Ground-based remote sensing of HDO/H2O ratio profiles: introduction and validation of an innovative retrieval approach

NASA Astrophysics Data System (ADS)

Schneider, M.; Hase, F.; Blumenstock, T.

2006-06-01

We propose an innovative approach for analysing ground-based FTIR spectra which allows us to detect variabilities of lower and middle/upper tropospheric HDO/H2O ratios. We show that the proposed method is superior to common approaches. We estimate that lower tropospheric HDO/H2O ratios can be detected with a noise to signal ratio of 15% and middle/upper tropospheric ratios with a noise to signal ratio of 50%. The method requires the inversion to be performed on a logarithmic scale and to introduce an inter-species constraint. While common methods calculate the isotope ratio posterior to an independent, optimal estimation of the HDO and H2O profile, the proposed approach is an optimal estimator for the ratio itself. We apply the innovative approach to spectra measured continuously during 15 months and present, for the first time, an annual cycle of tropospheric HDO/H2O ratio profiles as detected by ground-based measurements. Outliers in the detected middle/upper tropospheric ratios are interpreted by backward trajectories.

Rapid and sensitive quantification of isotopic mixtures using a rapidly-swept external cavity quantum cascade laser

DOE PAGES

Brumfield, Brian E.; Taubman, Matthew S.; Phillips, Mark C.

2016-05-23

A rapidly-swept external-cavity quantum cascade laser with an open-path Herriott cell is used to quantify gas-phase chemical mixtures of D 2O and HDO at a rate of 40 Hz (25-ms measurement time). The chemical mixtures were generated by evaporating D 2O liquid near the open-path Herriott cell, allowing the H/D exchange reaction with ambient H 2O to produce HDO. Fluctuations in the ratio of D 2O and HDO on timescales of <1 s due to the combined effects of plume transport and the H/D exchange chemical reaction are observed. Noise-equivalent concentrations (1σ) (NEC) of 147.0 ppbv and 151.6 ppbv inmore » a 25-ms measurement time are determined for D 2O and HDO, respectively, with a 127-m optical path. These NECs are improved to 23.0 and 24.0 ppbv with a 1-s averaging time for D 2O and HDO, respectively. NECs <200 ppbv are also estimated for N2O, 1,1,1,2–tetrafluoroethane (F134A), CH 4, acetone and SO 2 for a 25-ms measurement time. Finally, the isotopic precision for measurement of the [D 2O]/[HDO] concentration ratio of 33‰ and 5‰ is calculated for the current experimental conditions for measurement times of 25 ms and 1 s, respectively.« less

Simultaneous nitrification, denitrification, and phosphorus removal in single-tank low-dissolved-oxygen systems under cyclic aeration.

PubMed

Ju, Lu-Kwang; Huang, Lin; Trivedi, Hiren

2007-08-01

Simultaneous nitrification and denitrification (SND or SNdN) may occur at low dissolved oxygen concentrations. In this study, bench-scale (approximately 6 L) bioreactors treating a continuous feed of synthetic wastewater were used to evaluate the effects of solids retention time and low dissolved oxygen concentration, under cyclic aeration, on the removal of organics, nitrogen, and phosphorus. The cyclic aeration was carried out with repeated cycles of 1 hour at a higher dissolved oxygen concentration (HDO) and 30 minutes at a lower (or zero) dissolved oxygen concentration (LDO). Compared with aeration at constant dissolved oxygen concentrations, the cyclic aeration, when operated with proper combinations of HDO and LDO, produced better-settling sludge and more complete nitrogen and phosphorus removal. For nitrogen removal, the advantage resulted from the more readily available nitrate and nitrite (generated by nitrification during the HDO period) for denitrification (during the LDO period). For phosphorus removal, the advantage of cyclic aeration came from the development of a higher population of polyphosphate-accumulating organisms, as indicated by the higher phosphorus contents in the sludge solids of the cyclically aerated systems. Nitrite shunt was also observed to occur in the LDO systems. Higher ratios of nitrite to nitrate were found in the systems of lower HDO (and, to less dependency, higher LDO), suggesting that the nitrite shunt took place mainly because of the disrupted nitrification at lower HDO. The study results indicated that the HDO used should be kept reasonably high (approximately 0.8 mg/L) or the HDO period prolonged, to promote adequate nitrification, and the LDO kept low (< or =0.2 mg/L), to achieve more complete denitrification and higher phosphorus removal. The above findings in the laboratory systems find strong support from the results obtained in full-scale plant implementation. Two plant case studies using the cyclic low-dissolved-oxygen aeration for creating and maintaining SND are also presented.

