREMENTS AND IMPLICATIONS FOR THE EVOLUTION OF METHANE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mandt, Kathleen E.; Waite, J. Hunter; Teolis, Benjamin

2012-04-20

We have re-evaluated the Cassini Ion Neutral Mass Spectrometer (INMS) {sup 12}C/{sup 13}C ratios in the upper atmosphere of Titan based on new calibration sensitivities and an improved model for the NH{sub 3} background in the {sup 13}CH{sub 4} mass channel. The INMS measurements extrapolated to the surface give a {sup 12}C/{sup 13}C in CH{sub 4} of 88.5 {+-} 1.4. We compare the results to a revised ratio of 91.1 {+-} 1.4 provided by the Huygens Gas Chromatograph Mass Spectrometer and 86.5 {+-} 7.9 provided by the Cassini Infrared Spectrometer and determine implications of the revised ratios for the evolutionmore » of methane in Titan's atmosphere. Because the measured {sup 12}C/{sup 13}C is within the probable range of primordial values, we can only determine an upper boundary for the length of time since methane began outgassing from the interior, assuming that outgassing of methane (e.g., cryovolcanic activity) has been continuous ever since. We find that three factors play a crucial role in this timescale: (1) the escape rate of methane, (2) the difference between the current and initial ratios and the rate of methane, and (3) production or resupply due to cryovolcanic activity. We estimate an upper limit for the outgassing timescale of 470 Myr. This duration can be extended to 940 Myr if production rates are large enough to counteract the fractionation due to escape and photochemistry. There is no lower limit to the timescale because the current ratios are within the range of possible primordial values.« less

Light, Molecules, Action: Broadband UV-visible transient absorption studies of excited state dynamics in photoactive molecules

NASA Astrophysics Data System (ADS)

Sension, Roseanne

2015-03-01

Broadband UV-visible transient absorption spectroscopy provides a powerful tool for the investigation of the dynamics of electronically excited molecules in the condensed phase. It is now possible to obtain transient spectra on a routine basis spanning the range from <300 nm to >800 nm with femtosecond time resolution. We have used this method to study the excited state dynamics and internal conversion of a range of molecular systems with potential application as optically powered molecular devices. The cyclohexadiene ring-opening reaction is the basis of a class of important optical switches and of the biological synthesis of previtamin D3. The ring-opening reaction is ultrafast, occurring on a picosecond to subpicosecond times scale depending on the substituents around the ring. These have a significant influence on the dynamics and electronic structure of the electronically excited molecule. The results of a series of transient absorption studies as a function of chromophore substitution and environment will be presented. The cis-trans isomerization of polyene molecules, especially substituted stilbenes, provides another important class of functional molecular transformations. Again the excited state dynamics can be ultrafast with photochemistry controlled by details of the curve crossings and conical intersections. Finally the photochemistry of the even more complex set of cobalamin chromophores with a photoalabile C-Co bond has been proposed as a tool for spatio-temporal control of molecule delivery including drug delivery. Broadband transient absorption spectroscopy has been used to investigate the ultrafast electronic dynamics of a range of cobalamin compounds with comparison to detailed theoretical calculations. The results of these studies will be presented.

Analytical methods development for supramolecular design in solar hydrogen production

NASA Astrophysics Data System (ADS)

Brown, J. R.; Elvington, M.; Mongelli, M. T.; Zigler, D. F.; Brewer, K. J.

2006-08-01

In the investigation of alternative energy sources, specifically, solar hydrogen production from water, the ability to perform experiments with a consistent and reproducible light source is key to meaningful photochemistry. The design, construction, and evaluation of a series of LED array photolysis systems for high throughput photochemistry have been performed. Three array systems of increasing sophistication are evaluated using calorimetric measurements and potassium tris(oxalato)ferrate(II) chemical actinometry and compared with a traditional 1000 W Xe arc lamp source. The results are analyzed using descriptive statistics and analysis of variance (ANOVA). The third generation array is modular, and controllable in design. Furthermore, the third generation array system is shown to be comparable in both precision and photonic output to a 1000 W Xe arc lamp.

Photophysics and photochemistry of 2-aminobenzoic acid anion in aqueous solution.

PubMed

Pozdnyakov, Ivan P; Plyusnin, Victor F; Grivin, Vjacheslav P

2009-12-24

Nanosecond laser flash photolysis and absorption and fluorescence spectroscopy were used to study photochemical processes of 2-aminobenzoic acid anion (ABA(-)) in aqueous solutions. Excitation of this species gives rise to the ABA(-) triplet state to the ABA* radical and to the hydrated electron (e(aq)(-)). The last two species result from two-photon processes. In a neutral medium, the main decay channels of ABA(-) triplet state, the ABA* radical, and e(aq)(-) are T-T annihilation, recombination, and capture by the ABA(-) anion, respectively.

Photolysis of α-KETO Acids in Model Atmospheric Water

NASA Astrophysics Data System (ADS)

Eugene, A. J.; Guzman, M. I.

2017-12-01

Recent work has reported the potential of aqueous-phase photochemistry to promote secondary organic aerosol (SOA) formation. New aqueous photochemical SOA sources may contribute to bridging the gap between field measurements of SOA and models of SOA formation. The ubiquitous α-ketocarboxylic acids pyruvic and glyoxylic acid are known products of the atmospheric oxidation of polycyclic aromatic hydrocarbons (PAHs) as well as of biogenic volatile organic compounds (VOCs). The combination of a carbonyl chromophore (absorbing at wavelengths λ ≥ 300 nm) and hydrophilic functional groups makes these acids likely candidates for forming aqueous SOA by direct sunlight photolysis. We use a variety of analytical techniques including: 2,4-dinitrophenylhydrazine (DNPH) derivatization; ultra-high performance liquid chromatography (UHPLC) and ion chromatography (IC) coupled to mass spectrometry;1H and 13C NMR; and 13C gCOSY NMR to probe the kinetics and mechanisms of the direct photolysis of model solutions of pyruvic acid and glyoxylic acid. The results indicate that despite the structural similarity between the two acids, they each react via very different primary photochemical pathways. Pyruvic acid undergoes a proton-coupled electron transfer (PCET) mechanism with radical recombination, resulting in CO2 and 6-8 carbon organic acids. In contrast, glyoxylic acid primarily undergoes α-cleavage to generate CO, CO2, and glyoxal which is a key species in SOA formation. This work demonstrates that aqueous photolysis is a very competitive atmospheric sink for both pyruvic and glyoxylic acid, indicating that these photoreactions are capable of contributing substantially to SOA formation.

Photochemically Initiated Single Polymer Immobilization

PubMed Central

2015-01-01

This Concept article surveys methods for attaching single polymer molecules on solid substrates. A general approach to single polymer immobilization based on the photochemistry of perfluorophenylazides is elaborated. PMID:17444538

Measurements of PAN, PPN, and MPAN made during the 1994 and 1995 Nashville Intensives of the Southern Oxidant Study: Implications for regional ozone production from biogenic hydrocarbons

NASA Astrophysics Data System (ADS)

Roberts, James M.; Williams, Jonathan; Baumann, Karsten; Buhr, Martin P.; Goldan, Paul D.; Holloway, John; Hübler, Gerhard; Kuster, William C.; McKeen, Stuart A.; Ryerson, Thomas B.; Trainer, Michael; Williams, Eric J.; Fehsenfeld, Fredrick C.; Bertman, Steven B.; Nouaime, George; Seaver, Craig; Grodzinsky, Gil; Rodgers, Michael; Young, Valerie L.

1998-09-01

Isoprene and a variety of other reactive hydrocarbons are released in large quantities by vegetation in forested regions and are thought to participate in the NOx-catalyzed production of ozone, a serious air quality problem in North America and Europe [National Research Council, 1991]. The determination of the fraction of O3 formed from anthropogenic NOx and biogenic hydrocarbons (BHC) is a crucial step in the formulation of effective control strategies. Peroxymethacrylic nitric anhydride (MPAN, CH2C(CH3)C(O)OONO2) is formed almost entirely from the atmospheric oxidation of isoprene in the presence of NOx and is an excellent indicator of recent ozone production from isoprene and therefore biogenic hydrocarbons. Measurements are presented here of MPAN, peroxyacetic nitric anhydride (PAN, CH3C(O)OONO2), peroxypropionic nitric anhydride (PPN, CH3CH2C(O)OONO2) and ozone from separate data sets acquired during the 1994 and 1995 Nashville intensive studies of the Southern Oxidant Study. It was found that PAN, a general product of HC-NOx photochemistry, could be well represented as a simple linear combination of contributions from BHC and anthropogenic hydrocarbon (AHC) chemistries as indicated by MPAN and PPN, respectively. The PAN:MPAN ratios found to be characteristic of BHC-dominated chemistry ranged from 6 to 10. The PAN:PPN ratios found to be characteristic of AHC-dominated chemistry ranged from 5.8 to 7.4. These BHC and AHC attributions were used to estimate the contributions of anthropogenic and biogenic hydrocarbons to regional tropospheric ozone production, and substantial BHC-O3 (50-60 ppbv) was estimated in cases where high NOx from power plants was present in areas of high BHC emission. This estimation method provides direct evidence of significant photochemical ozone production from the oxidation of biogenic hydrocarbons in the presence of NOx.

On the utility of the ionosonde Doppler-derived EXB drift during the daytime

NASA Astrophysics Data System (ADS)

Joshi, L. M.; Sripathi, S.

2016-03-01

Vertical EXB drift measured using the ionosonde Doppler sounding during the daytime suffers from an underestimation of the actual EXB drift because the reflection height of the ionosonde signals is also affected by the photochemistry of the ionosphere. Systematic investigations have indicated a fair/good correlation to exist between the C/NOFS and ionosonde Doppler-measured vertical EXB drift during the daytime over magnetic equator. A detailed analysis, however, indicated that the linear relation between the ionosonde Doppler drift and C/NOFS EXB drift varied with seasons. Thus, solar, seasonal, and also geomagnetic variables were included in the Doppler drift correction, using the artificial neural network-based approach. The RMS error in the neural network was found to be smaller than that in the linear regression analysis. Daytime EXB drift was derived using the neural network which was also used to model the ionospheric redistribution in the SAMI2 model. SAMI2 model reproduced strong (weak) equatorial ionization anomaly (EIA) for cases when neural network corrected daytime vertical EXB drift was high (low). Similar features were also observed in GIM TEC maps. Thus, the results indicate that the neural network can be utilized to derive the vertical EXB drift from its proxies, like the ionosonde Doppler drift. These results indicate that the daytime ionosonde measured vertical EXB drift can be relied upon, provided that adequate corrections are applied to it.

Thermal effectiveness of different IR radiators employed in rheumatoid hand therapy as assessed by thermovisual examination.

PubMed

Rutkowski, Radosław; Straburzyńska-Lupa, Anna; Korman, Paweł; Romanowski, Wojciech; Gizińska, Małgorzata

2011-01-01

We conducted a thermovisual comparison of mean hand surface temperature changes upon local heating with two different IR sources. Sixty-six patients with rheumatoid arthritis (47 women and 19 men; average age, 56.1 ± 8.6 years) were subjected to topical heat therapy for one hand with either the standard IR radiator (SIR) or the water filter IRA (wIRA). The surface temperature of the dorsal side of both hands was measured, and thermal images were taken before and up to 2 h after treatment. At 1 min after treatment, SIR application increased the surface skin temperature of the heated hand from 31.5 ± 1.9 to 35.0 ± 1.9 °C (P<0.05), while wIRA increased it from 32.1 ± 1.6 to 34.2 ± 1.1 °C (P<0.05). Constant decline in temperature was observed immediately after treatment, with the temperatures reaching baseline in about 30 and 120 min after wIRA and SIR treatment, respectively. Similar temperature changes were observed in the heated hands for wIRA and SIR, except at 1 min after treatment. Changes in the untreated hands indicated contralateral reaction. The temperature of the warmed hand showed a correlation to the body mass index. © 2011 The Authors. Photochemistry and Photobiology © 2011 The American Society of Photobiology.

Antioxidant responses and photosynthetic behaviors of Kappaphycus alvarezii and Kappaphycus striatum (Rhodophyta, Solieriaceae) during low temperature stress.

PubMed

Li, Hu; Liu, Jianguo; Zhang, Litao; Pang, Tong

2016-12-01

Kappaphycus are farmed in tropical countries as raw material for carrageenan, which is widely used in food industry. The sea area available for farming is one limiting factor in the production of seaweeds. Though cultivation is spreading into subtropical regions, the lower seawater temperature is an important problem encountered in subtropical regions for the farming of Kappaphycus. This research of physiological response to low temperature stress will be helpful for screening Kappaphycus strains for growth in a lower temperature environment. Responses of antioxidant systems and photosystem II (PSII) behaviors in Kappaphycus alvarezii and Kappaphycus striatum were evaluated during low temperature treatments (23, 20, 17 °C). Compared with the controls at 26 °C, the H 2 O 2 concentrations increased in both species when the thalli were exposed to low temperatures (23, 20, 17 °C), but these increases were much greater in K. striatum than in K. alvarezii thalli, suggesting that K. striatum suffered more oxidative stress. The activities of some important antioxidant enzymes (e.g. superoxide dismutase and ascorbate peroxidase) and the hydroxyl free radical scavenging capacity were substantially higher at 23, 20 and 17 °C than at the control 26 °C in K. alvarezii, indicating that the antioxidant system of K. alvarezii enhanced its resistance to low temperature. However, no significant increases of antioxidant enzymes activities were observed at 20 and 17 °C in K. striatum. In addition, both the maximal efficiency of PSII photochemistry (F V /F m ) and the performance index (PI ABS ) decreased significantly in K. striatum at 23 °C, indicating that the photosynthetic apparatus was damaged at 23 °C. In contrast, no significant decreases of either F V /F m or PI ABS were observed in K. alvarezii at 23 °C. It is concluded that K. alvarezii has greater tolerance to low temperature than K. striatum.

Heterogeneous photochemistry of imidazole-2-carboxaldehyde: HO2 radical formation and aerosol growth

NASA Astrophysics Data System (ADS)

González Palacios, Laura; Corral Arroyo, Pablo; Aregahegn, Kifle Z.; Steimer, Sarah S.; Bartels-Rausch, Thorsten; Nozière, Barbara; George, Christian; Ammann, Markus; Volkamer, Rainer

2016-09-01

The multiphase chemistry of glyoxal is a source of secondary organic aerosol (SOA), including its light-absorbing product imidazole-2-carboxaldehyde (IC). IC is a photosensitizer that can contribute to additional aerosol ageing and growth when its excited triplet state oxidizes hydrocarbons (reactive uptake) via H-transfer chemistry. We have conducted a series of photochemical coated-wall flow tube (CWFT) experiments using films of IC and citric acid (CA), an organic proxy and H donor in the condensed phase. The formation rate of gas-phase HO2 radicals (PHO2) was measured indirectly by converting gas-phase NO into NO2. We report on experiments that relied on measurements of NO2 formation, NO loss and HONO formation. PHO2 was found to be a linear function of (1) the [IC] × [CA] concentration product and (2) the photon actinic flux. Additionally, (3) a more complex function of relative humidity (25 % < RH < 63 %) and of (4) the O2 / N2 ratio (15 % < O2 / N2 < 56 %) was observed, most likely indicating competing effects of dilution, HO2 mobility and losses in the film. The maximum PHO2 was observed at 25-55 % RH and at ambient O2 / N2. The HO2 radicals form in the condensed phase when excited IC triplet states are reduced by H transfer from a donor, CA in our system, and subsequently react with O2 to regenerate IC, leading to a catalytic cycle. OH does not appear to be formed as a primary product but is produced from the reaction of NO with HO2 in the gas phase. Further, seed aerosols containing IC and ammonium sulfate were exposed to gas-phase limonene and NOx in aerosol flow tube experiments, confirming significant PHO2 from aerosol surfaces. Our results indicate a potentially relevant contribution of triplet state photochemistry for gas-phase HO2 production, aerosol growth and ageing in the atmosphere.

Three-Dimensional Photochemical Machining with Lasers

DTIC Science & Technology

1983-11-30

559.91 (1.00) 4-Hydroxybenzophenone 27.78 79.42 359.97 (1.00) 0 19.42 55.52 514.93 (0.78) Benzoin 27.03 77.28 369.96 (1.00) 21.01 60.07 475.96 (0.95...Xanthone I x 104 3 x 103 2 x 10 2 -3 Photosensitizer x = 318-320 nm x 2 340-345 nm Benzoin 310 -- x-Methyl benzoin 200 -- X-Hydroxymethyl benzoin -- 150... Benzoin isopropyl ether -- 230 Benzoin phenyl ether -- 250 (a) From: V. 0. McGinniss, in "Oevelopments in Polymer Photochemistry - 3", N. S. Allen, Ed

X-ray-induced photo-chemistry and X-ray absorption spectroscopy of biological samples

PubMed Central

George, Graham N.; Pickering, Ingrid J.; Pushie, M. Jake; Nienaber, Kurt; Hackett, Mark J.; Ascone, Isabella; Hedman, Britt; Hodgson, Keith O.; Aitken, Jade B.; Levina, Aviva; Glover, Christopher; Lay, Peter A.

2012-01-01

As synchrotron light sources and optics deliver greater photon flux on samples, X-ray-induced photo-chemistry is increasingly encountered in X-ray absorption spectroscopy (XAS) experiments. The resulting problems are particularly pronounced for biological XAS experiments. This is because biological samples are very often quite dilute and therefore require signal averaging to achieve adequate signal-to-noise ratios, with correspondingly greater exposures to the X-ray beam. This paper reviews the origins of photo-reduction and photo-oxidation, the impact that they can have on active site structure, and the methods that can be used to provide relief from X-ray-induced photo-chemical artifacts. PMID:23093745

Fluorescence Microscopy of Single Molecules

ERIC Educational Resources Information Center

Zimmermann, Jan; van Dorp, Arthur; Renn, Alois

2004-01-01

The investigation of photochemistry and photophysics of individual quantum systems is described with the help of a wide-field fluorescence microscopy approach. The fluorescence single molecules are observed in real time.

The Effect of N2 Photoabsorption Cross Section Resolution on C2H6 Production in Titan’s Ionosphere

NASA Astrophysics Data System (ADS)

Luspay-Kuti, Adrienn; Mandt, Kathleen E.; Plessis, Sylvain; Greathouse, Thomas K.

2014-11-01

Titan’s rich organic chemistry begins with the photochemistry of only two molecules: N2 and CH4. The details on how higher-order hydrocarbons and nitriles are formed from these molecules have key implications for both the structure and evolution of Titan’s atmosphere, and for its surface-atmosphere interactions. Of high importance is the production of C2H6, which is a sink for CH4, and a main component in the polar lakes. Results of photochemical models, though, may be sensitive to the choice of input parameters, such as the N2 photoabsorption cross section resolution, as previously shown for nitrogen (Liang et al. (2007) ApJL 664, 115-118), and CH4 (Lavvas et al. (2011) Icarus 213, 233-251). Here we investigate the possibility of the same effect on the production rates of C2H6. We modeled production and loss rates, as well as mixing ratio and density profiles between an altitude of 600 and 1600 km for low and high resolution N2 cross sections via a coupled ion-neutral-thermal model (De La Haye et al. (2008) Icarus 197, 110-136; Mandt et al. (2012) JGR 117, E10006). Our results show a clear impact of photoabsorption cross section resolution used on all neutral and ion species contributing to C2H6 production. The magnitude of the influence varies amongst species. Ethane production profiles exhibit a significant increase with better resolution; a factor of 1.2 between 750 and 950 km, and a factor of 1.1 in the total column-integrated production rate. These values are lower limits, as additional reactions involving C2H5 not included in the model may also contribute to the production rates. The clear effect on C2H6 (which is not a parent molecule, nor does it bear nitrogen) may have important implications for other molecules in Titan’s atmosphere as well. The possible non-negligible impact of an isotope of nitrogen may argue for the inclusion of isotopes in photochemical models. For future analysis, development of a more efficient and streamlined model called Planet-INC is underway. This open source model is a high-performance probabilistic planetary model that includes detailed uncertainty analysis capabilities.

A study of hydrogen peroxide chemistry and photochemistry in tea stain solution with relevance to clinical tooth whitening.

PubMed

Young, Nigel; Fairley, Peter; Mohan, Veena; Jumeaux, Coline

2012-12-01

Tooth whitening using hydrogen peroxide is a complex process, and there is still some controversy about the roles of pH, temperature, chemical activators, and the use of light irradiation. In this work the basic interactions between whitening agents and stain molecules are studied in simple solutions, thus avoiding the physics of diffusion and light penetration in the tooth to give clarity on the basic chemistry which is occurring. The absorbance of tea stain solution at 450 nm was measured over a period of 40 min, with various compositions of whitening agent added (including hydrogen peroxide, ferrous gluconate and potassium hydroxide) and at the same time the samples were subjected to blue light (465 nm) or infra-red light (850 nm) irradiation, or alternatively they were heated to 37°C. It is shown that the reaction rates between chromogens in the tea solution and hydrogen peroxide can be accelerated significantly using ferrous gluconate activator and blue light irradiation. Infra red irradiation does not increase the reaction rate through photochemistry, it serves only to increase the temperature. Raising the temperature leads to inefficiency through the acceleration of exothermic decomposition reactions which produce only water and oxygen. By carrying out work in simple solution it was possible to show that ferrous activators and blue light irradiation significantly enhance the whitening process, whereas infra red irradiation has no significant effect over heating. The importance of controlling the pH within the tooth structure during whitening is also demonstrated. Copyright © 2012 Elsevier Ltd. All rights reserved.

Two-Dimensional Intercomparison of Stratospheric Models

NASA Technical Reports Server (NTRS)

Jackman, Charles H. (Editor); Seals, Robert K., Jr. (Editor); Prather, Michael J. (Editor)

1989-01-01

A detailed record is provided for the examination of fundamental differences in photochemistry and transport among atmospheric models. The results of 16 different modeling groups are presented for several model experiments.

Seasonal stratospheric photochemistry on Uranus and Neptune

NASA Astrophysics Data System (ADS)

Moses, Julianne I.; Fletcher, Leigh N.; Greathouse, Thomas K.; Orton, Glenn S.; Hue, Vincent

2018-06-01

A time-variable 1D photochemical model is used to study the distribution of stratospheric hydrocarbons as a function of altitude, latitude, and season on Uranus and Neptune. The results for Neptune indicate that in the absence of stratospheric circulation or other meridional transport processes, the hydrocarbon abundances exhibit strong seasonal and meridional variations in the upper stratosphere, but that these variations become increasingly damped with depth due to increasing dynamical and chemical time scales. At high altitudes, hydrocarbon mixing ratios are typically largest where the solar insolation is the greatest, leading to strong hemispheric dichotomies between the summer-to-fall hemisphere and winter-to-spring hemisphere. At mbar pressures and deeper, slower chemistry and diffusion lead to latitude variations that become more symmetric about the equator. On Uranus, the stagnant, poorly mixed stratosphere confines methane and its photochemical products to higher pressures, where chemistry and diffusion time scales remain large. Seasonal variations in hydrocarbons are therefore predicted to be more muted on Uranus, despite the planet's very large obliquity. Radiative-transfer simulations demonstrate that latitude variations in hydrocarbons on both planets are potentially observable with future JWST mid-infrared spectral imaging. Our seasonal model predictions for Neptune compare well with retrieved C2H2 and C2H6 abundances from spatially resolved ground-based observations (no such observations currently exist for Uranus), suggesting that stratospheric circulation - which was not included in these models - may have little influence on the large-scale meridional hydrocarbon distributions on Neptune, unlike the situation on Jupiter and Saturn.

Processes Influencing Ozone Levels in Alaskan Forest Fires Plumes during Long-Range Transport over the North Atlantic

NASA Technical Reports Server (NTRS)

Real, E.; Law, K. S.; Wienzierl, B.; Fiebig, M.; Petzold, A.; Wild, O.; Methven, J.; Arnold, S.; Stohl, A.; Huntrieser, H.;

Lower Troposphere Stratification and Pollutant Transport over Siberia in April 2006

NASA Astrophysics Data System (ADS)

Paris, J.; Nedelec, P.; Ramonet, M.; Golitsyn, G. S.; Belan, B. D.; Granberg, I. G.; Arshinov, M. Y.; Athier, G.; Boumard, F.; Cousin, J.; Ciais, P.

2006-12-01

In-situ airborne measurement of trace gases CO2, CO and O3 were performed during an intensive campaign over Central and Eastern Siberia, as part of the YAK-AEROSIB project. The campaign took place in April 11-14, 2006. At that time, the region was a weak source of CO2 (<1 gC m-2 d-1) but a number of fires occurred (http://maps.geog.umd.edu) south of the flight track, over north-eastern China. A total of 26 vertical profiles were collected from the ground level up to 7 km along a flight track of 5000 km between Novossibirsk and Yakutsk. The signature of local and more remote pollution sources was observed, associated with layers of elevated CO2 and CO concentrations, typically higher than 390 ppm and 250 ppb respectively. In most layers, a positive correlation between CO2 and CO is observed. The spatial extent of these layers can be tracked coherently on profiles up to 800 km apart. Layers are encountered above 3500 m, but they are more marked above 5000 m. This agrees well with a previously established climatology of ozone and water vapour layers in the troposphere from the MOZAIC programme. The representation of such layers in current chemistry transport is challenging, due to the model's limited vertical resolution and vertical mixing parameterization. The CO vertical distribution indicated a high variability near the surface (140-300 ppbv), more stable, but still variable concentrations between 1 and 4 km (120-200 ppbv) and surprisingly elevated CO values aloft, reaching up to 250 ppbv in the Eastern part of the flight track. High ozone values were occasionally found in the free troposphere (50-60 ppbv) with one intrusion of stratospheric air and one occurrence of active photochemistry in the Kemerovo area. Elsewhere, the lack of correlation between CO and ozone suggests the presence of aged air masses, without active photochemistry. Systematic back-trajectories calculated for each profile pointed out to zonal flow conditions, bringing pollution from Europe to Siberia. Some air masses originating from China and Mongolia south of the flight track were however sampled further to the South-East. High altitude CO concentrations are higher in the southern part of the track. The complementary use of the MOPITT space-borne CO observations suggested that the high CO concentrations measured during the YAK-AEROSIB campaign were probably caused by the transport of polluted air from China.

Determination of Spectroscopic Properties of Atmospheric Molecules from High Resolution Vacuum Ultraviolet Cross Section and Wavelength Measurements

NASA Technical Reports Server (NTRS)

Parkinson, W. H.; Yoshino, K.

1997-01-01

An account is given of progress during the period 8/l/96-7/31/97 on work on (a) cross section measurements of O2 S-R using a Fourier transform spectrometer (FTS) at the Photon Factory in Japan; (b) the determination of the predissociation linewidths of the Schumann-Runge bands (S-R) of 02; (c) cross section measurements of 02 Herzberg bands using a Fourier transform spectrometer (FTS) at Imperial College; and (d) cross section measurements of H2O in the wavelength region 120-188 nm. The experimental investigations are effected at high resolution with a 6.65 m scanning spectrometer and with the Fourier transform spectrometer. Below 175 nm, synchrotron radiation is most suitable for cross section measurements in combination with spectrometers at the Photon Factory Japan. Cross section measurements of the Doppler limited bands depend on using the very high resolution, available with the Fourier transform spectrometer, (0.025/cm resolution). All of these spectroscopic measurements are needed for accurate calculations of the production of atomic oxygen, the penetration of solar radiation into the Earth's atmosphere, and photochemistry of minor molecules.

Constraints on the microphysics of Pluto's photochemical haze from New Horizons observations

NASA Astrophysics Data System (ADS)

Gao, Peter; Fan, Siteng; Wong, Michael L.; Liang, Mao-Chang; Shia, Run-Lie; Kammer, Joshua A.; Yung, Yuk L.; Summers, Michael E.; Gladstone, G. Randall; Young, Leslie A.; Olkin, Catherine B.; Ennico, Kimberly; Weaver, Harold A.; Stern, S. Alan; New Horizons Science Team

2017-05-01

The New Horizons flyby of Pluto confirmed the existence of hazes in its atmosphere. Observations of a large high- to low- phase brightness ratio, combined with the blue color of the haze (indicative of Rayleigh scattering), suggest that the haze particles are fractal aggregates, perhaps analogous to the photochemical hazes on Titan. Therefore, studying the Pluto hazes can shed light on the similarities and differences between the Pluto and Titan atmospheres. We model the haze distribution using the Community Aerosol and Radiation Model for Atmospheres assuming that the distribution is shaped by downward transport and coagulation of particles originating from photochemistry. Hazes composed of both purely spherical and purely fractal aggregate particles are considered. General agreement between model results and solar occultation observations is obtained with aggregate particles when the downward mass flux of photochemical products is equal to the column-integrated methane destruction rate ∼1.2 × 10-14 g cm-2 s-1, while for spherical particles the mass flux must be 2-3 times greater. This flux is nearly identical to the haze production flux of Titan previously obtained by comparing microphysical model results to Cassini observations. The aggregate particle radius is sensitive to particle charging effects, and a particle charge to radius ratio of 30 e-/μm is necessary to produce ∼0.1-0.2 μm aggregates near Pluto's surface, in accordance with forward scattering measurements. Such a particle charge to radius ratio is 2-4 times higher than those previously obtained for Titan. Hazes composed of spheres with the same particle charge to radius ratio have particles that are 4 times smaller at Pluto's surface. These results further suggest that the haze particles are fractal aggregates. We also consider the effect of condensation of HCN, C2H2, C2H4, and C2H6 on the haze particles, which may play an important role in shaping their altitude and size distributions.

Infrared spectroscopy of Triton and Pluto ice analogs: the case for saturated hydrocarbons.

PubMed

Bohn, R B; Sandford, S A; Allamandola, L J; Cruikshank, D P

1994-09-01

The infrared transmission spectra and photochemical behavior of various organic compounds isolated in solid N2 ices, appropriate for applications to Triton and Pluto, are presented. It is shown that excess absorption in the surface spectra of Triton and Pluto, i.e., absorption not explained by present models incorporating molecules already identified on these bodies (N2, CH4, CO, and CO2), that starts near 4450 cm-1 (2.25 micrometers) and extends to lower frequencies, may be due to alkanes (C(n)H2n+2) and related molecules frozen in the nitrogen. Branched and linear alkanes may be responsible. Experiments in which the photochemistry of N2:CH4 and N(2):CH4:CO ices was explored demonstrate that the surface ices of Triton and Pluto may contain a wide variety of additional species containing H, C, O, and N. Of these, the reactive molecule diazomethane, CH2N2, is particularly important since it may be largely responsible for the synthesis of larger alkanes from CH4 and other small alkanes. Diazomethane would also be expected to drive chemical reactions involving organics in the surface ices of Triton and Pluto toward saturation, i.e., to reduce multiple CC bonds. The positions and intrinsic strengths (A values) of many of the infrared absorption bands of N2 matrix-isolated molecules of relevance to Triton and Pluto have also been determined. These can be used to aid in their search and to place constraints on their abundances. For example, using these A values the abundance ratios CH4/N2 approximately 1.3 x 10(-3), C2H4/N2 < or = 9.5 x 10(-7) and H2CO/N2 < or = 7.8 x 10(-7) are deduced for Triton and CH4/N2 approximately 3.1 x 10(-3), C2H4/N2 < or = 4.1 x 10(-6), and H2CO/N2 < or = 5.2 x 10(-6) deduced for Pluto. The small amounts of C2H4 and H2CO in the surface ices of these bodies are in disagreement with the large abundances expected from many theoretical models.

Observations of Dinitrogen Pentoxide and Nitryl Chloride at two inland sites in North China: Abundances, Origins, and Impact on Photochemistry

NASA Astrophysics Data System (ADS)

LI, Q.; Xue, L.; Tham, Y. J.; Wang, W.; Yun, H.; Wang, T.; Wang, Z.; Wang, X.; Zhang, L.; Yao, L.; Wen, L.; Lu, K.; Zhang, Y.; Wang, W.

2015-12-01

Dinitrogen pentoxide (N2O5) and nitryl chloride (ClNO2) are key players in the nocturnal tropospheric chemistry, and also have potential to perturb the next-day's photochemistry. We here present the first ambient measurements of N2O5 and ClNO2 in inland regions of northern China, which is suffering from severe photochemical smog and haze pollution. A chemical ionization mass spectrometer (CIMS) was deployed at a semi-rural site in Wangdu, Hebei and on the top of Mt Tai, Shandong (1500 m a.s.l.) during the summer of 2014. At Wangdu, significant levels of ClNO2 were observed persistently throughout the campaign, with the maximum concentration of up to 2.1 ppbv (1-min data). N2O5 were generally in small concentrations but on few occasions reached up to hundreds of pptv. Clear variation of ClNO2 and N2O5 from night to night suggests the variability of N2O5 heterogeneous reactivity under different conditions over the region. On the mountain-top, elevated ClNO2-laden plumes were frequently observed around mid-night with a 1-min maximum of 2.1 ppbv, whilst N2O5 was always in very low levels indicating a fast N2O5 hydrolysis. The elevated ClNO2 levels at both locations were significantly influenced by the high NOx-saturated urban plumes and non-oceanic sources of chloride like biomass burning and coal-fired power plants in the region. MCM (Master Chemical Mechanism) modeling analyses indicate the significance of ClNO2 photolysis to the daytime radical and ozone production. Our study implies that the N2O5 reactivity and chlorine activation are significant in North China, and should be also important in other non-marine regions of China where NOx and particle chloride are in great abundances.

Kinetics and photochemistry Golden, D. M.

NASA Technical Reports Server (NTRS)

Demore, W. B.; Golden, R. F.; Howard, C. J.; Kurylo, M. J.; Margitan, J. J.; Molina, M. J.; Ravishankara, A. R.; Watson, R. T.; Hampson, R. F.

1985-01-01

The data for chemical kinetics rate constants and photochemical cross sections taken from a compilation prepared in early 1985, entitled Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling, is presented.

The atmosphere simulation chamber SAPHIR: a tool for the investigation of photochemistry.

NASA Astrophysics Data System (ADS)

Brauers, T.; Bohn, B.; Johnen, F.-J.; Rohrer, R.; Rodriguez Bares, S.; Tillmann, R.; Wahner, A.

2003-04-01

On the campus of the Forschungszentrum Jülich we constructed SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber) which was accomplished in fall 2001. The chamber consists of a 280-m^3 double-wall Teflon bag of cylindrical shape that is held by a steel frame. Typically 75% of the outside actinic flux (290~nm~--~420~nm) is available inside the chamber. A louvre system allows switching between full sun light and dark within 40 s giving the opportunity to study relaxation processes of the photo chemical system. The SAPHIR chamber is equipped with a comprehensive set of sensitive instruments including the measurements of OH, HO_2, CO, hydrocarbons, aldehydes, nitrogen-oxides and solar radiation. Moreover, the modular concept of SAPHIR allows fast and flexible integration of new instruments and techniques. In this paper we will show the unique and new features of the SAPHIR chamber, namely the clean air supply and high purity water vapor supply providing a wide range of trace gas concentrations being accessible through the experiments. We will also present examples from the first year of SAPHIR experiment showing the scope of application from high quality instrument inter-comparison and kinetic studies to the simulation of complex mixtures of trace gases at ambient concentrations.

LABORATORY PHOTO-CHEMISTRY OF PAHS: IONIZATION VERSUS FRAGMENTATION

PubMed Central

Zhen, Junfeng; Castellanos, Pablo; Paardekooper, Daniel M.; Ligterink, Niels; Linnartz, Harold; Nahon, Laurent; Joblin, Christine; Tielens, Alexander G. G. M.

2015-01-01

Interstellar Polycyclic Aromatic Hydrocarbons (PAH) are expected to be strongly processed by Vacuum Ultra-Violet (VUV) photons. Here, we report experimental studies on the ionization and fragmentation of coronene (C24H12), ovalene (C32H14) and hexa-peri-hexabenzocoronene (HBC; C42H18) cations by exposure to synchrotron radiation in the range of 8–40 eV. The results show that for small PAH cations such as coronene, fragmentation (H-loss) is more important than ionization. However, as the size increases, ionization becomes more and more important and for the HBC cation, ionization dominates. These results are discussed and it is concluded that, for large PAHs, fragmentation only becomes important when the photon energy has reached the highest ionization potential accessible. This implies that PAHs are even more photo-stable than previously thought. The implications of this experimental study for the photo-chemical evolution of PAHs in the interstellar medium (ISM) are briefly discussed. PMID:26688710

LABORATORY PHOTO-CHEMISTRY OF PAHs: IONIZATION VERSUS FRAGMENTATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhen, Junfeng; Castellanos, Pablo; Ligterink, Niels

2015-05-01

Interstellar polycyclic aromatic hydrocarbons (PAHs) are expected to be strongly processed by vacuum ultraviolet photons. Here, we report experimental studies on the ionization and fragmentation of coronene (C{sub 24}H{sub 12}), ovalene (C{sub 32}H{sub 14}) and hexa-peri-hexabenzocoronene (HBC; C{sub 42}H{sub 18}) cations by exposure to synchrotron radiation in the range of 8–40 eV. The results show that for small PAH cations such as coronene, fragmentation (H-loss) is more important than ionization. However, as the size increases, ionization becomes more and more important and for the HBC cation, ionization dominates. These results are discussed and it is concluded that, for large PAHs,more » fragmentation only becomes important when the photon energy has reached the highest ionization potential accessible. This implies that PAHs are even more photo-stable than previously thought. The implications of this experimental study for the photo-chemical evolution of PAHs in the interstellar medium are briefly discussed.« less

Solid state photochemistry of polycarbonates

NASA Technical Reports Server (NTRS)

Gupta, A.; Rembaum, A.; Moacanin, J.

1978-01-01

The quantum yield of photoFries rearrangement in a polycarbonate film has been analyzed as a function of temperature and humidity on the basis of previously reported (Koyler and Mann, 1977) experimental data. Results indicate that in the homogeneous amorphous phase, photoFries rearrangement is a concerted process proceeding either from the pi star reversed arrow n singlet, in which case it must be subject to considerable self quenching, or from a triplet, presumably the first triplet since the lifetime of higher triplets is expected to be very short in the solid phase. If the parent excited state is the first triplet, chain scission is possibly an independent process, probably occurring from the pi star reversed arrow n singlet. Evidence of chain scission on photodegradation in the solid state includes loss of C-O and C-C bond intensities revealed in the Fourier transform infrared spectra, gel permeation chromotography elution profiles of degraded film samples dissolved in CHCl3, and a decrease in tensile strength and T sub g as photodegradation proceeds. Chain scission is apparently inhibited as photoFries products accumulate.

Pluto's Nonvolatile Chemical Compounds

NASA Astrophysics Data System (ADS)

Grundy, William M.; Binzel, Richard; Cook, Jason C.; Cruikshank, Dale P.; Dalle Ore, Cristina M.; Earle, Alissa M.; Ennico, Kimberly; Jennings, Donald; Howett, Carly; Kaiser, Ralf-Ingo; Linscott, Ivan; Lunsford, A. W.; Olkin, Catherine B.; Parker, Alex Harrison; Parker, Joel Wm.; Philippe, Sylvain; Protopapa, Silvia; Quirico, Eric; Reuter, D. C.; Schmitt, Bernard; Singer, Kelsi N.; Spencer, John R.; Stansberry, John A.; Stern, S. Alan; Tsang, Constantine; Verbiscer, Anne J.; Weaver, Harold A.; Weigle, G. E.; Young, Leslie

2016-10-01

Despite the migration of Pluto's volatile ices (N2, CO, and CH4) around the surface on seasonal timescales, the planet's non-volatile materials are not completely hidden from view. They occur in a variety of provinces formed over a wide range of timescales, including rugged mountains and chasms, the floors of mid-latitude craters, and an equatorial belt of especially dark and reddish material typified by the informally named Cthulhu Regio. NASA's New Horizons probe observed several of these regions at spatial resolutions as fine as 3 km/pixel with its LEISA imaging spectrometer, covering wavelengths from 1.25 to 2.5 microns. Various compounds that are much lighter than the tholin-like macromolecules responsible for the reddish coloration, but that are not volatile at Pluto surface temperatures such as methanol (CH3OH) and ethane (C2H6) have characteristic absorption bands within LEISA's wavelength range. This presentation will describe their geographic distributions and attempt to constrain their origins. Possibilities include an inheritance from Pluto's primordial composition (the likely source of H2O ice seen on Pluto's surface) or ongoing production from volatile precursors through photochemistry in Pluto's atmosphere or through radiolysis on Pluto's surface. New laboratory data inform the analysis.This work was supported by NASA's New Horizons project.