Hydrodeoxygenation processes: advances on catalytic transformations of biomass-derived platform chemicals into hydrocarbon fuels.

PubMed

De, Sudipta; Saha, Basudeb; Luque, Rafael

2015-02-01

Lignocellulosic biomass provides an attractive source of renewable carbon that can be sustainably converted into chemicals and fuels. Hydrodeoxygenation (HDO) processes have recently received considerable attention to upgrade biomass-derived feedstocks into liquid transportation fuels. The selection and design of HDO catalysts plays an important role to determine the success of the process. This review has been aimed to emphasize recent developments on HDO catalysts in effective transformations of biomass-derived platform molecules into hydrocarbon fuels with reduced oxygen content and improved H/C ratios. Liquid hydrocarbon fuels can be obtained by combining oxygen removal processes (e.g. dehydration, hydrogenation, hydrogenolysis, decarbonylation etc.) as well as by increasing the molecular weight via C-C coupling reactions (e.g. aldol condensation, ketonization, oligomerization, hydroxyalkylation etc.). Fundamentals and mechanistic aspects of the use of HDO catalysts in deoxygenation reactions will also be discussed. Copyright © 2014 Elsevier Ltd. All rights reserved.

Directing Reaction Pathways through Controlled Reactant Binding at Pd-TiO2 Interfaces.

PubMed

Zhang, Jing; Wang, Bingwen; Nikolla, Eranda; Medlin, J Will

2017-06-01

Recent efforts to design selective catalysts for multi-step reactions, such as hydrodeoxygenation (HDO), have emphasized the preparation of active sites at the interface between two materials having different properties. However, achieving precise control over interfacial properties, and thus reaction selectivity, has remained a challenge. Here, we encapsulated Pd nanoparticles (NPs) with TiO 2 films of regulated porosity to gain a new level of control over catalyst performance, resulting in essentially 100 % HDO selectivity for two biomass-derived alcohols. This catalyst also showed exceptional reaction specificity in HDO of furfural and m-cresol. In addition to improving HDO activity by maximizing the interfacial contact between the metal and metal oxide sites, encapsulation by the nanoporous oxide film provided a significant selectivity boost by restricting the accessible conformations of aromatics on the surface. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanistic Effects of Water on the Fe-Catalyzed Hydrodeoxygenation of Phenol. The Role of Brønsted Acid Sites

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

Hensley, Alyssa J. R.; Wang, Yong; Mei, Donghai

A mechanistic understanding of the roles of water is essential for developing highly active and selective catalysts for hydrodeoxygenation (HDO) reactions since water is ubiquitous in such reaction systems. Here, we present a study for phenol HDO on Fe catalysts using density functional theory which examines the effect of water on three elementary pathways for phenol HDO using an explicit solvation model. The presence of water is found to significantly decrease activation barriers required by hydrogenation reactions via two pathways. First, the proton transfer in the hydrogen bonding network of the liquid water phase is nearly barrierless, which significantly promotesmore » the direct through space tautomerization of phenol. Second, due to the high degree of oxophilicity on Fe, liquid water molecules are found to be easily dissociated into surface hydroxyl groups that can act as Brønsted acid sites. These sites dramatically promote hydrogenation reactions on the Fe surface. As a result, the hydrogen assisted dehydroxylation becomes the dominant phenol HDO pathway. This work provides new fundamental insights into aqueous phase HDO of biomass-derived oxygenates over Fe-based catalysts; e.g., the activity of Fe-based catalysts can be optimized by tuning the surface coverage of Brønsted acid sites via surface doping.« less

Effects of lignin structure on hydrodeoxygenation reactivity of pine wood lignin to valuable chemicals

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

Wang, Hongliang; Ben, Haoxi; Southeast Univ., Nanjing

Hydrodeoxygenation (HDO) of two dilute acid flow through pretreated softwood lignin samples, including residual lignin in pretreated solid residues (ReL) and recovered insoluble lignin in pretreated liquid (RISL), with apparent different physical and chemical structures, was comprehensively studied. A combination of catalysts (HY zeolite and Ru/Al 2O 3) was employed to investigate the effects of lignin structures, especially condensed structures, on the HDO upgrading process. Results indicated that the condensed structure and short side chains in lignin hindered its HDO conversion under different reaction conditions, including catalyst loading and composition, hydrogen pressure, and reaction time. In addition to lignin structure,more » HY zeolite was found crucial for lignin depolymerization, while Ru/Al 2O 3 and relatively high hydrogen pressure (4 MPa) were necessary for upgrading unstable oxy-compounds to cyclohexanes at high selectivity (>95 wt %). Since the lignin structure essentially affects its reactivity during HDO conversion, the yield and selectivity of HDO products can be predicted by detailed characterization of the lignin structure. Furthermore, the insights gained from this study in the fundamental reaction mechanisms based on the lignin structure will facilitate upgrading of lignin to high-value products for applications in the production of both fuels and chemicals.« less

Effects of lignin structure on hydrodeoxygenation reactivity of pine wood lignin to valuable chemicals

DOE PAGES

Wang, Hongliang; Ben, Haoxi; Southeast Univ., Nanjing; ...