Net ozone photochemical production over the eastern and central North Pacific as inferred from GTE/CITE 1 observations during fall 1983

NASA Technical Reports Server (NTRS)

Chameides, W. L.; Davis, D. D.; Rodgers, M. O.; Bradshaw, J.; Sandholm, S.; Sachse, G.; Hill, G.; Gregory, G.

1987-01-01

The role of photochemistry in the budget of tropospheric ozone is studied. Measurements of O3, NO, CO, H2O vapor, and temperature obtained during the fall of 1983 during the GTE/CITE project over the eastern and central North Pacific Ocean are analyzed. The effect of altitude on the measurements is discussed. The analysis reveals a correlation between ozone and NO levels; both increase in concentration and variability with altitude. It is observed that an additional source of secondary importance associated wih CO-rich air parcels exists. A photochemical model is utilized to calculate the net rate of ozone production by photochemical reactions. A net photochemical source of ozone in the free troposphere and a net sink in the boundary layer are detected. The relation between the ozone source in the free troposphere and NO is examined. It is estimated that photochemistry provides a net ozone source to the free troposphere overlying the eastern and central North Pacific Ocean of about 5 x 10 to the 10th molecules/sq cm sec and a net sink of ozone to the boundary layer overlying this region of about 3 x 10 to the 10th molecules/sq cm sec.

Photoresist: Fabrication, Characterization and Its Sensitivity on the Exposures of X-Ray and Ultraviolet

NASA Astrophysics Data System (ADS)

Sutikno; Susilo; Raharja, H. D.

2018-05-01

The epoxy resin-based photoresist is fabricated by mixing of resin (polymer), sodium acetate trihydrate and ethanol in mass variation using heated magnetic stirrer at 100 rpm speed and temperature of 75 °C. Sodium acetate trihydrate and ethanol each play role as photoactive compound (PAC) and solvent, respectively. Photoresist thin films were grown through spin coating method in voltage 5 V during the 60 s and heating temperature of 150 °C for 15 min. To determine photoresist sensitivity, ultraviolet and X-ray were exposed on the photoresist surfaces. The fabricated photoresist properties are densities of 1 g·mL‑1 to 1.23 g·mL‑1, dynamic viscosities of 7 Cp to 22 Cp and kinematic viscosities of 7 Cst to 18 Cst. The absorbances of thin films are in the wavelength range of 350 nm to 1050 nm at the maximum absorbances of 0.2 to 0.5 in the wavelength g-line, h-line, and i-line. The generated maximum current achieved (1.84 × 10‑8) A. The microstructures of epoxy-based photoresist seem homogeneous. The sensitivities of UV exposures show a photochemistry reaction on photoresist occurred, however for X-ray exposure no reaction found.

Observations of CO above Venus cloud top near 4.53 μm

NASA Astrophysics Data System (ADS)

Marcq, E.; Encrenaz, T.; Widemann, T.; Bertaux, J. L.

2013-09-01

Venus' cloud top region exhibits a higher level of variability both in space and time than previously thought. The interplay between photochemistry, dynamics and cloud microphysics requires more observational constraints in order to be fully grasped. Recent observations of sulfur dioxide (SO2) variability [2, 8, 7, 9] have evidenced both short-term, longterm and latitudinal variability whose origin remains mysterious (volcanogenic emissions? dynamic variability?). A better knowledge of the variability of other minor species would be highly welcome in this context. Carbon monoxide (CO), whose pattern of sinks and sources is opposite to SO2, is a prime candidate.

The origin and evolution of dust in interstellar and circumstellar environments

NASA Technical Reports Server (NTRS)

Whittet, Douglas C. B.; Leung, Chun M.

1993-01-01

This status report covers the period from the commencement of the research program on 1 Jul. 1992 through 30 Apr. 1993. Progress is reported for research in the following areas: (1) grain formation in circumstellar envelopes; (2) photochemistry in circumstellar envelopes; (3) modeling ice features in circumstellar envelopes; (4) episodic dust formation in circumstellar envelopes; (5) grain evolution in the diffuse interstellar medium; and (6) grain evolution in dense molecular clouds.

Changes in the photochemical environment of the temperate North Pacific troposphere in response to increased Asian emissions

NASA Astrophysics Data System (ADS)

Parrish, D. D.; Dunlea, E. J.; Atlas, E. L.; Schauffler, S.; Donnelly, S.; Stroud, V.; Goldstein, A. H.; Millet, D. B.; McKay, M.; Jaffe, D. A.; Price, H. U.; Hess, P. G.; Flocke, F.; Roberts, J. M.

2004-12-01

Measurements during the Intercontinental Transport and Chemical Transformation 2002 (ITCT 2K2) field study characterized the springtime, eastern Pacific ozone distribution at two ground sites, from the National Oceanic and Atmospheric Administration WP-3D aircraft, and from a light aircraft operated by the University of Washington. D. Jaffe and colleagues compared the 2002 ozone distribution with measurements made in the region over the two previous decades and show that average ozone levels over the eastern midlatitude Pacific have systematically increased by ˜10 ppbv in the last two decades. Here we provide substantial evidence that a marked change in the photochemical environment in the springtime troposphere of the North Pacific is responsible for this increased O3. This change is evidenced in the eastern North Pacific ITCT 2K2 study region by (1) larger increases in the minimum observed ozone levels compared to more modest increases in the maximum levels, (2) increased peroxyacetyl nitrate (PAN) levels that parallel trends in NOx emissions, and (3) decreased efficiency of photochemical O3 destruction, i.e., less negative O3 photochemical tendency (or net rate of O3 photochemical production; P(O3)). This changed photochemical environment is hypothesized to be due to anthropogenic emissions from Asia, which are believed to have substantially increased over the two decades preceding the study. We propose that their influence has changed the springtime Pacific tropospheric photochemistry from predominately ozone destroying to more nearly ozone producing. However, chemical transport model calculations indicate the possible influence of a confounding factor; unusual transport of tropical air to the western North Pacific during one early field study may have played a role in this apparent change in the photochemistry.

The Gas Production Rate and Coma Structure of Comet C/1995 O1 (Hale-Bopp)

NASA Astrophysics Data System (ADS)

Morgenthaler, Jeffrey P.; Harris, Walter M.; Roesler, Frederick L.; Scherb, Frank; Anderson, Christopher M.; Doane, Nathaniel E.; Oliversen, Ronald J.

2002-06-01

The University of Wisconsin-Madison and NASA-Goddard conducted acomprehensive multi-wavelength observing campaign of coma emissionsfrom comet Hale-Bopp, including OH 3080 Å, [O I] 6300 Å H2O+ 6158 Å, H Balmer-α 6563 Å, NH2 6330 Å, [C I] 9850 ÅCN 3879 Å, C2 5141 Å, C3 4062 Å,C I 1657 Å, and the UV and optical continua. In thiswork, we concentrate on the results of the H2O daughter studies.Our wide-field OH 3080 Å measured flux agrees with other, similarobservations and the expected value calculated from published waterproduction rates using standard H2O and OH photochemistry.However, the total [O I] 6300 Å flux determined spectroscopically overa similar field-of-view was a factor of 3-4 higher than expected.Narrow-band [O I] images show this excess came from beyond theH2O scale length, suggesting either a previously unknown source of[O I] or an error in the standard OH + ν→ O(1 D) + H branching ratio. The Hale-Bopp OH and[O I] distributions, both of which were imaged tocometocentric distances >1 × 106 km, were more spatiallyextended than those of comet Halley (after correcting for brightnessdifferences), suggesting a higher bulk outflow velocity. Evidence ofthe driving mechanism for this outflow is found in the Hα lineprofile, which was narrower than in comet Halley (though likelybecause of opacity effects, not as narrow as predicted by Monte-Carlomodels). This is consistent with greater collisional coupling betweenthe suprathermal H photodissociation products and Hale-Bopp's densecoma. Presumably because of mass loading of the solar wind by ionsand ions by the neutrals, the measured acceleration of H2O+ downthe ion tail was much smaller than in comet Halley. Tailwardextensions in the azimuthal distributions of OH 3080 Å,[O I], and [C I] , as well as a Doppler asymmetry in the[O I] line profile, suggest ion-neutral coupling. While thetailward extension in the OH can be explained by increased neutralacceleration, the [O I] 6300 Å and [C I] 9850 Å emissions show 13%and >200% excesses in this direction (respectively), suggesting anon-negligible contribution from dissociative recombination of CO+and/or electron collisional excitation. Thus, models including theeffects of photo- and collisional chemistry are necessary for the fullinterpretation of these data.

Multiple active site residues are important for photochemical efficiency in the light-activated enzyme protochlorophyllide oxidoreductase (POR).

PubMed

Menon, Binuraj R K; Hardman, Samantha J O; Scrutton, Nigel S; Heyes, Derren J

2016-08-01

Protochlorophyllide oxidoreductase (POR) catalyzes the light-driven reduction of protochlorophyllide (Pchlide), an essential, regulatory step in chlorophyll biosynthesis. The unique requirement of the enzyme for light has provided the opportunity to investigate how light energy can be harnessed to power biological catalysis and enzyme dynamics. Excited state interactions between the Pchlide molecule and the protein are known to drive the subsequent reaction chemistry. However, the structural features of POR and active site residues that are important for photochemistry and catalysis are currently unknown, because there is no crystal structure for POR. Here, we have used static and time-resolved spectroscopic measurements of a number of active site variants to study the role of a number of residues, which are located in the proposed NADPH/Pchlide binding site based on previous homology models, in the reaction mechanism of POR. Our findings, which are interpreted in the context of a new improved structural model, have identified several residues that are predicted to interact with the coenzyme or substrate. Several of the POR variants have a profound effect on the photochemistry, suggesting that multiple residues are important in stabilizing the excited state required for catalysis. Our work offers insight into how the POR active site geometry is finely tuned by multiple active site residues to support enzyme-mediated photochemistry and reduction of Pchlide, both of which are crucial to the existence of life on Earth. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Science Update: Inorganic Chemistry.

ERIC Educational Resources Information Center

Rawls, Rebecca

1981-01-01

Describes areas of inorganic chemistry which have changed dramatically in the past year or two, including photochemistry, electrochemistry, organometallic complexes, inorganic reaction theory, and solid state chemistry. (DS)

In Situ Detection of OH, HO2, ClO, BrO, NO2, ClONO2, BrONO2, ClOOCl, H2O, and O3 from the ER2

NASA Technical Reports Server (NTRS)

Anderson, James G.

2001-01-01

We review here the scientific progress that has emerged during the period January 1, 1998 through March 31, 2001. Results from the Sage III Ozone Loss and Validation Experiment (SOLVE) and Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) mission, and continuing work on prior missions, taken in order, including radical control of ozone on the northern hemisphere stratosphere, evolution of NO2 over the arctic winter and its effects on reactive chlorine, and the first measurements of ClOOCl in the stratosphere.

Atmospheric degradation of 2-chloroethyl vinyl ether, allyl ether and allyl ethyl ether: Kinetics with OH radicals and UV photochemistry.

PubMed

Antiñolo, M; Ocaña, A J; Aranguren, J P; Lane, S I; Albaladejo, J; Jiménez, E

2017-08-01

Unsaturated ethers are oxygenated volatile organic compounds (OVOCs) emitted by anthropogenic sources. Potential removal processes in the troposphere are initiated by hydroxyl (OH) radicals and photochemistry. In this work, we report for the first time the rate coefficients of the gas-phase reaction with OH radicals (k OH ) of 2-chloroethyl vinyl ether (2ClEVE), allyl ether (AE), and allyl ethyl ether (AEE) as a function of temperature in the 263-358 K range, measured by the pulsed laser photolysis-laser induced fluorescence technique. No pressure dependence of k OH was observed in the 50-500 Torr range in He as bath gas, while a slightly negative T-dependence was observed. The temperature dependent expressions for the rate coefficients determined in this work are: The estimated atmospheric lifetimes (τ OH ) assuming k OH at 288 K were 3, 2, and 4 h for 2ClEVE, AE and AEE, respectively. The kinetic results are discussed in terms of the chemical structure of the unsaturated ethers by comparison with similar compounds. We also report ultraviolet (UV) and infrared (IR) absorption cross sections (σ λ and σ(ν˜), respectively). We estimate the photolysis rate coefficients in the solar UV actinic region to be less than 10 -7 s -1 , implying that these compounds are not removed from the atmosphere by this process. In addition, from σ(ν˜) and τ OH , the global warming potential of each unsaturated ether was calculated to be almost zero. A discussion on the atmospheric implications of the titled compounds is presented. Copyright © 2017 Elsevier Ltd. All rights reserved.

Probing how initial retinal configuration controls photochemical dynamics in retinal proteins

NASA Astrophysics Data System (ADS)

Wand, A.; Rozin, R.; Eliash, T.; Friedman, N.; Jung, K. H.; Sheves, M.; Ruhman, S.

2013-03-01

The effects of the initial retinal configuration and the active isomerization coordinate on the photochemistry of retinal proteins (RPs) are assessed by comparing photochemical dynamics of two stable retinal ground state configurations (all-trans,15-anti vs. 13-cis,15-syn), within two RPs: Bacteriorhodopsin (BR) and Anabaena Sensory Rhodopsin (ASR). Hyperspectral pump-probe spectroscopy shows that photochemistry starting from 13-cis retinal in both proteins is 3-10 times faster than when started in the all-trans state, suggesting that the hastening is ubiquitous to microbial RPs, regardless of their different biological functions and origin. This may also relate to the known disparity of photochemical rates between microbial RPs and visual pigments. Importance and possible underlying mechanisms are discussed as well.

Photochemistry of transition-metal phthalocyanines. Analysis of the photochemical and photophysical properties of the acido(phthalocyaninato)rhodium(III) complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferraudi, G.; Muralidharan, S.

1983-01-01

The ultraviolet photochemistry of the rhodium(III) phthalocyanines Rh(ph)(CH/sub 3/OH)X with X = Cl/sup -/, Br/sup -/, and I/sup -/ was investigated at different wavelengths. The same action spectrum for the photoinduced hydrogen abstraction was obtained for the three compounds. The photonic energy of the excitation is degraded in part by emission at short wavelengths, e.g. lambda/sub max/ approx. = 420 nm. Such a violet emission, observed with phthalocyanines of Al(III), Rh(III), Co(III), and Ru(II), has been attributed to the relaxation of an upper /sup 3/pipi* excited state. The emission spectra at 77 K exhibited vibronic components with a separation betweenmore » successive peaks ..delta..v approx. = 1.3 x 10/sup 3/ cm/sup -1/. A comparison between the excitation and action spectra shows the difference in the paths that populate the reactive npi* and upper emissive pipi* states. An investigation of the time dependence of the upper /sup 3/pipi* emission and lowest /sup 3/pipi* absorptions reveals the participation of triplet sublevels in the degradation of the excitation energy. The relationship between photoemissive and photoreactive states is discussed. 40 references, 6 figures, 2 tables.« less

Excited state dynamics & optical control of molecular motors

NASA Astrophysics Data System (ADS)

Wiley, Ted; Sension, Roseanne

2014-03-01

Chiral overcrowded alkenes are likely candidates for light driven rotary molecular motors. At their core, these molecular motors are based on the chromophore stilbene, undergoing ultrafast cis/trans photoisomerization about their central double bond. Unlike stilbene, the photochemistry of molecular motors proceeds in one direction only. This unidirectional rotation is a result of helicity in the molecule induced by steric hindrance. However, the steric hindrance which ensures unidirectional excited state rotation, has the unfortunate consequence of producing large ground state barriers which dramatically decrease the overall rate of rotation. These molecular scale ultrafast motors have only recently been studied by ultrafast spectroscopy. Our lab has studied the photochemistry and photophysics of a ``first generation'' molecular motor with UV-visible transient absorption spectroscopy. We hope to use optical pulse shaping to enhance the efficiency and turnover rate of these molecular motors.

The Variation of Hydrocarbon Abundances with Latitude and Season in Saturn's Stratosphere

NASA Technical Reports Server (NTRS)

Moses, J. I.; Greathouse, T. K.

2005-01-01

We have developed a realistic, time-variable, one-dimensional, seasonal model for stratospheric photochemistry on Saturn using the Caltech/ JPL KINETICS code [1,2,3]. The model accounts for variations in ultraviolet flux due to orbital position, solar-cycle variations, and ring-shadowing effects. The results for two Saturnian years, starting at Ls = 0 in 1950 and running until the upcoming northern vernal equinox in 2009, are presented for numerous latitudes. The same two model years are run over and over again until the model convergences to make sure that high-altitude effects have had a chance to propagate down through the atmosphere. We use the SOLAR2000 model [4,5], in combination with the spectra presented in [6], to predict the ultraviolet flux at any wavelength and any point in time during the simulation. Saturn's orbital position during the simulation was taken from the ephemeris calculator at http://ssd.jpl.nasa.gov/horizons.html [7]. The photochemical model is derived from "Model C" of [8] and uses a hydrocarbon reaction list that has been extensively updated from that presented in [3].

Comparison of HIPWAC and Mars Express SPICAM Observations of Ozone on Mars 2006-2008 and Variation from 1993 IRHS Observations

NASA Technical Reports Server (NTRS)

Fast, Kelly E.; Kostiuk, Theodor; Lefevre, Frank; Hewagama, Tilak; Livengood, Timothy A.; Delgado, Juan D.; Annen, John; Sonnabend, Guido

2009-01-01

Ozone is a tracer of photochemistry in the atmosphere of Mars and an observable used to test predictions of photochemical models. We present a comparison of retrieved ozone abundances on Mars using ground-based infrared heterodyne measurements by NASA Goddard Space Flight Center's Heterodyne Instrument for Planetary Wind And Composition (HIPWAC) and space-based Mars Express Spectroscopy for the Investigation of the Characteristics of the Atmosphere of Mars (SPICAM) ultraviolet measurements. Ozone retrievals from simultaneous measurements in February 2008 were very consistent (0.8 microns-atm), as were measurements made close in time (ranging from less than 1 to greater than 8 microns-atm) during this period and during opportunities in October 2006 and February 2007. The consistency of retrievals from the two different observational techniques supports combining the measurements for testing photochemistry-coupled general circulation models and for investigating variability over the long-term between spacecraft missions. Quantitative comparison with ground-based measurements by NASA'GSFC's Infrared Heterodyne Spectrometer (IRHS) in 1993 reveals 2-4 times more ozone at low latitudes than in 2008 at the same season, and such variability was not evident over the shorter period of the Mars Express mission. This variability may be due to cloud activity.

Triplet state dissolved organic matter in aquatic photochemistry: reaction mechanisms, substrate scope, and photophysical properties.

PubMed

McNeill, Kristopher; Canonica, Silvio

2016-11-09

Excited triplet states of chromophoric dissolved organic matter ( 3 CDOM*) play a major role among the reactive intermediates produced upon absorption of sunlight by surface waters. After more than two decades of research on the aquatic photochemistry of 3 CDOM*, the need for improving the knowledge about the photophysical and photochemical properties of these elusive reactive species remains considerable. This critical review examines the efforts to date to characterize 3 CDOM*. Information on 3 CDOM* relies mainly on the use of probe compounds because of the difficulties associated with directly observing 3 CDOM* using transient spectroscopic methods. Singlet molecular oxygen ( 1 O 2 ), which is a product of the reaction between 3 CDOM* and dissolved oxygen, is probably the simplest indicator that can be used to estimate steady-state concentrations of 3 CDOM*. There are two major modes of reaction of 3 CDOM* with substrates, namely triplet energy transfer or oxidation (via electron transfer, proton-coupled electron transfer or related mechanisms). Organic molecules, including several environmental contaminants, that are susceptible to degradation by these two different reaction modes are reviewed. It is proposed that through the use of appropriate sets of probe compounds and model photosensitizers an improved estimation of the distribution of triplet energies and one-electron reduction potentials of 3 CDOM* can be achieved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Hsiao-Chi; Lo, Jen-Iu; Peng, Yu-Chain

Irradiation of solid nitrogen at 4 K with far-ultraviolet light from a synchrotron caused excitation to the upper state of the Vegard–Kaplan (VK) system; the emission in that system was simultaneously recorded in wavelength region 200–440 nm. The lifetimes of emission lines for VK (0, 1) to (0, 12) transitions were measured in the range of 2.12 ∼ 2.65 s. The threshold wavelength to observe the VK emission was 175.0 ± 3.5 nm, corresponding to energy 7.08 ± 0.14 eV. This investigation of the generation of icy VK nitrogen enhances our understanding of its photochemistry in space.

Selected specific rates of reactions of transients from water in aqueous solution. III. Hydroxyl radical and perhydroxyl radical and their radical ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ross, F; Ross, A B

1977-01-01

Rates of reactions of OH and HO/sub 2/ with organic and inorganic molecules, ions and transients in aqueous solution have been tabulated, as well as the rates for the corresponding radical ions in aqueous solution (O/sup -/ and O/sub 2//sup -/). Most of the rates have been obtained by radiation chemistry methods, both pulsed and steady-state; data from photochemistry and thermal methods are also included. Rates for over one thousand reactions are listed.

Is microbiolgy an alternative route to photochemistry in atmospheric chemistry?

NASA Astrophysics Data System (ADS)

Vaitilingom, M.; Parazols, M.; Sancelme, M.; Deguillaume, L.; Mailhot, G.; Delort, A.-M.

2009-04-01

Until very recently scientists from atmospheric sciences focussed their studies on physical and chemical phenomena taking place in cloud water phase neglecting the presence of active microorganisms in this medium. For instance, considering atmospheric chemistry, solar light is considered as the predominant catalyser for chemical reactions occurring in the atmosphere. However recent studies show that living and active microorganisms, including bacteria, yeasts and fungi, are present in the atmospheric water phase and could play an active role in chemistry of clouds. Indeed living microorganisms are clearly biocatalysts which could transform organic compounds as an alternative route to photochemistry. The objective of our project is to bring answers to this new scientific question by a multidisciplinary approach involving atmospheric physicists, photochemists and microbiologists. Microorganisms have been isolated and identified in cloud water sampled at the puy de Dôme summit which is an atmospheric observatory and a European referenced site. Laboratory experiments were carried out to evaluate the potential of organic species (carboxylic acids) degradation by the photochemical or microbiological ways. The project was centred on few carboxylic acids among them succinic, acetic, formic and oxalic acids (the most important organic acids in cloud water sampled at Puy de Dôme). Degradation rates were measured during biodegradation alone (Pseudomonas syringae), photochemistry alone (hydrogen peroxide + light) and combing both processed using artificial reconstituted cloud water. Our first results show that the obtained degradation rates are in the range of order.

Investigation of power-plant plume photochemistry using a reactive plume model

NASA Astrophysics Data System (ADS)

Kim, Y. H.; Kim, H. S.; Song, C. H.

2016-12-01

Emissions from large-scale point sources have continuously increased due to the rapid industrial growth. In particular, primary and secondary air pollutants are directly relevant to atmospheric environment and human health. Thus, we tried to precisely describe the atmospheric photochemical conversion from primary to secondary air pollutants inside the plumes emitted from large-scale point sources. A reactive plume model (RPM) was developed to comprehensively consider power-plant plume photochemistry with 255 condensed photochemical reactions. The RPM can simulate two main components of power-plant plumes: turbulent dispersion of plumes and compositional changes of plumes via photochemical reactions. In order to evaluate the performance of the RPM developed in the present study, two sets of observational data obtained from the TexAQS II 2006 (Texas Air Quality Study II 2006) campaign were compared with RPM-simulated data. Comparison shows that the RPM produces relatively accurate concentrations for major primary and secondary in-plume species such as NO2, SO2, ozone, and H2SO4. Statistical analyses show good correlation, with correlation coefficients (R) ranging from 0.61 to 0.92, and good agreement with the Index of Agreement (IOA) ranging from 0.70 to 0.95. Following evaluation of the performance of the RPM, a demonstration was also carried out to show the applicability of the RPM. The RPM can calculate NOx photochemical lifetimes inside the two plumes (Monticello and Welsh power plants). Further applicability and possible uses of the RPM are also discussed together with some limitations of the current version of the RPM.

Adenine and 2-aminopurine: Paradigms of modern theoretical photochemistry

PubMed Central

Serrano-Andrés, Luis; Merchán, Manuela; Borin, Antonio C.

2006-01-01

Distinct photophysical behavior of nucleobase adenine and its constitutional isomer, 2-aminopurine, has been studied by using quantum chemical methods, in particular an accurate ab initio multiconfigurational second-order perturbation theory. After light irradiation, the efficient, ultrafast energy dissipation observed for nonfluorescent 9H-adenine is explained here by the nonradiative internal conversion process taking place along a barrierless reaction path from the initially populated 1(ππ* La) excited state toward a low-lying conical intersection (CI) connected with the ground state. In contrast, the strong fluorescence recorded for 2-aminopurine at 4.0 eV with large decay lifetime is interpreted by the presence of a minimum in the 1(ππ* La) hypersurface lying below the lowest CI and the subsequent potential energy barrier required to reach the funnel to the ground state. Secondary deactivation channels were found in the two systems related to additional CIs involving the 1(ππ* Lb) and 1(nπ*) states. Although in 9H-adenine a population switch between both states is proposed, in 7H-adenine this may be perturbed by a relatively larger barrier to access the 1(nπ*) state, and, therefore, the 1(ππ* Lb) state becomes responsible for the weak fluorescence measured in aqueous adenine at ≈4.5 eV. In contrast to previous models that explained fluorescence quenching in adenine, unlike in 2-aminopurine, on the basis of the vibronic coupling of the nearby 1(ππ*) and 1(nπ*) states, the present results indicate that the 1(nπ*) state does not contribute to the leading photophysical event and establish the prevalence of a model based on the CI concept in modern photochemistry. PMID:16731617

Enantiomeric excesses induced in amino acids by ultraviolet circularly polarized light irradiation of extraterrestrial ice analogs: A possible source of asymmetry for prebiotic chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Modica, Paola; De Marcellus, Pierre; D'Hendecourt, Louis Le Sergeant

2014-06-10

The discovery of meteoritic amino acids with enantiomeric excesses of the L-form (ee {sub L}) has suggested that extraterrestrial organic materials may have contributed to prebiotic chemistry and directed the initial occurrence of the ee {sub L} that further led to homochirality of amino acids on Earth. A proposed mechanism for the origin of ee {sub L} in meteorites involves an asymmetric photochemistry of extraterrestrial ices by UV circularly polarized light (CPL). We have performed the asymmetric synthesis of amino acids on achiral extraterrestrial ice analogs by VUV CPL, investigating the chiral asymmetry transfer at two different evolutionary stages atmore » which the analogs were irradiated (regular ices and/or organic residues) and at two different photon energies (6.6 and 10.2 eV). We identify 16 distinct amino acids and precisely measure the L-enantiomeric excesses using the enantioselective GC × GC-TOFMS technique in five of them: α-alanine, 2,3-diaminopropionic acid, 2-aminobutyric acid, valine, and norvaline, with values ranging from ee {sub L} = –0.20% ± 0.14% to ee {sub L} = –2.54% ± 0.28%. The sign of the induced ee {sub L} depends on the helicity and the energy of CPL, but not on the evolutionary stage of the samples, and is the same for all five considered amino acids. Our results support an astrophysical scenario in which the solar system was formed in a high-mass star-forming region where icy grains were irradiated during the protoplanetary phase by an external source of CPL of a given helicity and a dominant energy, inducing a stereo-specific photochemistry.« less

Adenine and 2-aminopurine: paradigms of modern theoretical photochemistry.

PubMed

Serrano-Andrés, Luis; Merchán, Manuela; Borin, Antonio C

2006-06-06

Distinct photophysical behavior of nucleobase adenine and its constitutional isomer, 2-aminopurine, has been studied by using quantum chemical methods, in particular an accurate ab initio multiconfigurational second-order perturbation theory. After light irradiation, the efficient, ultrafast energy dissipation observed for nonfluorescent 9H-adenine is explained here by the nonradiative internal conversion process taking place along a barrierless reaction path from the initially populated 1(pipi* La) excited state toward a low-lying conical intersection (CI) connected with the ground state. In contrast, the strong fluorescence recorded for 2-aminopurine at 4.0 eV with large decay lifetime is interpreted by the presence of a minimum in the 1(pipi* La) hypersurface lying below the lowest CI and the subsequent potential energy barrier required to reach the funnel to the ground state. Secondary deactivation channels were found in the two systems related to additional CIs involving the 1(pipi* Lb) and 1(npi*) states. Although in 9H-adenine a population switch between both states is proposed, in 7H-adenine this may be perturbed by a relatively larger barrier to access the 1(npi*) state, and, therefore, the 1(pipi* Lb) state becomes responsible for the weak fluorescence measured in aqueous adenine at approximately 4.5 eV. In contrast to previous models that explained fluorescence quenching in adenine, unlike in 2-aminopurine, on the basis of the vibronic coupling of the nearby 1(pipi*) and 1(npi*) states, the present results indicate that the 1(npi*) state does not contribute to the leading photophysical event and establish the prevalence of a model based on the CI concept in modern photochemistry.

Enantiomeric Excesses Induced in Amino Acids by Ultraviolet Circularly Polarized Light Irradiation of Extraterrestrial Ice Analogs: A Possible Source of Asymmetry for Prebiotic Chemistry

NASA Astrophysics Data System (ADS)

Modica, Paola; Meinert, Cornelia; de Marcellus, Pierre; Nahon, Laurent; Meierhenrich, Uwe J.; Le Sergeant d'Hendecourt, Louis

2014-06-01

The discovery of meteoritic amino acids with enantiomeric excesses of the L-form (ee L) has suggested that extraterrestrial organic materials may have contributed to prebiotic chemistry and directed the initial occurrence of the ee L that further led to homochirality of amino acids on Earth. A proposed mechanism for the origin of ee L in meteorites involves an asymmetric photochemistry of extraterrestrial ices by UV circularly polarized light (CPL). We have performed the asymmetric synthesis of amino acids on achiral extraterrestrial ice analogs by VUV CPL, investigating the chiral asymmetry transfer at two different evolutionary stages at which the analogs were irradiated (regular ices and/or organic residues) and at two different photon energies (6.6 and 10.2 eV). We identify 16 distinct amino acids and precisely measure the L-enantiomeric excesses using the enantioselective GC × GC-TOFMS technique in five of them: α-alanine, 2,3-diaminopropionic acid, 2-aminobutyric acid, valine, and norvaline, with values ranging from ee L = -0.20% ± 0.14% to ee L = -2.54% ± 0.28%. The sign of the induced ee L depends on the helicity and the energy of CPL, but not on the evolutionary stage of the samples, and is the same for all five considered amino acids. Our results support an astrophysical scenario in which the solar system was formed in a high-mass star-forming region where icy grains were irradiated during the protoplanetary phase by an external source of CPL of a given helicity and a dominant energy, inducing a stereo-specific photochemistry.

Isoprene photochemistry over the Amazon rainforest.

PubMed

Liu, Yingjun; Brito, Joel; Dorris, Matthew R; Rivera-Rios, Jean C; Seco, Roger; Bates, Kelvin H; Artaxo, Paulo; Duvoisin, Sergio; Keutsch, Frank N; Kim, Saewung; Goldstein, Allen H; Guenther, Alex B; Manzi, Antonio O; Souza, Rodrigo A F; Springston, Stephen R; Watson, Thomas B; McKinney, Karena A; Martin, Scot T

2016-05-31

Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO2) to dominantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK + MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4-0.6. This result implies a ratio of the reaction rate of ISOPOO with HO2 to that with NO of approximately unity. A value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (<60 ppt). This abrupt shift in isoprene photooxidation, sparked by human activities, speaks to ongoing and possible future changes in the photochemistry active over the Amazon rainforest.

Isoprene photochemistry over the Amazon rainforest

NASA Astrophysics Data System (ADS)

Liu, Yingjun; Brito, Joel; Dorris, Matthew R.; Rivera-Rios, Jean C.; Seco, Roger; Bates, Kelvin H.; Artaxo, Paulo; Duvoisin, Sergio; Keutsch, Frank N.; Kim, Saewung; Goldstein, Allen H.; Guenther, Alex B.; Manzi, Antonio O.; Souza, Rodrigo A. F.; Springston, Stephen R.; Watson, Thomas B.; McKinney, Karena A.; Martin, Scot T.

2016-05-01

Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO2) to dominantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK + MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4-0.6. This result implies a ratio of the reaction rate of ISOPOO with HO2 to that with NO of approximately unity. A value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (<60 ppt). This abrupt shift in isoprene photooxidation, sparked by human activities, speaks to ongoing and possible future changes in the photochemistry active over the Amazon rainforest.

Kinetic and spectroscopic studies of peroxy radical reactions related to tropospheric photo-oxidation chemistry

NASA Astrophysics Data System (ADS)

Jenkin, Michael Edwin

Over the past 30 years, man has become increasingly aware that the presence of relatively small quantities of pollutants in the atmosphere as a result of his activities, can have a profound impact on both its chemistry, and its meteorology. Photochemistry in the atmosphere is not restricted to the behavior of pollutants; indeed, certain photochemical phenomena necessarily occur naturally in a 'pollution free' atmosphere. It is the interaction of the photochemistry of trace pollutants with the naturally established chemistry, either inhibiting or exaggerating natural processes, which has given rise to the environment threatening consequences. The chemistry that leads to the phenomena mentioned above is complex, involving many hundreds of chemical reactions of reactive atomic and radical species. Over the years, a great deal of chemical kinetic data for elementary atmospheric reactions has accumulated, and the fundamental gas phase chemistry is well established. Computer models provide a useful means of assembling these data, and describing the likely behavior and interconversion of various atmospheric pollutants, thereby enabling policy decision. For these models to be truly predictive, however, they must be based, first on reliable field measurements of primary trace pollutants and, secondly, on accurate kinetic and mechanistic data for key reactions of atmospheric importance. The work presented in this dissertation is concerned with the kinetics and mechanisms of reactions of the hydroperoxy radial (HO2), and various organic peroxy radicals (RO2), which are formed as intermediates in the atmospheric oxidation of volatile organic compounds. In the sections that follow, our current understanding of the chemistry in general of the lower atmosphere (0-50 km) will be discussed in some detail, but with particular reference to the role played by HO2 and RO2 radicals.

Combined In Situ Illumination-NMR-UV/Vis Spectroscopy: A New Mechanistic Tool in Photochemistry.

PubMed

Seegerer, Andreas; Nitschke, Philipp; Gschwind, Ruth M

2018-06-18

Synthetic applications in photochemistry are booming. Despite great progress in the development of new reactions, mechanistic investigations are still challenging. Therefore, we present a fully automated in situ combination of NMR spectroscopy, UV/Vis spectroscopy, and illumination to allow simultaneous and time-resolved detection of paramagnetic and diamagnetic species. This optical fiber-based setup enables the first acquisition of combined UV/Vis and NMR spectra in photocatalysis, as demonstrated on a conPET process. Furthermore, the broad applicability of combined UVNMR spectroscopy for light-induced processes is demonstrated on a structural and quantitative analysis of a photoswitch, including rate modulation and stabilization of transient species by temperature variation. Owing to the flexibility regarding the NMR hardware, temperature, and light sources, we expect wide-ranging applications of this setup in various research fields. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Estimated SAGE II ozone mixing ratios in early 1993 and comparisons with Stratospheric Photochemistry, Aerosols and Dynamic Expedition measurements

NASA Technical Reports Server (NTRS)

Yue, G. K.; Veiga, R. E.; Poole, L. R.; Zawodny, J. M.; Proffitt, M. H.

1994-01-01

An empirical time-series model for estimating ozone mixing ratios based on Stratospheric Aerosols and Gas Experiment II (SAGE II) monthly mean ozone data for the period October 1984 through June 1991 has been developed. The modeling results for ozone mixing ratios in the 10- to 30- km region in early months of 1993 are presented. In situ ozone profiles obtained by a dual-beam UV-absorption ozone photometer during the Stratospheric Photochemistry, Aerosols and Dynamics Expedition (SPADE) campaign, May 1-14, 1993, are compared with the model results. With the exception of two profiles at altitudes below 16 km, ozone mixing ratios derived by the model and measured by the ozone photometer are in relatively good agreement within their individual uncertainties. The identified discrepancies in the two profiles are discussed.

Multi-electron transfer photochemistry: Caught in the act

NASA Astrophysics Data System (ADS)

Beiler, Anna M.; Moore, Gary F.

2018-01-01

The accumulation of multiple redox equivalents is essential in photo-driven catalytic reactions such as solar water splitting. However, direct spectroscopic observation of a twice-oxidized species under diffuse illumination has proved elusive until now.

Photodissociable dimer reduction products of 2-thiopyrimidine derivatives.

PubMed Central

Wrona, M; Giziewicz, J; Shugar, D

1975-01-01

Both 4,6-dimethyl-2-thipyrimidine and its 1-methyl derivative undergo polarographic reduction in aqueous medium, via a 1e/1H+ reduction to a free radical which rapidly dimerizes to products isolates and identified as 4,4'-bis-(4,6-dimethyl-3,4-dihydropyrimidin-2-thione) and the corresponding 1-methyl dimer. The dimers may be oxidized electrolytically to regenerate the parent monomers. Both dimers also undergo photodissociation to quantitatively regenerate the parent monomers, in high quantum yield, 0.23 and 0.35 M/Einstein. The correlation between electrochemical and photochemical reductions of 2-thiopyrimidines are discussed, as well as the significance of the dimer photodissociation reactions in relation to nucleic acid photochemistry. PMID:28516

A diabatic circulation two-dimensional model with photochemistry - Simulations of ozone and long-lived tracers with surface sources

NASA Technical Reports Server (NTRS)

Stordal, F.; Isaksen, I. S. A.; Horntveth, K.

1985-01-01

Numerous studies have been concerned with the possibility of a reduction of the stratospheric ozone layer. Such a reduction could lead to an enhanced penetration of ultraviolet (UV) radiation to the ground, and, as a result, to damage in the case of several biological processes. It is pointed out that the distributions of many trace gases, such as ozone, are governed in part by transport processes. The present investigation presents a two-dimensional photochemistry-transport model using the residual circulation. The global distribution of both ozone and components with ground sources computed in this model is in good agreement with the observations even though slow diffusion is adopted. The agreement is particularly good in the Northern Hemisphere. The results provide additional support for the idea that tracer transport in the stratosphere is mainly of advective nature.

Current State of Modeling the Photochemistry of Titan's Mutually Dependent Atmosphere and Ionosphere

NASA Technical Reports Server (NTRS)

Wilson, Eric H.; Atreya, S. K.

2004-01-01

In the context of recent observations, microphysical models, and laboratory data, a photochemical model of Titan's atmosphere, including updated chemistry focusing on rate coefficients and cross sections measured under appropriate conditions, has been developed to increase understanding of these processes and improve upon previous Titan photochemical models. The model employs a two-stream discrete ordinates method to characterize the transfer of solar radiation, and the effects of electron-impact, cosmic-ray deposition, and aerosol opacities from fractal and Mie particles are analyzed. Sensitivity studies demonstrate that an eddy diffusion profile with a homopause level of 850 km and a methane stratospheric mole fraction of 2.2% provides the best fit of stratospheric and upper atmosphere observations and an improved fit over previous Titan photochemical models. Lack of fits for C3H8, HC3N, and possibly C2H3CN can be resolved with adjustments in aerosol opacity. The model presents a benzene profile consistent with its detection in Titan's stratosphere [Coustenis et al., 2003], which may play an important role in the formation of Titan hazes. An electron peak concentration of 4200 cm(exp -3) is calculated, which exceeds observations by 20%, considerably lower than previous ionosphere models. With adjustments in aerosol opacities and surface fluxes the model illustrates that reasonable fits to existing observations are possible with a single eddy diffusion profile, contrary to the conclusions of previous Titan models. These results will aid in the receipt and interpretation of data from Cassini-Huygens, which will arrive at Titan in 2004 and deploy a probe into Titan's atmosphere in January 2005.

Photochemistry of 1,4-dihydronaphtho(1,8-de)(1,2)diazepine. Preparation and electron spin resonance observation of the unsubstituted 1,8-naphthoquinodimethane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pagni, R.M.; Burnett, M.N.; Dodd, J.R.