2017-01-05

Hydrodeoxygenation (HDO) of two dilute acid flow through pretreated softwood lignin samples, including residual lignin in pretreated solid residues (ReL) and recovered insoluble lignin in pretreated liquid (RISL), with apparent different physical and chemical structures, was comprehensively studied. A combination of catalysts (HY zeolite and Ru/Al 2O 3) was employed to investigate the effects of lignin structures, especially condensed structures, on the HDO upgrading process. Results indicated that the condensed structure and short side chains in lignin hindered its HDO conversion under different reaction conditions, including catalyst loading and composition, hydrogen pressure, and reaction time. In addition to lignin structure,more » HY zeolite was found crucial for lignin depolymerization, while Ru/Al 2O 3 and relatively high hydrogen pressure (4 MPa) were necessary for upgrading unstable oxy-compounds to cyclohexanes at high selectivity (>95 wt %). Since the lignin structure essentially affects its reactivity during HDO conversion, the yield and selectivity of HDO products can be predicted by detailed characterization of the lignin structure. Furthermore, the insights gained from this study in the fundamental reaction mechanisms based on the lignin structure will facilitate upgrading of lignin to high-value products for applications in the production of both fuels and chemicals.« less

Systolic arterial blood pressure estimated by mitral regurgitation velocity, high definition oscillometry, and Doppler ultrasonography in dogs with naturally occurring degenerative mitral valve disease.

PubMed

Hanzlicek, A S; Baumwart, R D; Payton, M E

2016-09-01

To determine if systolic blood pressure estimated by mitral regurgitation (MR) velocity can be used interchangeably with that estimated by high definition oscillometry (HDO) and Doppler ultrasonography (DU) in dogs with naturally occurring mitral valve disease (MVD). Forty-nine client-owned dogs with naturally occurring MVD. This is a retrospective study. Medical records were reviewed and dogs with MR caused by degenerative MVD were included if systolic blood pressure was estimated from MR velocity determined by continuous wave Doppler (CW), DU and HDO at the same visit. A Pearson product moment correlation coefficient was determined for each combination of measures and tested for significance with a paired t-test. Limits of agreement between 2 measures were determined by the 95% confidence interval of the average difference of the means and illustrated by Bland-Altman plots. Systolic pressure estimated from CW was significantly but only moderately correlated to DU (r = 0.42, p=0.0015) and HDO (r = 0.40, p=0.0021). Pressure estimated from DU was significantly but only moderately correlated to HDO (r = 0.57, p≤0.0001). Limits of agreement were wide for all measures including DU and CW (-61.9to 44.6 mmHg), HDO and CW (-65.2to 26.9 mmHg), and HDO and DU (-63.1 to 42.06 mmHg). Systolic blood pressure estimated by CW cannot be used interchangeably with HDO or DU in dogs with naturally occurring MVD. Copyright © 2016 Elsevier B.V. All rights reserved.

Amino acid repletion does not decrease muscle protein catabolism during hemodialysis.

PubMed

Raj, Dominic S C; Adeniyi, Oladipo; Dominic, Elizabeth A; Boivin, Michel A; McClelland, Sandra; Tzamaloukas, Antonios H; Morgan, Nancy; Gonzales, Lawrence; Wolfe, Robert; Ferrando, Arny