1977-03-16

In an attempt to prepare selenated tRNA, transformation of 4-thiouridine to selenouridine in tRNA was attempted. Feasibility studies were performed by spectrophotometrically monitored conversion of 1 methyl-4- thiocyanatouracil to 1-methyl-4-selenouracil by NaHSe. E.coli mixed tRNA were exposed to the same sequence of reactions and the identity of the products was confirmed. (DDA)

A model for the origin of photosynthesis--III. The ultraviolet photochemistry of uroporphyrinogen

NASA Technical Reports Server (NTRS)

Mercer-Smith, J. A.; Raudino, A.; Mauzerall, D. C.

1985-01-01

The photochemical ramifications of the high ultraviolet flux on the primordial earth prior to the formation of the ozone layer have been considered in a study of the ultraviolet photochemistry of uroporphyrinogen (urohexahydroporphyrin), a colorless compound which absorbs strongly at wavelengths less than 220 nanometers. Urohexahydroporphyrin was investigated since it is the first macrocycle formed on the biosynthetic pathway of chlorophyll and can be used to test the hypothesis that the biosynthetic pathway to chlorophyll recapitulates the evolutionary history of photosynthesis. When urohexahydroporphyrin is illuminated in aqueous anaerobic solution, hydrogen gas is produced. More hydrogen gas is produced in the presence of a colloidal platinum catalyst. The products of the photooxidation of urohexahydroporphyrin are urotetrahydroporphyrin (uroporphomethene) and uroporphyrin. This research shows how the oxidation of uroporphyrinogen to uroporphyrin, the first biogenetic porphyrin, could have occurred anaerobically and abiotically on the primordial earth.

What limits photosynthetic energy conversion efficiency in nature? Lessons from the oceans.

PubMed

Falkowski, Paul G; Lin, Hanzhi; Gorbunov, Maxim Y

2017-09-26

Constraining photosynthetic energy conversion efficiency in nature is challenging. In principle, two yield measurements must be made simultaneously: photochemistry, fluorescence and/or thermal dissipation. We constructed two different, extremely sensitive and precise active fluorometers: one measures the quantum yield of photochemistry from changes in variable fluorescence, the other measures fluorescence lifetimes in the picosecond time domain. By deploying the pair of instruments on eight transoceanic cruises over six years, we obtained over 200 000 measurements of fluorescence yields and lifetimes from surface waters in five ocean basins. Our results revealed that the average quantum yield of photochemistry was approximately 0.35 while the average quantum yield of fluorescence was approximately 0.07. Thus, closure on the energy budget suggests that, on average, approximately 58% of the photons absorbed by phytoplankton in the world oceans are dissipated as heat. This extraordinary inefficiency is associated with the paucity of nutrients in the upper ocean, especially dissolved inorganic nitrogen and iron. Our results strongly suggest that, in nature, most of the time, most of the phytoplankton community operates at approximately half of its maximal photosynthetic energy conversion efficiency because nutrients limit the synthesis or function of essential components in the photosynthetic apparatus.This article is part of the themed issue 'Enhancing photosynthesis in crop plants: targets for improvement'. © 2017 The Author(s).

Redox Evolution via Gravitational Differentiation on Low-mass Planets: Implications for Abiotic Oxygen, Water Loss, and Habitability

NASA Astrophysics Data System (ADS)

Wordsworth, R. D.; Schaefer, L. K.; Fischer, R. A.

2018-05-01

The oxidation of rocky planet surfaces and atmospheres, which arises from the twin forces of stellar nucleosynthesis and gravitational differentiation, is a universal process of key importance to habitability and exoplanet biosignature detection. Here we take a generalized approach to this phenomenon. Using a single parameter to describe the redox state, we model the evolution of terrestrial planets around nearby M stars and the Sun. Our model includes atmospheric photochemistry, diffusion and escape, line-by-line climate calculations, and interior thermodynamics and chemistry. In most cases, we find abiotic atmospheric {{{O}}}2 buildup around M stars during the pre-main-sequence phase to be much less than calculated previously, because the planet’s magma ocean absorbs most oxygen liberated from {{{H}}}2{{O}} photolysis. However, loss of noncondensing atmospheric gases after the mantle solidifies remains a significant potential route to abiotic atmospheric {{{O}}}2 subsequently. In all cases, we predict that exoplanets that receive lower stellar fluxes, such as LHS1140b and TRAPPIST-1f and g, have the lowest probability of abiotic {{{O}}}2 buildup and hence may be the most interesting targets for future searches for biogenic {{{O}}}2. Key remaining uncertainties can be minimized in future by comparing our predictions for the atmospheres of hot, sterile exoplanets such as GJ1132b and TRAPPIST-1b and c with observations.

Photophysics and Photochemistry

ERIC Educational Resources Information Center

Letokhov, V. S.

1977-01-01

Discusses recent progress in using tunable lasers to selectively separate substances at the atomic and molecular level. Emphasizes biological applications, such as selective excitation and breaking of hydrogen bonds in DNA. (MLH)

Aerosols from fires: an examination of the effects on ozone photochemistry in the Western United States.

PubMed

Jiang, Xiaoyan; Wiedinmyer, Christine; Carlton, Annmarie G

2012-11-06

This study presents a first attempt to investigate the roles of fire aerosols in ozone (O(3)) photochemistry using an online coupled meteorology-chemistry model, the Weather Research and Foresting model with Chemistry (WRF-Chem). Four 1-month WRF-Chem simulations for August 2007, with and without fire emissions, were carried out to assess the sensitivity of O(3) predictions to the emissions and subsequent radiative feedbacks associated with large-scale fires in the Western United States (U.S.). Results show that decreases in planetary boundary layer height (PBLH) resulting from the radiative effects of fire aerosols and increases in emissions of nitrogen oxides (NO(x)) and volatile organic compounds (VOCs) from the fires tend to increase modeled O(3) concentrations near the source. Reductions in downward shortwave radiation reaching the surface and surface temperature due to fire aerosols cause decreases in biogenic isoprene emissions and J(NO(2)) photolysis rates, resulting in reductions in O(3) concentrations by as much as 15%. Thus, the results presented in this study imply that considering the radiative effects of fire aerosols may reduce O(3) overestimation by traditional photochemical models that do not consider fire-induced changes in meteorology; implementation of coupled meteorology-chemistry models are required to simulate the atmospheric chemistry impacted by large-scale fires.

Photochemistry of furyl- and thienyldiazomethanes: spectroscopic characterization of triplet 3-thienylcarbene.

PubMed

Pharr, Caroline R; Kopff, Laura A; Bennett, Brian; Reid, Scott A; McMahon, Robert J

2012-04-11

Photolysis (λ > 543 nm) of 3-thienyldiazomethane (1), matrix isolated in Ar or N(2) at 10 K, yields triplet 3-thienylcarbene (13) and α-thial-methylenecyclopropene (9). Carbene 13 was characterized by IR, UV/vis, and EPR spectroscopy. The conformational isomers of 3-thienylcarbene (s-E and s-Z) exhibit an unusually large difference in zero-field splitting parameters in the triplet EPR spectrum (|D/hc| = 0.508 cm(-1), |E/hc| = 0.0554 cm(-1); |D/hc| = 0.579 cm(-1), |E/hc| = 0.0315 cm(-1)). Natural Bond Orbital (NBO) calculations reveal substantially differing spin densities in the 3-thienyl ring at the positions adjacent to the carbene center, which is one factor contributing to the large difference in D values. NBO calculations also reveal a stabilizing interaction between the sp orbital of the carbene carbon in the s-Z rotamer of 13 and the antibonding σ orbital between sulfur and the neighboring carbon-an interaction that is not observed in the s-E rotamer of 13. In contrast to the EPR spectra, the electronic absorption spectra of the rotamers of triplet 3-thienylcarbene (13) are indistinguishable under our experimental conditions. The carbene exhibits a weak electronic absorption in the visible spectrum (λ(max) = 467 nm) that is characteristic of triplet arylcarbenes. Although studies of 2-thienyldiazomethane (2), 3-furyldiazomethane (3), or 2-furyldiazomethane (4) provided further insight into the photochemical interconversions among C(5)H(4)S or C(5)H(4)O isomers, these studies did not lead to the spectroscopic detection of the corresponding triplet carbenes (2-thienylcarbene (11), 3-furylcarbene (23), or 2-furylcarbene (22), respectively). © 2012 American Chemical Society

UV photoprocessing of CO2 ice: a complete quantification of photochemistry and photon-induced desorption processes

NASA Astrophysics Data System (ADS)

Martín-Doménech, R.; Manzano-Santamaría, J.; Muñoz Caro, G. M.; Cruz-Díaz, G. A.; Chen, Y.-J.; Herrero, V. J.; Tanarro, I.

2015-12-01

Context. Ice mantles that formed on top of dust grains are photoprocessed by the secondary ultraviolet (UV) field in cold and dense molecular clouds. UV photons induce photochemistry and desorption of ice molecules. Experimental simulations dedicated to ice analogs under astrophysically relevant conditions are needed to understand these processes. Aims: We present UV-irradiation experiments of a pure CO2 ice analog. Calibration of the quadrupole mass spectrometer allowed us to quantify the photodesorption of molecules to the gas phase. This information was added to the data provided by the Fourier transform infrared spectrometer on the solid phase to obtain a complete quantitative study of the UV photoprocessing of an ice analog. Methods: Experimental simulations were performed in an ultra-high vacuum chamber. Ice samples were deposited onto an infrared transparent window at 8K and were subsequently irradiated with a microwave-discharged hydrogen flow lamp. After irradiation, ice samples were warmed up until complete sublimation was attained. Results: Photolysis of CO2 molecules initiates a network of photon-induced chemical reactions leading to the formation of CO, CO3, O2, and O3. During irradiation, photon-induced desorption of CO and, to a lesser extent, O2 and CO2 took place through a process called indirect desorption induced by electronic transitions, with maximum photodesorption yields (Ypd) of ~1.2 × 10-2 molecules incident photon-1, ~9.3 × 10-4 molecules incident photon-1, and ~1.1 × 10-4 molecules incident photon-1, respectively. Conclusions: Calibration of mass spectrometers allows a direct quantification of photodesorption yields instead of the indirect values that were obtained from infrared spectra in most previous works. Supplementary information provided by infrared spectroscopy leads to a complete quantification, and therefore a better understanding, of the processes taking place in UV-irradiated ice mantles. Appendix A is available in electronic form at http://www.aanda.org

Soil emissions of gaseous reactive nitrogen from North American arid lands: an overlooked source.

NASA Astrophysics Data System (ADS)

Sparks, J. P.; McCalley, C. K.; Strahm, B. D.

2008-12-01

The biosphere-atmosphere exchange and transformation of nitrogen has important ramifications for both terrestrial biogeochemistry and atmospheric chemistry. Several important mechanisms within this process (e.g., photochemistry, nitrogen deposition, aerosol formation) are strongly influenced by the emission of reactive nitrogen compounds from the Earth's surface. Therefore, a quantification of emission sources is a high priority for future conceptual understanding. One source largely overlooked in most global treatments are the soil emissions from arid and semi-arid landscapes worldwide. Approximately 35-40% of global terrestrial land cover is aridland and emission of reactive nitrogen from soils in these regions has the potential to strongly influence both regional and global biogeochemistry. Here we present estimates of soil emission of oxidized (NO, total NOy including NO2 and HONO) and reduced (NH3) forms of reactive nitrogen from two North American arid regions: the Mojave Desert and the Colorado Plateau. Soil fluxes in these regions are highly dependent on soil moisture conditions. Soil moisture is largely driven by pulsed rain events with fluxes increasing 20-40 fold after a rain event. Using field measurements made across seasons under an array of moisture conditions, precipitation records, and spatially explicit cover type information we have estimated annual estimates for the Mojave Desert (1.5 ± 0.7 g N ha-1 yr-1), the shale derived (1.4 ± 0.9 g N ha-1 yr-1), and sandy soil derived (2.8 ± 1.2 g N ha-1 yr-1) regions of the Colorado Plateau. The chemical composition of soil emissions varies significantly both with season and soil moisture content. Emissions from dry soils tend to be dominated by ammonia and forms of NOy other than NO. In contrast, NO becomes a dominant portion of the flux post rain events (~30% of the total flux). This variability in chemical form has significant implications for the tropospheric fate of the emitted N. NO and other nitrogen oxides are likely to participate in photochemistry, ozone production, and production of organic nitrates and nitric acid. In contrast, NH3 is likely to locally redeposit or form secondary aerosols in the presence of sulphate. Given the vastly different influence of oxidized versus reduced forms of N on atmospheric chemistry, the variable chemical partitioning of soil emissions based on season and water availability observed in this study is likely to improve the performance of regional photochemistry models.

Efficient photochemistry of coronene:water complexes

NASA Astrophysics Data System (ADS)

Noble, J. A.; Jouvet, C.; Aupetit, C.; Moudens, A.; Mascetti, J.

2017-03-01

The photochemistry of ices with polycyclic aromatic hydrocarbons (PAHs) has been extensively studied, but to date no investigation has been made of PAHs in interaction with low numbers (n< 4) of molecules of water. We performed photochemical matrix isolation studies of coronene:water complexes, probing the argon matrix with FTIR spectroscopy. We find that coronene readily reacts with water upon irradiation with a mercury vapour lamp to produce oxygenated PAH photoproducts, and we postulate a reaction mechanism via a charge transfer Rydberg state. This result suggests that oxygenated PAHs should be widely observed in regions of the ISM with sufficiently high water abundances, for example near the edges of molecular clouds where water molecules begin to form, but before icy layers are observed, that is at AV< 3. In order to explain the low derived observational abundances of oxygenated PAHs, additional destruction routes must be invoked.

Photochemistry of Polycyclic Aromatic Hydrocarbons in Cosmic Water Ice: The Role of PAH Ionization and Concentration

NASA Astrophysics Data System (ADS)

Cook, Amanda M.; Ricca, Alessandra; Mattioda, Andrew L.; Bouwman, Jordy; Roser, Joseph; Linnartz, Harold; Bregman, Jonathan; Allamandola, Louis J.

2015-01-01

Infrared spectroscopic studies of ultraviolet (UV) irradiated, water-rich, cosmic ice analogs containing small polycyclic aromatic hydrocarbons (PAHs) are described. The irradiation studies of anthracene:H2O, pyrene:H2O, and benzo[ghi]perylene:H2O ices (14 K) at various concentrations reported by Bouwman et al. are extended. While aromatic alcohols and ketones have been reported in residues after irradiated PAH:H2O ices were warmed to 270 K, it was not known if they formed during ice irradiation or during warm-up when reactants interact as H2O sublimes. Recent work has shown that they form in low temperature ice. Using DFT computed IR spectra to identify photoproducts and PAH cations, we tentatively identify the production of specific alcohols [PAH(OH) n ] and quinones [PAH(O) n ] for all PAH:H2O ices considered here. Little evidence is found for hydrogenation at 14 K, consistent with the findings of Gudipati & Yang. Addition of O and OH to the parent PAH is the dominant photochemical reaction, but PAH erosion to smaller PAHs (producing CO2 and H2CO) is also important. DFT spectra are used to assess the contribution of PAH-related species to interstellar absorption features from 5 to 9 μm. The case is made that PAH cations are important contributors to the C2 component and PAH(OH) n and PAH(O) n to the C5 component described by Boogert et al. Thus, interstellar ices should contain neutral and ionized PAHs, alcohols, ketones and quinones at the ~2%-4% level relative to H2O. PAHs, their photoproducts, and ion-mediated processes should therefore be considered when modeling interstellar ice processes.

Charge transfer photodissociation of phenol on Ag(111)

NASA Astrophysics Data System (ADS)

Lee, Junseok; Ryu, Sunmin; Ku, Jong Seok; Kim, Seong Keun

2001-12-01

The photochemistry of phenol on Ag(111) has been investigated by post-irradiation temperature programmed desorption (TPD). Ultraviolet (UV) irradiation at 355 and 266 nm was found to affect only the chemisorption layer in direct contact with the metal surface, while leaving the multilayer virtually intact. The main photoinduced reaction was found to be photodissociation of the O-H bond of phenol. Two new peaks were observed at the mass of phenol in the post-irradiation TPD spectrum at 335 K and 455 K. These peaks were assigned to the recombinative desorption of phenoxy with the hydrogen from O-H bond photodissociation and from thermal C-H bond fission, respectively. The photodissociation cross section was measured at different wavelengths and coverages. A charge transfer type photodissociation mechanism was proposed, where hot electrons generated in the substrate by UV photons attach to the affinity level of the adsorbed phenol. The transition to the transient anionic potential then leads to facile dissociation of O-H bond. The affinity level of phenol has been estimated to lie at 3.2-3.5 eV above the Fermi level for the 1 ML case.

Exciplex ensemble modulated by excitation mode in intramolecular charge-transfer dyad: effects of temperature, solvent polarity, and wavelength on photochemistry and photophysics of tethered naphthalene-dicyanoethene system.

PubMed

Aoki, Yoshiaki; Matsuki, Nobuo; Mori, Tadashi; Ikeda, Hiroshi; Inoue, Yoshihisa

2014-09-19

Solvent, temperature, and excitation wavelength significantly affected the photochemical outcomes of a naphthalene-dicyanoethene system tethered by different number (n) of methylene groups (1-3). The effect of irradiation wavelength was almost negligible for 2a but pronounced for 3a. The temperature dependence and theoretical calculations indicated the diversity of exciplex conformations, an ensemble of which can be effectively altered by changing excitation wavelength to eventually switch the regioselectivity of photoreactions.

Radiative Effect of Clouds on Tropospheric Chemistry in a Global Three-Dimensional Chemical Transport Model

NASA Technical Reports Server (NTRS)

Liu, Hongyu; Crawford, James H.; Pierce, Robert B.; Norris, Peter; Platnick, Steven E.; Chen, Gao; Logan, Jennifer A.; Yantosca, Robert M.; Evans, Mat J.; Kittaka, Chieko;

On the utility of the ionosonde Doppler derived EXB drift during the daytime

NASA Astrophysics Data System (ADS)

Mohan Joshi, Lalit; Sripathi, Samireddipelle

2016-07-01

Vertical EXB drift measured using the ionosonde Doppler sounding during the daytime suffers from an underestimation of the actual EXB drift. This is due to the photochemistry that determines the height of the F layer during the daytime, in addition to the zonal electric field. Systematic investigations have indicated a fair/good correlation to exist between the C/NOFS and ionosonde Doppler measured vertical EXB drift during the daytime over magnetic equator. A detailed analysis, however, indicated that the linear relation between the ionosonde Doppler drift and C/NOFS EXB drift varied with seasons. Thus, solar, seasonal and also geomagnetic variables were included in the Doppler drift correction, using the artificial neural network based approach. The RMS error in the neural network was found to be lesser than that in the linear regression analysis. Daytime EXB drift was derived using the neural network which was also used to model the ionospheic redistribution in the SAMI2 model. SAMI2 model reproduced strong (/weak) equatorial ionization anomaly (EIA) for cases when neural network corrected daytime vertical EXB drift was high (/low). Similar features were also observed in GIM TEC maps. Thus, the results indicate that the neural network can be utilized to derive the vertical EXB drift from its proxies, like the ionosonde Doppler drift. These results indicate that the daytime ionosonde measured vertical EXB drift can be relied upon, provided adequate corrections are applied to it.

Additional chain-branching pathways in the low-temperature oxidation of branched alkanes

DOE PAGES

Wang, Zhandong; Zhang, Lidong; Moshammer, Kai; ...

2015-12-31

Chain-branching reactions represent a general motif in chemistry, encountered in atmospheric chemistry, combustion, polymerization, and photochemistry; the nature and amount of radicals generated by chain-branching are decisive for the reaction progress, its energy signature, and the time towards its completion. In this study, experimental evidence for two new types of chain-branching reactions is presented, based upon detection of highly oxidized multifunctional molecules (HOM) formed during the gas-phase low-temperature oxidation of a branched alkane under conditions relevant to combustion. The oxidation of 2,5-dimethylhexane (DMH) in a jet-stirred reactor (JSR) was studied using synchrotron vacuum ultra-violet photoionization molecular beam mass spectrometry (SVUV-PI-MBMS).more » Specifically, species with four and five oxygen atoms were probed, having molecular formulas of C 8H 14O 4 (e.g., diketo-hydroperoxide/keto-hydroperoxy cyclic ether) and C 8H 16O 5 (e.g., keto-dihydroperoxide/dihydroperoxy cyclic ether), respectively. The formation of C 8H 16O 5 species involves alternative isomerization of OOQOOH radicals via intramolecular H-atom migration, followed by third O 2 addition, intramolecular isomerization, and OH release; C 8H 14O 4 species are proposed to result from subsequent reactions of C 8H 16O 5 species. The mechanistic pathways involving these species are related to those proposed as a source of low-volatility highly oxygenated species in Earth's troposphere. At the higher temperatures relevant to auto-ignition, they can result in a net increase of hydroxyl radical production, so these are additional radical chain-branching pathways for ignition. Furthermore, the results presented herein extend the conceptual basis of reaction mechanisms used to predict the reaction behavior of ignition, and have implications on atmospheric gas-phase chemistry and the oxidative stability of organic substances.« less

Effects of the natural colloidal particles from one freshwater lake on the photochemistry reaction kinetics of ofloxacin and enrofloxacin.

PubMed

Cheng, Dengmiao; Liu, Xinhui; Li, Jinpeng; Feng, Yao; Wang, Juan; Li, Zhaojun

2018-06-11

Understanding the effect of natural colloidal particles (NCPs) on the photochemistry of organic pollutants is crucial to predict the environmental persistence and fate of them in surface waters, and it is, yet, scarcely elucidated. In this study, the pre-filtered surface water (through a 1 μm capsule filter) from Baiyangdian Lake was further separated into four different size NCPs: F1 (0.65-1.0 μm), F2 (100 kD-0.65 μm), F3 (10-100 kD) and F4 (1-10 kD) by cross-flow ultrafiltration (CFUF), and the photochemical kinetics and mechanisms of ofloxacin (OFL) and enrofloxacin (ENR) were investigated in the presence of those particles under simulated sunlight. Results showed that OFL and ENR underwent both direct and indirect photolysis in F1-F4 solutions, and the observed pseudo first-order rate constants (k obs ) for target compounds differed depending on the size of NCPs. Direct photolysis accounted for >50% of the degradation in all cases and was the dominant degradation pathway for the two target antibiotics with the exception of OFL in F1 solution. Except for ENR in both F3 and F4 solutions, nearly all NCPs enhanced the degradation of both target compounds by indirect photolytic pathways, especially in F1 solution that showed the largest reactivity for OFL and ENR, promoting the reactions by 63% and 41%, respectively. The excited state colloidal organic matter ( 3 COM ∗ ) plays a significant role in the indirect photolysis, and the adsorptions of OFL and ENR to NCPs were likely to have a pronounced effect in the photochemistry process. Pearson's correlations analysis showed that the k obs(OFL) was significant positive correlated with binding of Fe (r = 0.963, P < 0.05), and the k obs(ENR) was significant positive correlated with the adsorption percentage of OFL (r = 0.999, P < 0.01). This paper has demonstrated that different size NCPs showed the different photochemical contribution to the reaction rate for OFL and ENR. Copyright © 2018. Published by Elsevier Ltd.

Impacts on Hubble Space Telescope solar arrays: discrimination between natural and man-made particles.

NASA Astrophysics Data System (ADS)

Kearsley, A. T.; Drolshagen, G.; McDonnell, J. A. M.; Mandeville, J.-C.; Moussi, A.

A Post-Flight Investigation was initiated by the European Space Agency to analyze impact fluxes on solar arrays of the Hubble Space Telescope (HST), exposed to space for 8.25 years at approximately 600 km altitude. The solar cells were deployed during servicing mission SM-1 (December 1993), and retrieved by shuttle orbiter Columbia in March 2002 (SM-3B). A sub-panel of 2 m2 was cut from the --V2 wing and cells were selected for in-depth analysis. Twelve cells (9.6x10-3 m2) were surveyed for flux of all craters of sizes greater than 5 microns Dco; six at the NHM, and six at ONERA. Cumulative flux plots reveal slightly greater abundance of very small craters than in a comparable survey of SM-1 cells. Analytical scanning electron microscopy was used to locate impact features and to analyse residues at the NHM. 103 features of 3 -- 4000 micron conchoidal detachment diameter (Dco) were located on a total of 17 solar cells. 78 features show identifiable residue: 36 are Space Debris impacts and 42 Micrometeoroid impacts. Of the remaining 25: 4 contain residue of ambiguous origin, 1 is a minor manufacturing flaw, 1 is obscured by contamination, and 19 are unresolved, lacking recognizable residue. Space debris impacts on the SM-3B cells are all less than 80 microns Dco, dominated by Al- rich residue, probably of solid rocket motor origin, some may be unburnt fuel. Three craters may be sodium metal droplet impacts. No residues from paint pigment, aluminium or ferrous alloys, or copper- and tin-bearing metal were found. All craters larger than 100 microns are of micrometeoroid origin, or unresolved. Most residues are magnesium-iron silicate or iron sulfide. A few craters show vesicular Mg, S, Fe and Ni residue. A single Fe Ni metal residue was found, as well as enigmatic Mg- and S-bearing residues, all considered of micrometeoroid origin. A few Fe-, O- and C-bearing residues were classified as of ambiguous origin. The quality and quantity of residue is clearly linked to the crater pit morphology, with oval pit features containing more identifiable residue, perhaps due to lower peak shock pressures experienced in these oblique-incidence impacts.

Are there interactions of iodine and sulfur species in marine air photochemistry?

NASA Technical Reports Server (NTRS)

Chatfield, Robert B.; Crutzen, Paul J.

1990-01-01

The effects of dimethyl sulfide (DMS) and methyl iodide (MI) emissions are analyzed using a two-dimensional photochemical model of a marine tropical tropospheric synoptic system. The model traces the atmospheric transformation cycles of the emissions to aerosols. The study is focused on remote tropical ocean regions and includes simulations of the spatial and diurnal variations of various iodine and sulfur species, and the species OH, HO2, and H2O2. One line of analysis leads to the conclusion that the reaction IO + DMS yields DMSO + I may play a significant role in destroying DMS if it proceeds at the published fast rate. Alternative lines of analyses are presented.

Ultrafast Infrared and UV-vis Studies of the Photochemistry of Methoxycarbonylphenyl Azides in Solution

PubMed Central

Xue, Jiadan; Luk, Hoi Ling; Eswaran, S. V.; Hadad, Christopher M.; Platz, Matthew S.

2012-01-01

The photochemistry of 4-methoxycarbonylphenyl azide (2a), 2-methoxycarbonylphenyl azide (3a) and 2-methoxy-6-methoxycarbonylphenyl azide (4a) were studied by ultrafast time-resolved infrared (IR) and UV-vis spectroscopies in solution. Singlet nitrenes and ketenimines were observed and characterized for all three azides. Isoxazole species 3g and 4g are generated after photolysis of 3a and 4a, respectively, in acetonitrile. Triplet nitrene 4e formation correlated with the decay of singlet nitrene 4b. The presence of water does not change the chemistry or kinetics of singlet nitrenes 2b and 3b, but leads to protonation of 4b to produce nitrenium ion 4f. Singlet nitrenes 2b and 3b have lifetimes of 2 ns and 400 ps, respectively, in solution at ambient temperature. The singlet nitrene 4b in acetonitrile has a lifetime of about 800 ps, and reacts with water with a rate constant of 1.9 × 108 L·mol−1·s−1 at room temperature. These results indicate that a methoxycarbonyl group at either the para or ortho positions has little influence on the ISC rate, but that the presence of a 2-methoxy group dramatically accelerates the ISC rate relative to the unsubstituted phenylnitrene. An ortho methoxy group highly stabilizes the corresponding nitrenium ion and favors its formation in aqueous solvents. This substituent has little influence on the ring-expansion rate. These results are consistent with theoretical calculations for the various intermediates and their transition states. Cyclization from the nitrene to the azirine intermediate is favored to proceed towards the electron-deficient ester group; however, the higher energy barrier is the ring-opening process, that is azirine to ketenimine formation, rendering the formation of the ester-ketenimine to be less favorable than the isomeric MeO-ketenimine. PMID:22568477

Ultrafast infrared and UV-vis studies of the photochemistry of methoxycarbonylphenyl azides in solution.

PubMed

Xue, Jiadan; Luk, Hoi Ling; Eswaran, S V; Hadad, Christopher M; Platz, Matthew S

2012-06-07

The photochemistry of 4-methoxycarbonylphenyl azide (2a), 2-methoxycarbonylphenyl azide (3a), and 2-methoxy-6-methoxycarbonylphenyl azide (4a) were studied by ultrafast time-resolved infrared (IR) and UV-vis spectroscopies in solution. Singlet nitrenes and ketenimines were observed and characterized for all three azides. Isoxazole species 3g and 4g are generated after photolysis of 3a and 4a, respectively, in acetonitrile. Triplet nitrene 4e formation correlated with the decay of singlet nitrene 4b. The presence of water does not change the chemistry or kinetics of singlet nitrenes 2b and 3b, but leads to protonation of 4b to produce nitrenium ion 4f. Singlet nitrenes 2b and 3b have lifetimes of 2 ns and 400 ps, respectively, in solution at ambient temperature. The singlet nitrene 4b in acetonitrile has a lifetime of about 800 ps, and reacts with water with a rate constant of 1.9 × 10(8) L·mol(-1)·s(-1) at room temperature. These results indicate that a methoxycarbonyl group at either the para or ortho positions has little influence on the ISC rate, but that the presence of a 2-methoxy group dramatically accelerates the ISC rate relative to the unsubstituted phenylnitrene. An ortho-methoxy group highly stabilizes the corresponding nitrenium ion and favors its formation in aqueous solvents. This substituent has little influence on the ring-expansion rate. These results are consistent with theoretical calculations for the various intermediates and their transition states. Cyclization from the nitrene to the azirine intermediate is favored to proceed toward the electron-deficient ester group; however, the higher energy barrier is the ring-opening process, that is, azirine to ketenimine formation, rendering the formation of the ester-ketenimine (4d') to be less favorable than the isomeric MeO-ketenimine (4d).

Characterization and photochemistry of 13-desmethyl bacteriorhodopsin.

PubMed

Gillespie, Nathan B; Ren, Lei; Ramos, Lavoisier; Daniell, Heather; Dews, Deborah; Utzat, Karissa A; Stuart, Jeffrey A; Buck, Charles H; Birge, Robert R

2005-08-25

The photochemistry of the 13-desmethyl (DM) analogue of bacteriorhodopsin (BR) is examined by using spectroscopy, molecular orbital theory, and chromophore extraction followed by conformational analysis. The removal of the 13-methyl group permits the direct photochemical formation of a thermally stable, photochemically reversible state, P1(DM) (lambda(max) = 525 nm), which can be generated efficiently by exciting the resting state, bR(DM) with yellow or red light (lambda > 590 nm). Chromophore extraction analysis reveals that the retinal configuration in P1(DM) is 9-cis, identical to that of the retinal configuration in the native BR P1 state. Fourier transform infrared and Raman experiments on P1(DM) indicate an anti configuration around the C15=N bond, as would be expected of an O-state photoproduct. However, low-temperature spectroscopy and ambient, time-resolved studies indicate that the P1(DM) state forms primarily via thermal relaxation from the L(D)(DM) state. Theoretical studies on the BR binding site show that 13-dm retinal is capable of isomerizing into a 9-cis configuration with minimal steric hindrance from surrounding residues, in contrast to the native chromophore in which surrounding residues significantly obstruct the corresponding motion. Analysis of the photokinetic experiments indicates that the Arrhenius activation energy of the bR(DM) --> P1(DM) transition in 13-dm-BR is less than 0.6 kcal/mol (vs 22 +/-5 kcal/mol measured for the bR --> P (P1 and P2) reaction in 85:15 glycerol:water suspensions of wild type). Consequently, the P1(DM) state in 13-dm-BR can form directly from all-trans, 15-anti intermediates (bR(DM) and O(DM)) or all-trans, 15-syn (K(D)(DM)/L(D)(DM)) intermediates. This study demonstrates that the 13-methyl group, and its interactions with nearby binding site residues, is primarily responsible for channeling one-photon photochemical and thermal reactions and is limited to the all-trans and 13-cis species interconversions in the native protein.

Ultrafast studies of organometallic photochemistry: The mechanism of carbon-hydrogen bond activation in solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bromberg, S.E.

1998-05-01

When certain organometallic compounds are photoexcited in room temperature alkane solution, they are able to break or activate the C-H bonds of the solvent. Understanding this potentially practical reaction requires a detailed knowledge of the entire reaction mechanism. Because of the dynamic nature of chemical reactions, time-resolved spectroscopy is commonly employed to follow the important events that take place as reactants are converted to products. For the organometallic reactions examined here, the electronic/structural characteristics of the chemical systems along with the time scales for the key steps in the reaction make ultrafast UV/Vis and IR spectroscopy along with nanosecond Step-Scanmore » FTIR spectroscopy the ideal techniques to use for this study. An initial study of the photophysics of (non-activating) model metal carbonyls centering on the photodissociation of M(CO){sub 6} (M = Cr, W, Mo) was carried out in alkane solutions using ultrafast IR spectroscopy. Next, picosecond UV/vis studies of the C-H bond activation reaction of Cp{sup *}M(CO){sub 2} (M = Rh, Ir), conducted in room temperature alkane solution, are described in an effort to investigate the origin of the low quantum yield for bond cleavage ({approximately}1%). To monitor the chemistry that takes place in the reaction after CO is lost, a system with higher quantum yield is required. The reaction of Tp{sup *}Rh(CO){sub 2} (Tp{sup *} = HB-Pz{sub 3}{sup *}, Pz{sup *} = 3,5-dimethylpyrazolyl) in alkanes has a quantum yield of {approximately}30%, making time resolved spectroscopic measurements possible. From ultrafast IR experiments, two subsequently formed intermediates were observed. The nature of these intermediates are discussed and the first comprehensive reaction mechanism for a photochemical C-H activating organometallic complex is presented.« less

Organic haze on Titan and the early Earth

PubMed Central

Trainer, Melissa G.; Pavlov, Alexander A.; DeWitt, H. Langley; Jimenez, Jose L.; McKay, Christopher P.; Toon, Owen B.; Tolbert, Margaret A.

2006-01-01

Recent exploration by the Cassini/Huygens mission has stimulated a great deal of interest in Saturn's moon, Titan. One of Titan's most captivating features is the thick organic haze layer surrounding the moon, believed to be formed from photochemistry high in the CH4/N2 atmosphere. It has been suggested that a similar haze layer may have formed on the early Earth. Here we report laboratory experiments that demonstrate the properties of haze likely to form through photochemistry on Titan and early Earth. We have used a deuterium lamp to initiate particle production in these simulated atmospheres from UV photolysis. Using a unique analysis technique, the aerosol mass spectrometer, we have studied the chemical composition, size, and shape of the particles produced as a function of initial trace gas composition. Our results show that the aerosols produced in the laboratory can serve as analogs for the observed haze in Titan's atmosphere. Experiments performed under possible conditions for early Earth suggest a significant optical depth of haze may have dominated the early Earth's atmosphere. Aerosol size measurements are presented, and implications for the haze layer properties are discussed. We estimate that aerosol production on the early Earth may have been on the order of 1014 g·year−1 and thus could have served as a primary source of organic material to the surface. PMID:17101962

An Effective and Facile Demonstration of Organic Photochemistry.

ERIC Educational Resources Information Center

Brown, Trevor M.; And Others

1990-01-01

Described is an experiment which may be carried out quickly using tungsten-filament irradiation. Materials, experimental procedures, and results are discussed. Procedures for filtration on silica gel are appended. (CW)

Vertical mixing and methane photochemistry in the atmosphere of Uranus: Analysis of Voyager UVS occultation experiments

NASA Technical Reports Server (NTRS)

Bishop, James

1991-01-01

Extensive capabilities were developed in the analysis of ultraviolet spectrometer (UVS) absorptive lightcurves. The application of these capabilities to the Voyager UVS data sets from Uranus and Neptune has provided significant findings regarding the stratospheres of these planets. In particular, the direct comparison between photochemical models and UVS measurements accomplished by these efforts is unique, and it helps to guarantee that the information returned by the Voyager 2 spacecraft is being used to the fullest extent possible.

A two-dimensional model with coupled dynamics, radiative transfer, and photochemistry. 2: Assessment of the response of stratospheric ozone to increased levels of CO2, N2O, CH4, and CFC

NASA Technical Reports Server (NTRS)

Schneider, Hans R.; Ko, Malcolm K. W.; Shia, Run-Lie; Sze, Nien-Dak

1993-01-01

The impact of increased levels of carbon dioxide (CO2), chlorofluorocarbons (CFCs), and other trace gases on stratospheric ozone is investigated with an interactive, two-dimensional model of gas phase chemistry, dynamics, and radiation. The scenarios considered are (1) a doubling of the CO2 concentration, (2) increases of CFCs, (3) CFC increases combined with increases of nitrous oxide (N2O) and methane CH4, and (4) the simultaneous increase of CO2, CFCs, N2O, and CH4. The radiative feedback and the effect of temperature and circulation changes are studied for each scenario. For the double CO2 calculations the tropospheric warming was specified. The CO2 doubling leads to a 3.1% increase in the global ozone content. Doubling of the CO2 concentrations would lead to a maximum cooling of about 12 C at 45 km if the ozone concentration were held fixed. The cooling of the stratosphere leads to an ozone increase with an associated increase in solar heating, reducing the maximum temperature drop by about 3 C. The CFC increase from continuous emissions at 1985 rate causes a 4.5% loss of ozone. For the combined perturbations a net loss of 1.3% is calculated. The structure of the perturbations shows a north-south asymmetry. Ozone losses (when expressed in terms of percent changes) are generally larger in the high latitudes of the southern hemisphere as a result of the eddy mixing being smaller than in the northern hemisphere. Increase of chlorine leads to ozone losses above 30 km altitude where the radiative feedback results in a cooler temperature and an ozone recovery of about one quarter of the losses predicted with a noninteractive model. In all the cases, changes in circulation are small. In the chlorine case, circulation changes reduce the calculated column depletion by about one tenth compared to offline calculations.

CHEMISTRY AND PHOTOCHEMISTRY OF LOW-VOLATILITY ORGANIC CHEMICALS ON ENVIRONMENTAL SURFACES

EPA Science Inventory

Hydrophobic organic xenobiotics such as polychlorinated dibenzodioxins and polycyclic aromatic hydrocarbons have strong tendencies to sorb on environmental surfaces. The paper summarizes a workshop in which scientists and modelers assembled to discuss nonbiological processes that...

The Gas Production Rate and Coma Structure of Comet C/1995 01 (Hale-Bopp)

NASA Technical Reports Server (NTRS)

Morgenthaler, Jeffrey P.; Harris, Walter M.; Roesler, Frederick L.; Scherb, Frank; Anderson, Christopher M.; Doane, Nathaniel E.; Oliversen, Ronald J.

2002-01-01

The University of Wisconsin-Madison and NASA-Goddard conducted a comprehensive multi-wavelength observing campaign of coma emissions from comet Hale-Bopp, including OH 3080 A, [O I] 6300 A, H2O(+) 6158 A, H Balmer-alpha 6563 A, NH2 6330 A, [C I] 9850 A CN 3879 A, C2 5141 A, C3 4062 A, C I 1657 A, and the UV and optical continua. In this work, we concentrate on the results of the H2O daughter studies. Our wide-field OH 3080 A measured flux agrees with other, similar observations and the expected value calculated from published water production rates using standard H2O and OH photochemistry. However, the total [O I] 6300 A flux determined spectroscopically over a similar field-of-view was a factor of 3 - 4 higher than expected. Narrow-band [O I] images show this excess came from beyond the H2O scale length, suggesting either a previously unknown source of [O I] or an error in the standard OH + upsilon to O((sup I)D) + H branching ratio. The Hale-Bopp OH and [O I] distributions, both of which were imaged to cometocentric distances greater than 1 x 10(exp 6) km, were more spatially extended than those of comet Halley (after correcting for brightness differences), suggesting a higher bulk outflow velocity. Evidence of the driving mechanism for this outflow is found in the H(alpha) line profile, which was narrower than in comet Halley (though likely because of opacity effects, not as narrow as predicted by Monte-Carlo models). This is consistent with greater collisional coupling between the suprathermal H photodissociation products and Hale-Bopp's dense coma. Presumably because of mass loading of the solar wind by ions and ions by the neutrals, the measured acceleration of H2O(+) down the ion tail was much smaller than in comet Halley. Tailward extensions in the azimuthal distributions of OH 3080 A, [O I], and [C I], as well as a Doppler asymmetry in the [O I] line profile, suggest ion-neutral coupling. While the tailward extension in the OH can be explained by increased neutral acceleration, the [O I] 6300 A and [C I] 9850 A emissions show 13% and less than 200% excesses in this direction (respectively), suggesting a non-negligible contribution from dissociative recombination of CO(+) and/or electron collisional excitation. Thus, models including the effects of photo-and collisional chemistry are necessary for the full interpretation of these data.

The Coupled Photochemistry of Ammonia and Acetylene: Applications to the Atmospheric Chemistry on Jupiter

NASA Astrophysics Data System (ADS)

Keane, Thomas Christopher

1995-01-01

The existence of hydrogen cyanide (HCN) in the highly reducing atmosphere of Jupiter was a surprising discovery (Tokunaga et al., 1981). Previous studies that tested the theoretical proposal of Kaye and Strobel (1983a) that the HCN observed on Jupiter is the result of NH _3 photolysis in the presence of C _2H_2 established that acetonitrile (CH_3CN) and acetaldazine (CH _3CH=NN=CHCH_3) are important intermediates in HCN formation (Ferris and Ishikawa, 1988). In this study the rates of formation of these compounds, and of other recently detected intermediates, have been determined in static photolysis experiments at 296 K and at temperatures which are closer to those found in the Jovian atmosphere. Experiments were also performed, using a photochemical flow reactor, that allowed for a better approximation of the mixing ratios of reactant gases (8 times 10^{ -4} for NH_3 and 1 times 10^{-5} for C_2H_2) and the process of advection in the Jovian atmosphere. An overall reaction pathway for HCN formation is proposed. Major intermediates and products found in these laboratory simulations that have not yet been observed on Jupiter are acetonitrile (CH_3CN), acetaldazine (CH_3CH=NN=CHCH _3), acetaldehyde hydrazone (CH_3 CH=NNH_2), N-ethylethylideneimine (CH_3CH=NC_2H _5), ethylamine (C_2H _5NH_2) and methylamine (CH _3NH_2). HCN is formed by the photolysis of NH_3/C _2H_2 mixtures (40:5 torr) at 296 K and at low temperature (208 K, 195 K and 180 K) with the highest quantum efficiency for HCN formation observed at 180 K. In static experiments using a high partial pressure of H_2 the quantum yield for HCN formation decreased three-fold relative to the 296 K photolyses when no H_2 was used. An additional ten-fold decrease in the quantum yield for HCN formation occurred when using the flow system. The quantum yields for acetaldazine and acetaldehyde hydrazone formation were found to vary inversely to that for HCN formation. For those static experiments which best simulate Jovian reaction conditions (H_2: NH_3 : C_2H_2 = 600: 7.5: 5 torr, 180 K) the following products and their quantum yields for formation were obtained: C_2H_4 (0.129), CH_3 CH=NN=CHCH_3 (0.079), CH _3CH=NNH_2 (0.049), C_2H_5NH_2 (0.038), CH_3NH_2 (0.003), CH_3CN (0.002), HCN (0.001) and CH_3CH=NC _2H_5 (0.001).

How fast do hydrocarbons condense in Titan's atmosphere? Insights from the laboratory

NASA Astrophysics Data System (ADS)

Biennier, L.; Bourgalais, J.; Capron, M.; Roussel, V.; Le Picard, S. D.

2014-04-01

Titan's dense atmosphere shows a complex photochemistry initiated by the dissociation of its two most abundant components, nitrogen N2 and methane CH4. This cold chemistry generates a plethora of hydrocarbons and nitriles and takes part in the production of a thick haze. According to a recent scenario constructed from Cassini-Huygens measurements, the chemical reactions and physical processes occurring at high altitudes near 1000 km could be the haze source [1]. This haze material could act as a nucleus for the condensation of organic vapors in Titan's stratosphere and troposphere. However, the pathways leading to the formation and growth of haze aerosols remain far to be well understood. Hydrocarbons, which are formed in Titan's cold atmosphere, starting with ethane C2H6, ethylene C2H4, acetylene C2H2, propane C3H8… up to benzene C6H6, play also some active role in aerosol production, cloud processes, rain generation and Titan's lakes formation. Our goal is to study in the laboratory the kinetics of the first steps of condensation of these hydrocarbon molecules. Several studies have investigated the phase of e.g. ethane and propane and their spectral signatures. At the exception of our recent studies on the dimerization of pyrene C16H10 [2] and anthracene C14H10 [3] performed over the 50-300 K temperature range, there is however no other work on the first elementary steps of the kinetics of nucleation for hydrocarbons. Here we present the first experimental kinetics study of the dimerization of a small hydrocarbon: propane C3H8. We have performed experiments to identify the temperature range over which small propane clusters form in saturated uniform supersonic flows. Using our unique reactor based on a Laval nozzle [4], the kinetics of the formation has also been investigated over the 15-300 K temperature range. The chemical species present in the reactor are probed by a time of flight mass spectrometer equipped with an electron gun for soft ionization of the neutral reagents and products. The experimental data is combined with state-of-the-art theoretical calculations that employ careful consideration of the intermolecular interaction energies and intermolecular dynamics to estimate the binding energy, equilibrium constant, and rate coefficients. This work aims at putting some constraints on the role of small hydrocarbon condensation in the formation of haze particles in the dense atmosphere of Titan.

The establishment of the atmospheric emission inventories of the ESCOMPTE program

NASA Astrophysics Data System (ADS)

François, S.; Grondin, E.; Fayet, S.; Ponche, J.-L.

2005-03-01

Within the frame of the ESCOMPTE program, a spatial emission inventory and an emission database aimed at tropospheric photochemistry intercomparison modeling has been developed under the scientific supervision of the LPCA with the help of the regional coordination of Air Quality network AIRMARAIX. This inventory has been established for all categories of sources (stationary, mobile and biogenic sources) over a domain of 19,600 km 2 centered on the cities of Marseilles-Aix-en-Provence in the southeastern part of France with a spatial resolution of 1 km 2. A yearly inventory for 1999 has been established, and hourly emission inventories for 23 days of June and July 2000 and 2001, corresponding to the intensive measurement periods, have been produced. The 104 chemical species in the inventory have been selected to be relevant with respect to photochemistry modeling according to available data. The entire list of species in the inventory numbers 216 which will allow other future applications of this database. This database is presently the most detailed and complete regional emission database in France. In addition, the database structure and the emission calculation modules have been designed to ensure a better sustainability and upgradeability, being provided with appropriate maintenance software. The general organization and method is summarized and the results obtained for both yearly and hourly emissions are detailed and discussed. Some comparisons have been performed with the existing results in this region to ensure the congruency of the results. This leads to confirm the relevance and the consistency of the ESCOMPTE emission inventory.

Detection of the Simplest Sugar, Glycolaldehyde, in a Solar-type Protostar with ALMA

NASA Astrophysics Data System (ADS)

Jørgensen, Jes K.; Favre, Cécile; Bisschop, Suzanne E.; Bourke, Tyler L.; van Dishoeck, Ewine F.; Schmalzl, Markus

2012-09-01

Glycolaldehyde (HCOCH2OH) is the simplest sugar and an important intermediate in the path toward forming more complex biologically relevant molecules. In this Letter we present the first detection of 13 transitions of glycolaldehyde around a solar-type young star, through Atacama Large Millimeter Array (ALMA) observations of the Class 0 protostellar binary IRAS 16293-2422 at 220 GHz (6 transitions) and 690 GHz (7 transitions). The glycolaldehyde lines have their origin in warm (200-300 K) gas close to the individual components of the binary. Glycolaldehyde co-exists with its isomer, methyl formate (HCOOCH3), which is a factor 10-15 more abundant toward the two sources. The data also show a tentative detection of ethylene glycol, the reduced alcohol of glycolaldehyde. In the 690 GHz data, the seven transitions predicted to have the highest optical depths based on modeling of the 220 GHz lines all show redshifted absorption profiles toward one of the components in the binary (IRAS 16293B) indicative of infall and emission at the systemic velocity offset from this by about 0farcs2 (25 AU). We discuss the constraints on the chemical formation of glycolaldehyde and other organic species—in particular, in the context of laboratory experiments of photochemistry of methanol-containing ices. The relative abundances appear to be consistent with UV photochemistry of a CH3OH-CO mixed ice that has undergone mild heating. The order of magnitude increase in line density in these early ALMA data illustrates its huge potential to reveal the full chemical complexity associated with the formation of solar system analogs.

Pyrimidinone: versatile Trojan horse in DNA photodamage?

PubMed

Micheel, Mathias; Torres Ziegenbein, Christian; Gilch, Peter; Ryseck, Gerald

2015-09-26

(6-4) Photolesions between adjacent pyrimidine DNA bases are prone to secondary photochemistry. It has been shown that singlet excited (6-4) moieties form Dewar valence isomers as well as triplet excitations. We here report on the triplet state of a minimal model for the (6-4) photolesion, 1-methyl-2(1H)-pyrimidinone. Emphasis is laid on its ability to abstract hydrogen atoms from alcohols and carbohydrates. Steady-state and time-resolved experiments consistently yield bimolecular rate constants of ∼10(4) M(-1) s(-1) for the hydrogen abstraction. The process also occurs intramolecularly as experiments on zebularine (1-(β-d-ribofuranosyl)-2(1H)-pyrimidinone) show.

Indian Academy of Sciences. Volume 105. Number 6. December 1993. Proceedings of the International Conference on Solar Energy Storage Applied Photochemistry (2nd) Held in Cairo, Egypt on 6-11 January 1993

DTIC Science & Technology

1993-12-01

Printed in India. Kinetics of sunlight photodegradation of 2,3,4,7, 8-pentachlorodi- benzofuran in natural water KEN J FRIESEN* and MYROSIA M FOGA...Wellington Laboratories (Guelph, *For correspondence 399 400 Ken J Friesen and Myrosia M Foga ON) and purified (to a radiopurity of 99.9%) by RP-HPLC with...destruction of P5 CDF. Photooxidation 402 Ken J Friesen and Myrosia M Foya 10.0 -. ?:CD DIRECT 0 U- INDIRECT 0.1 0 20 40 80 00 TIME (days) Figure I

Sulfur Chemistry in the Early and Present Atmosphere of Mars

NASA Technical Reports Server (NTRS)

Levine, Joel S.; Summers, M. E.

2011-01-01

Atmospheric sulfur species resulting from volcanic emissions impact the composition and chemistry of the atmosphere, impact the climate, and hence, the habitability of Mars and impact the mineralogy and composition of the surface of Mars. The geochemical/ photochemical cycling of sulfur species between the interior (via volcanism), the atmosphere (atmospheric photochemical and chemical processes) and the deposition of sulfuric acid on the surface of Mars is an important, but as yet poorly understood geochemical/ photochemical cycle on Mars. There is no observational evidence to indicate that Mars is volcanically active at the present time, however, there is strong evidence that volcanism was an important and widespread process on early Mars. The chemistry and photochemistry of sulfur species in the early and present atmosphere of Mars will be assessed using a one-dimensional photochemical model. Since it is generally assumed that the atmosphere of early Mars was significantly denser than the present 6-millibar atmosphere, photochemical calculations were performed for the present atmosphere and for the atmosphere of early Mars with assumed surface pressures of 60 and 350-millibars, where higher surface pressure resulted from enhanced atmospheric concentrations of carbon dioxide (CO2). The following sections include the results of earlier modeling studies, a summary of the one-dimensional photochemical model used in this study, a summary of the photochemistry and chemistry of sulfur species in the atmosphere of Mars and some of the results of the calculations.

Photosystem II Photoinactivation, Repair, and Protection in Marine Centric Diatoms1[OA

PubMed Central

Wu, Hongyan; Roy, Suzanne; Alami, Meriem; Green, Beverley R.; Campbell, Douglas A.

2012-01-01

Revised Version Diatoms are important contributors to aquatic primary production, and can dominate phytoplankton communities under variable light regimes. We grew two marine diatoms, the small Thalassiosira pseudonana and the large Coscinodiscus radiatus, across a range of temperatures and treated them with a light challenge to understand their exploitation of variable light environments. In the smaller T. pseudonana, photosystem II (PSII) photoinactivation outran the clearance of PSII protein subunits, particularly in cells grown at sub- or supraoptimal temperatures. In turn the absorption cross section serving PSII photochemistry was down-regulated in T. pseudonana through induction of a sustained phase of nonphotochemical quenching that relaxed only slowly over 30 min of subsequent low-light incubation. In contrast, in the larger diatom C. radiatus, PSII subunit turnover was sufficient to counteract a lower intrinsic susceptibility to photoinactivation, and C. radiatus thus did not need to induce sustained nonphotochemical quenching under the high-light treatment. T. pseudonana thus incurs an opportunity cost of sustained photosynthetic down-regulation after the end of an upward light shift, whereas the larger C. radiatus can maintain a balanced PSII repair cycle under comparable conditions. PMID:22829321

Uv Spectroscopy on Gas Phase Cu(I)-BIPYRIDYL Complexes

NASA Astrophysics Data System (ADS)

Xu, Shuang; Christopher, Casey; Weber, J. Mathias

2015-06-01

Transition metal complexes with bipyridine ligands are of great interest in metal-organic chemistry, since they are prototypes for many applications in photochemistry and homogeneous catalysis. Under-coordinated bipyridyl complexes are elusive species in the condensed phase, and the ligand-induced changes in electronic structure are of fundamental interest. We present UV photodissociation spectra of mass-selected monocationic copper(I)-bipyridyl complexes [bpy-Cu-L]+ with different ligands (L = H2O, D2, N2, MeOH, Cl). Complexes were prepared via electrospray ionization of copper/bipyridine solutions followed by accumulation and buffer gas cooling in a cryogenic Paul trap. In addition, we show spectra of similar species based on copper oxide, [bpy-CuO-L]+.

Hydrogen Bond Switching among Flavin and Amino Acid Side Chains in the BLUF Photoreceptor Observed by Ultrafast Infrared Spectroscopy

PubMed Central

Bonetti, Cosimo; Mathes, Tilo; van Stokkum, Ivo H. M.; Mullen, Katharine M.; Groot, Marie-Louise; van Grondelle, Rienk; Hegemann, Peter; Kennis, John T. M.

2008-01-01

BLUF domains constitute a recently discovered class of photoreceptor proteins found in bacteria and eukaryotic algae. BLUF domains are blue-light sensitive through a FAD cofactor that is involved in an extensive hydrogen-bond network with nearby amino acid side chains, including a highly conserved tyrosine and glutamine. The participation of particular amino acid side chains in the ultrafast hydrogen-bond switching reaction with FAD that underlies photoactivation of BLUF domains is assessed by means of ultrafast infrared spectroscopy. Blue-light absorption by FAD results in formation of FAD•− and a bleach of the tyrosine ring vibrational mode on a picosecond timescale, showing that electron transfer from tyrosine to FAD constitutes the primary photochemistry. This interpretation is supported by the absence of a kinetic isotope effect on the fluorescence decay on H/D exchange. Subsequent protonation of FAD•− to result in FADH• on a picosecond timescale is evidenced by the appearance of a N-H bending mode at the FAD N5 protonation site and of a FADH• C=N stretch marker mode, with tyrosine as the likely proton donor. FADH• is reoxidized in 67 ps (180 ps in D2O) to result in a long-lived hydrogen-bond switched network around FAD. This hydrogen-bond switch shows infrared signatures from the C-OH stretch of tyrosine and the FAD C4=O and C=N stretches, which indicate increased hydrogen-bond strength at all these sites. The results support a previously hypothesized rotation of glutamine by ∼180° through a light-driven radical-pair mechanism as the determinant of the hydrogen-bond switch. PMID:18708458

Laboratory studies of VUV photochemistry of water ice: measurements of photodesorption rates and implication for Polar Mesospheric Clouds

NASA Astrophysics Data System (ADS)

Kulikov, Mikhail; Feigin, Alexander; Ignatov, Stanislav; Sennikov, Petr; Schrems, Otto

Polar Mesospheric Clouds (PMC) are the highest clouds of the Earth's atmosphere. They are formed during summer at middle to high latitudes in an altitude range between 80 and 90 km when the air temperature drops below 150K. The particles of PMC consist primarily of ice [1] and are formed as a result of water vapor condensation. In the day time, PMC are subjected to strong solar Lyman -α irradiation with the wavelength of 121.6 nm which penetrates into ice particles and is absorbed essentially. This leads to photodissociation of H2 O molecules and to formation of mobile and chemically active components in the solid phase. As a result, a whole spectrum of physicochemical processes can be initiated inside the particles: diffusion of primary products, chemical formation of secondary products, accumulation of both type of products in the ice matrix and their escaping into gas-phase. Murray and Plane [2] hypothesized that the last process is dominant, i.e. each Lyman -α photon absorbed by a particle of PMC results in the ejection of one H atom and one OH radical into gas phase that provides essential enhancement of HOx concentration with a corresponding increase in Ox removal. Nevertheless, they justly pointed to the need of laboratory measurements of the H and OH yield from ice under conditions pertinent to the summer mesosphere. We have carried out first laboratory studies of water ice photochemistry to acquiring knowledge about physicochemical processes inside particles of PMC initiated by solar irradiation. The experimental set-up used includes a high-vacuum chamber, a gas-inlet system, a refrigerator-cryostat with temperature controller, a FTIR spectrometer, a vacuum ultraviolet hydrogen lamp and a microwave generator. This work presents results of measurements of the absolute photodesorption rate (loss of substance due to the escape of photoproducts into gas phase) from thin (20-100nm) water ice samples at temperatures of 120-150 K. The data obtained demonstrate that the flow of photoproducts into the gas phase is essentially less as predicted by Murray and Plane [2]. Nearly all the photoproducts remain in the solid phase, and the principal chemical reaction between them is the recombination reaction H+OH->H2O which is evidently very fast. 1. M. Hervig, R.E. Thompson, M. McHugh, L.L. Gordley, J.M. Russell III, and M.E. Sum-mers, First confirmation that water ice is the primary component of polar mesospheric clouds, Geophys. Res. Lett., 28, 971-974, 2001. 2. B.J. Murray and J.M.C. Plane, Modelling the impact of noctilucent cloud formation on atomic oxygen and other minor constituents of the summer mesosphere, Atmos. Chem. Phys., 5, 1027-1038, 2005.

International Conference on Photochemistry (15th) Abstracts of Invited Lectures and Oral and Poster Contributions Held in Paris, France on 28 July-2 August 1991 (XVeme Conference Internationale de Photochimie, Paris, France 28 Juillet-2 Aout 1991)

DTIC Science & Technology

1991-08-01

pyrene-labelled palmitoyl-phosphatidylcholine (PyPPC) and DPPA the pyrene is located at the monolayer-air interface. The ad- sorption of the electron...chemical transfor- mation of many trace compounds. Photodissociation of atmospheric species occurs by ab- sorption of solar ultraviolet and visible radiation...bakable one, and its inner surface is coated with PFA . The solar simulator and the end windows to introduce UV light were modified in order to utilize

Research in photobiology and photochemistry

NASA Technical Reports Server (NTRS)

Gaffron, H.

1973-01-01

Publications are listed covering NASA research from 1966 to 1973. Several major works covering chloroplast reactions, aerobic green algae and hydrogenease, production of molecular hydrogen, and hydrogen and nitrogen metabolism in purple bacteria are summarized.

Photochemistry of transition-metal phthalocyanines. Mechanistic aspects of the photochemistry of the acido(phthalocyanine)rhodium(III) complexes investigated by continuous, flash, and laser flash photolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muralidharan, S.; Ferraudi, G.; Schmatz, K.

1982-08-01

Rh(ph)(CH/sub 3/OH)X, X = Cl, Br, or I, has been prepared and characterized. Continuous-wave irradiations of these phthalocyanines in the ultraviolet region of the spectrum, in acetonitrile and acetonitrile-isopropyl alcohol mixtures, result in the redox-induced substitution of the axially coordinated halide ions by the solvent. Even though the overall reaction was photosubstitution, the intermediates observed by conventional and laser flash photolysis were found to be rhodium(II) phthalocyanine and rhodium(III) phthalocyanine ligand radicals. The photoredox processes were attributed to the population of (n..pi..*) ligand-centered excited states that involve the lone electron pair from the bridge nitrogens of the phthalocyanine ligand. 9more » figures, 3 tables.« less

Continuous Flow Science in an Undergraduate Teaching Laboratory: Photocatalytic Thiol-Ene Reaction Using Visible Light

ERIC Educational Resources Information Center

Santandrea, Jeffrey; Kairouz, Vanessa; Collins, Shawn K.

2018-01-01

An undergraduate teaching laboratory experiment involving a continuous flow, photocatalytic thiol-ene reaction using visible-light irradiation is described that allows students to explore concepts of green chemistry, photochemistry, photocatalysis, and continuous flow chemistry.

Assessing Photosynthesis by Fluorescence Imaging

ERIC Educational Resources Information Center

Saura, Pedro; Quiles, Maria Jose

2011-01-01

This practical paper describes a novel fluorescence imaging experiment to study the three processes of photochemistry, fluorescence and thermal energy dissipation, which compete during the dissipation of excitation energy in photosynthesis. The technique represents a non-invasive tool for revealing and understanding the spatial heterogeneity in…

Exploring matrix effects on photochemistry of organic aerosols

PubMed Central

Lignell, Hanna; Hinks, Mallory L.; Nizkorodov, Sergey A.

2014-01-01

This work explores the effect of the environment on the rate of photolysis of 2,4-dinitrophenol (24-DNP), an important environmental toxin. In stark contrast to the slow photolysis of 24-DNP in an aqueous solution, the photolysis rate is increased by more than an order of magnitude for 24-DNP dissolved in 1-octanol or embedded in secondary organic material (SOM) produced by ozonolysis of α-pinene. Lowering the temperature decreased the photolysis rate of 24-DNP in SOM much more significantly than that of 24-DNP in octanol, with effective activation energies of 53 kJ/mol and 12 kJ/mol, respectively. We discuss the possibility that the increasing viscosity of the SOM matrix constrains the molecular motion, thereby suppressing the hydrogen atom transfer reaction to the photo-excited 24-DNP. This is, to our knowledge, the first report of a significant effect of the matrix, and possibly viscosity, on the rate of an atmospheric photochemical reaction within SOM. It suggests that rates of photochemical processes in organic aerosols will depend on both relative humidity and temperature and thus altitude. The results further suggest that photochemistry in SOM may play a key role in transformations of atmospheric organics. For example, 24-DNP and other nitro-aromatic compounds should readily photodegrade in organic particulate matter, which has important consequences for predicting their environmental fates and impacts. PMID:25201953

Isoprene photochemistry over the Amazon rainforest

DOE PAGES

Liu, Yingjun; Brito, Joel; Dorris, Matthew R.; ...

2016-05-31

Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO 2) to dominantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK +more » MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4–0.6. This result implies a ratio of the reaction rate of ISOPOO with HO2 to that with NO of approximately unity. Also, a value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (<60 ppt). In conclusion, this abrupt shift in isoprene photooxidation, sparked by human activities, speaks to ongoing and possible future changes in the photochemistry active over the Amazon rainforest.« less

Isoprene photochemistry over the Amazon rainforest

PubMed Central

Liu, Yingjun; Brito, Joel; Dorris, Matthew R.; Rivera-Rios, Jean C.; Seco, Roger; Bates, Kelvin H.; Artaxo, Paulo; Duvoisin, Sergio; Keutsch, Frank N.; Kim, Saewung; Goldstein, Allen H.; Guenther, Alex B.; Manzi, Antonio O.; Souza, Rodrigo A. F.; Springston, Stephen R.; Watson, Thomas B.; McKinney, Karena A.

2016-01-01

Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO2) to dominantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK + MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4–0.6. This result implies a ratio of the reaction rate of ISOPOO with HO2 to that with NO of approximately unity. A value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (<60 ppt). This abrupt shift in isoprene photooxidation, sparked by human activities, speaks to ongoing and possible future changes in the photochemistry active over the Amazon rainforest. PMID:27185928

The Origin of Titan’s External Oxygen: Further Constraints from ALMA Upper Limits on CS and CH2NH

NASA Astrophysics Data System (ADS)

Teanby, N. A.; Cordiner, M. A.; Nixon, C. A.; Irwin, P. G. J.; Hörst, S. M.; Sylvestre, M.; Serigano, J.; Thelen, A. E.; Richards, A. M. S.; Charnley, S. B.

2018-06-01

Titan’s atmospheric inventory of oxygen compounds (H2O, CO2, CO) are thought to result from photochemistry acting on externally supplied oxygen species (O+, OH, H2O). These species potentially originate from two main sources: (1) cryogenic plumes from the active moon Enceladus and (2) micrometeoroid ablation. Enceladus is already suspected to be the major O+ source, which is required for CO creation. However, photochemical models also require H2O and OH influx to reproduce observed quantities of CO2 and H2O. Here, we exploit sulphur as a tracer to investigate the oxygen source because it has very different relative abundances in micrometeorites (S/O ∼ 10‑2) and Enceladus’ plumes (S/O ∼ 10‑5). Photochemical models predict most sulphur is converted to CS in the upper atmosphere, so we use Atacama Large Millimeter/submillimeter Array (ALMA) observations at ∼340 GHz to search for CS emission. We determined stringent CS 3σ stratospheric upper limits of 0.0074 ppb (uniform above 100 km) and 0.0256 ppb (uniform above 200 km). These upper limits are not quite stringent enough to distinguish between Enceladus and micrometeorite sources at the 3σ level and a contribution from micrometeorites cannot be ruled out, especially if external flux is toward the lower end of current estimates. Only the high-flux micrometeorite source model of Hickson et al. can be rejected at 3σ. We determined a 3σ stratospheric upper limit for CH2NH of 0.35 ppb, which suggests cosmic rays may have a smaller influence in the lower stratosphere than predicted by some photochemical models. Disk-averaged C3H4 and C2H5CN profiles were determined and are consistent with previous ALMA and Cassini/CIRS measurements.

Photosynthetic characteristics and mycosporine-like amino acids under UV radiation: a competitive advantage of Mastocarpus stellatus over Chondrus crispus at the Helgoland shoreline?

NASA Astrophysics Data System (ADS)

Bischof, K.; Kräbs, G.; Hanelt, D.; Wiencke, C.

2000-05-01

Chondrus crispus and Mastocarpus stellatus both inhabit the intertidal and upper sublittoral zone of Helgoland, but with C. crispus generally taking a lower position. Measurements of chlorophyll fluorescence, activity of ribulose-1,5-bisphosphate carboxylase/oxygenase (RubisCO), and content and composition of UV absorbing mycosporine-like amino acids (MAAs) were conducted in the laboratory, to test whether susceptibility to UV radiation may play a role in the vertical distribution of these two species. Effective and maximal quantum yield of photochemistry as well as maximal electron transport rate (ETRmax) in C. crispus were more strongly affected by UV-B radiation than in M. stellatus. In both species, no negative effects of the respective radiation conditions were found on total activity of RubisCO. Total MAA content in M. stellatus was up to 6-fold higher than in C. crispus and the composition of MAAs in the two species was different. The results indicate that, among others, UV-B sensitivity may be a factor restricting C. crispus to the lower intertidal and upper sublittoral zone, whereas M. stellatus is better adapted to UV radiation and is therefore more competitive in the upper intertidal zone.

Two-photon-induced cycloreversion reaction of chalcone photodimers

NASA Astrophysics Data System (ADS)

Träger, J.; Härtner, S.; Heinzer, J.; Kim, H.-C.; Hampp, N.

2008-04-01

The photocleavage reaction of chalcone photodimers has been studied using a two-photon process. For this purpose, a novel chalcone dimer has been synthesized as a low molecular weight model substance for polymer bound chalcones and its photochemistry triggered by two-photon-absorption (2PA) has been investigated using a pulsed frequency-doubled Nd:YAG-laser. The 2PA-induced cycloreversion reaction selectively leads to the cleavage of the chalcone photodimers resulting in the formation of monomeric chalcone molecules. Hence, as an application chalcones can be used as a photosensitive linker which can be cleaved beyond an UV-absorbing barrier. The 2PA cross section of the chalcone photodimer was determined to be of 1.1 × 10 -49 cm 4 s photon -1 (11 GM).

Photochemical Concepts on the Origin of Biomolecular Asymmetry

NASA Astrophysics Data System (ADS)

Meierhenrich, Uwe J.; Thiemann, Wolfram H.-P.

2004-02-01

Biopolymers like DNA and proteins are strongly selective towards the chirality of their monomer units. The use of homochiral monomers is regarded as essential for the construction and function of biopolymers; the emergence of the molecular asymmetry is therefore considered as a fundamental step in Chemical Evolution. This work focuses on physicochemical mechanisms for the origin of biomolecular asymmetry. Very recently two groups, one from Allamandola at NASA Ames and the other from our Inter-European team, demonstrated simultaneously the spontaneous photoformation of a variety of chiral amino acid structures under simulated interstellar conditions. Since both groups used unpolarized light for the photoreaction the obtained amino acids turned out racemic as expected. The obtained experimental data support the assumption that tiny ice grains can furthermore play host to important asymmetric reactions when irradiated by interstellar circularly polarized ultraviolet light. It is possible that such ice grains could have become incorporated into the early cloud that formed our Solar System and ended up on Earth, assisting life to start. Several lines of evidence suggest that some of the building blocks of life were delivered to the primitive Earth via (micro-) meteoroids and/or comets. These results suggest that asymmetric interstellar photochemistry may have played a significant part in supplying Earth with some of the enantioenriched organic materials needed to trigger life. The search for the origin of biomolecular homochirality leads to a strong interest in the fields of asymmetric photochemistry with special emphasis on absolute asymmetric synthesis. We outline here the theoretical background on asymmetric interstellar ice photochemistry, summarize recent concepts and advances in the field, and discuss briefly its implications. The obtained data are crucial for the design of the enantioselective COSAC GC-MS experiment onboard the ROSETTA spacecraft to a comet to be launched in the very near future.

Photochemistry of nucleic acid bases and their thio- and aza-analogues in solution.

PubMed

Pollum, Marvin; Martínez-Fernández, Lara; Crespo-Hernández, Carlos E

2015-01-01

The steady-state and time-resolved photochemistry of the natural nucleic acid bases and their sulfur- and nitrogen-substituted analogues in solution is reviewed. Emphasis is given to the experimental studies performed over the last 3-5 years that showcase topical areas of scientific inquiry and those that require further scrutiny. Significant progress has been made toward mapping the radiative and nonradiative decay pathways of nucleic acid bases. There is a consensus that ultrafast internal conversion to the ground state is the primary relaxation pathway in the nucleic acid bases, whereas the mechanism of this relaxation and the level of participation of the (1)πσ*, (1) nπ*, and (3)ππ* states are still matters of debate. Although impressive research has been performed in recent years, the microscopic mechanism(s) by which the nucleic acid bases dissipate excess vibrational energy to their environment, and the role of the N-glycosidic group in this and in other nonradiative decay pathways, are still poorly understood. The simple replacement of a single atom in a nucleobase with a sulfur or nitrogen atom severely restricts access to the conical intersections responsible for the intrinsic internal conversion pathways to the ground state in the nucleic acid bases. It also enhances access to ultrafast and efficient inter-system crossing pathways that populate the triplet manifold in yields close to unity. Determining the coupled nuclear and electronic pathways responsible for the significantly different photochemistry in these nucleic acid base analogues serves as a convenient platform to examine the current state of knowledge regarding the photodynamic properties of the DNA and RNA bases from both experimental and computational perspectives. Further investigations should also aid in forecasting the prospective use of sulfur- and nitrogen-substituted base analogues in photochemotherapeutic applications.

Micro-Scale Sulfur and Carbon Isotope Analysis of a Neoarchean Stromatolite: Evidence for a Profound Redox Transition in Shelf Margins prior to the Great Oxidation Event

NASA Astrophysics Data System (ADS)

Ilhardt, P.; House, C. H.; Altermann, W.

2016-12-01

Neoarchean shelf margin environments such as the Campbellrand-Malmani platform are believed to have been sites of substantial O2 accumulation and nutrient cycling prior to the Great Oxidation Event (GOE). Stromatolites in particular serve as biogeochemical "hotspots" where evidence of various metabolic pathways and bacterial lineages can be traced through geochemical fingerprints. We identified morphologically-unique, organic-rimmed pyrite grains embedded in the dolomitic lamina of a Campbellrand Subgroup stromatolite (2.6 Ga). Carbon and sulfur isotopes measured in situ revealed a multi-layered microbial community employing photoautotrophic carbon fixation, organic matter respiration, sulfate reduction, and potentially assimilation of methane. In particular, unusually high kerogen δ13Corg and pyrite δ34S compositions are consistent with a semi-aerobic ecosystem recycling photosynthetic biomass and sulfate reduction in sulfate-limited porewaters, respectively. In addition, an array of positive Δ33S values suggests incorporation of atmospherically-derived sulfur formed from volcanic SO2 photochemistry and isolated in particulate form. We argue the Δ33S-δ34S trend is best explained by mixing between a δ34S-enriched coastal marine sulfate reservoir and stratospheric Δ33S-positive sulfate or elemental sulfur aerosols. The hypothesized buildup of sulfur gases at higher altitudes agrees with prior arguments for increased subaerial felsic volcanism and intense plume activity coinciding with oxidation of the upper mantle. We suggest explosive subaerial eruptions sustained a stratospheric SO2 reservoir that underwent photochemistry via long-wavelength (250-330 nm) UV radiation to produce positive MIF-carrying aerosol particles (sulfate or sulfur) in the Neoarchean. This contrasts with Paleoarchean sulfur chemistry dominated by SO2 photolysis in the 190-220 nm excitation band and points to an evolving Archean atmosphere, culminating in a coupled biogeochemical-tectonic redox transformation that fundamentally changed the atmospheric sulfur cycle and ultimately prompted the GOE.

Aerosol optical extinction during the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ) 2014 summertime field campaign, Colorado, USA

NASA Astrophysics Data System (ADS)

Dingle, Justin H.; Vu, Kennedy; Bahreini, Roya; Apel, Eric C.; Campos, Teresa L.; Flocke, Frank; Fried, Alan; Herndon, Scott; Hills, Alan J.; Hornbrook, Rebecca S.; Huey, Greg; Kaser, Lisa; Montzka, Denise D.; Nowak, John B.; Reeves, Mike; Richter, Dirk; Roscioli, Joseph R.; Shertz, Stephen; Stell, Meghan; Tanner, David; Tyndall, Geoff; Walega, James; Weibring, Petter; Weinheimer, Andrew

2016-09-01

Summertime aerosol optical extinction (βext) was measured in the Colorado Front Range and Denver metropolitan area as part of the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ) campaign during July-August 2014. An Aerodyne cavity attenuated phase shift particle light extinction monitor (CAPS-PMex) was deployed to measure βext (at average relative humidity of 20 ± 7 %) of submicron aerosols at λ = 632 nm at 1 Hz. Data from a suite of gas-phase instrumentation were used to interpret βext behavior in various categories of air masses and sources. Extinction enhancement ratios relative to CO (Δβext / ΔCO) were higher in aged urban air masses compared to fresh air masses by ˜ 50 %. The resulting increase in Δβext / ΔCO for highly aged air masses was accompanied by formation of secondary organic aerosols (SOAs). In addition, the impacts of aerosol composition on βext in air masses under the influence of urban, natural oil and gas operations (O&G), and agriculture and livestock operations were evaluated. Estimated non-refractory mass extinction efficiency (MEE) values for different air mass types ranged from 1.51 to 2.27 m2 g-1, with the minimum and maximum values observed in urban and agriculture-influenced air masses, respectively. The mass distribution for organic, nitrate, and sulfate aerosols presented distinct profiles in different air mass types. During 11-12 August, regional influence of a biomass burning event was observed, increasing the background βext and estimated MEE values in the Front Range.

Enantioselective photochemistry via Lewis acid catalyzed triplet energy transfer

PubMed Central

Blum, Travis R.; Miller, Zachary D.; Bates, Desiree M.; Guzei, Ilia A.; Yoon, Tehshik P.

2017-01-01

Relatively few catalytic systems are able to control the stereochemistry of electronically excited organic intermediates. Here we report the discovery that a chiral Lewis acid complex can catalyze triplet energy transfer from an electronically excited photosensitizer. This strategy is applied to asymmetric [2+2] photocycloadditions of 2′-hydroxychalcones using tris(bipyridyl) ruthenium(II) as a sensitizer. A variety of electrochemical, computational, and spectroscopic data rule out substrate activation via photoinduced electron transfer and instead support a mechanism in which Lewis acid coordination dramatically lowers the triplet energy of the chalcone substrate. We expect that this approach will enable chemists to more broadly apply their detailed understanding of chiral Lewis acid catalysis to stereocontrol in reactions of electronically excited states. PMID:27980203

Cl2O photochemistry: ultraviolet/vis absorption spectrum temperature dependence and O(3P) quantum yield at 193 and 248 nm.

PubMed

Papanastasiou, Dimitrios K; Feierabend, Karl J; Burkholder, James B

2011-05-28

The photochemistry of Cl(2)O (dichlorine monoxide) was studied using measurements of its UV/vis absorption spectrum temperature dependence and the O((3)P) atom quantum yield, Φ(Cl(2)O)(O)(λ), in its photolysis at 193 and 248 nm. The Cl(2)O UV/vis absorption spectrum was measured over the temperature range 201-296 K between 200 and 500 nm using diode array spectroscopy. Cl(2)O absorption cross sections, σ(Cl(2)O)(λ,T), at temperatures <296 K were determined relative to its well established room temperature values. A wavelength and temperature dependent parameterization of the Cl(2)O spectrum using the sum of six Gaussian functions, which empirically represent transitions from the ground (1)A(1) electronic state to excited states, is presented. The Gaussian functions are found to correlate well with published theoretically calculated vertical excitation energies. O((3)P) quantum yields in the photolysis of Cl(2)O at 193 and 248 nm were measured using pulsed laser photolysis combined with atomic resonance fluorescence detection of O((3)P) atoms. O((3)P) quantum yields were measured to be 0.85 ± 0.15 for 193 nm photolysis at 296 K and 0.20 ± 0.03 at 248 nm, which was also found to be independent of temperature (220-352 K) and pressure (17 and 28 Torr, N(2)). The quoted uncertainties are at the 2σ (95% confidence) level and include estimated systematic errors. ClO radical temporal profiles obtained following the photolysis of Cl(2)O at 248 nm, as reported previously in Feierabend et al. [J. Phys. Chem. A 114, 12052, (2010)], were interpreted to establish a <5% upper-limit for the O + Cl(2) photodissociation channel, which indicates that O((3)P) is primarily formed in the three-body, O + 2Cl, photodissociation channel at 248 nm. The analysis also indirectly provided a Cl atom quantum yield of 1.2 ± 0.1 at 248 nm. The results from this work are compared with previous studies where possible. © 2011 American Institute of Physics

Leaf age and methodology impact assessments of thermotolerance of Coffea arabica

Treesearch

Danielle E. Marias; Frederick C. Meinzer; Christopher Still

2017-01-01

Key message Mature Coffea arabica leaves were more heat tolerant than expanding leaves, longer recovery time yielded more accurate thermotolerance assessments, and photochemistry was more heat sensitive than cell membranes. Abstract Given...

Clues from defect photochemistry

NASA Astrophysics Data System (ADS)

De Angelis, Filippo; Petrozza, Annamaria

2018-05-01

Charge carriers in metal halide perovskites seem to be only marginally affected by defect-related trap states. Filippo De Angelis and Annamaria Petrozza suggest that the key to this behaviour lies in the redox chemistry of halide defects.

A Tractable Numerical Model for Exploring Nonadiabatic Quantum Dynamics

ERIC Educational Resources Information Center

Camrud, Evan; Turner, Daniel B.

2017-01-01

Numerous computational and spectroscopic studies have demonstrated the decisive role played by nonadiabatic coupling in photochemical reactions. Nonadiabatic coupling drives photochemistry when potential energy surfaces are nearly degenerate at avoided crossings or truly degenerate at unavoided crossings. The dynamics induced by nonadiabatic…