2007-06-01

Intradialytic protein catabolism is attributed to loss of amino acids in the dialysate. We investigated the effect of amino acid infusion during hemodialysis (HD) on muscle protein turnover and amino acid transport kinetics by using stable isotopes of phenylalanine, leucine, and lysine in eight patients with end-stage renal disease (ESRD). Subjects were studied at baseline (pre-HD), 2 h of HD without amino acid infusion (HD-O), and 2 h of HD with amino acid infusion (HD+AA). Amino acid depletion during HD-O augmented the outward transport of amino acids from muscle into the vein. Increased delivery of amino acids to the leg during HD+AA facilitated the transport of amino acids from the artery into the intracellular compartment. Increase in muscle protein breakdown was more than the increase in synthesis during HD-O (46.7 vs. 22.3%, P < 0.001). Net balance (nmol.min(-1).100 ml (-1)) was more negative during HD-O compared with pre-HD (-33.7 +/- 1.5 vs. -6.0 +/- 2.3, P < 0.001). Despite an abundant supply of amino acids, the net balance (-16.9 +/- 1.8) did not switch from net release to net uptake. HD+AA induced a proportional increase in muscle protein synthesis and catabolism. Branched chain amino acid catabolism increased significantly from baseline during HD-O and did not decrease during HD+AA. Protein synthesis efficiency, the fraction of amino acid in the intracellular pool that is utilized for muscle protein synthesis decreased from 42.1% pre-HD to 33.7 and 32.6% during HD-O and HD+AA, respectively (P < 0.01). Thus amino acid repletion during HD increased muscle protein synthesis but did not decrease muscle protein breakdown.

Absorption spectra of deuterated water at DF laser wavelengths.

PubMed

Bruce, C W; Jelinek, A V

1982-11-15

Absorption coefficients for deuterated water have been measured at twenty-two deuterium fluoride (DF) laser wavelengths and presented for atmospheric conditions classified as midlatitude-summer (14.3 T water vapor, standard temperature, and pressure). The HDO vapor was produced from a liquid mixture of H(2)O and D(2)O. The proportions of the resulting equilibrium mixture involving these constituents and HDO were calculated using previously measured constants and produced strong HDO absorption at the 3.5-4.1-microm DF laser wavelengths relative to those of the H(2)O and D(2)O vapors. Predicted and measured pressure dependencies at constant mixing ratios are compared for several laser wavelengths having strong HDO absorption. Absorption coefficients are in fairly close agreement with those of the current Air Force Geophysical Laboratory line-by-line model for standard temperature and pressure conditions. At lower total pressures, the comparison is less satisfactory and suggests inaccurate line parameters in the predictive data base.

Hydrodeoxygenation of heavy oils derived from low-temperature coal gasification over NiW catalysts-effect of pore structure

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

Dieter Leckel

2008-01-15

The effect of the pore structure on the hydroprocessing of heavy distillate oils derived from low-temperature coal gasification residues was studied using four NiW catalysts with different pore size distributions. The hydroprocessing was conducted at a pressure of 17.5 MPa, a temperature range of 370-410{sup o}C, and a 0.50 h{sup -1} space velocity. The degree of hydrodeoxygenation (HDO) in terms of phenolics removal was influenced by the catalyst pore structure, with the most preferable peak pore diameter for HDO ranging between 6.8 and 16 nm. The catalyst with the highest volume of pores in the 3.5-6 nm range showed themore » lowest HDO activity. The apparent activation energies for the HDO reaction varied between 59 and 87 kJ/mol, whereby the lowest values are obtained for the catalysts with a peak pore diameter of 11 and 16 nm. 30 refs., 5 figs., 6 tabs.« less

Stratospheric O3, H2O, and HDO distributions from balloon-based far-infrared observations

NASA Technical Reports Server (NTRS)

Abbas, M. M.; Guo, J.; Carli, B.; Mencaraglia, F.; Bonetti, A.

1987-01-01

Limb thermal emission spectra of the earth's stratosphere in the FIR obtained as part of the Balloon Intercomparison Campaign (BIC), have been analyzed for retrieval of trace constituent distributions. The observations analyzed here were made with a balloon-borne high-resolution Michelson interferometer operating in the 20-100/cm region, with an unapodized spectral resolution of 0.0033/cm. In this paper the vertical profiles of O3, H2O, and HDO retrieved from the observed spectra are presented and compared with the results from other BIC experiments. The retrieved profiles are found to be in good agreement with other measurements. The measurement of the HDO profile provides information about the sources of stratospheric water vapor. The variation of the D/H ratio of water vapor is derived from an analysis of HDO and H2O lines observed in the FIR spectra and is compared with the available measurements in the literature.

Analyses of the wood preservative component N-cyclohexyl-diazeniumdioxide in impregnated pine sapwood by direct thermal desorption-gas chromatography-mass spectrometry.

PubMed

Jüngel, Peter; de Koning, Sjaak; Brinkman, Udo A Th; Melcher, Eckhard

2002-04-12

Investigations concerning the qualitative and quantitative determination of the organic wood preservative component N-cyclohexyl-diazeniumdioxide (HDO) in treated timber were carried out by means of direct thermal desorption-gas chromatography-mass spectrometry (DTD-GC-MS). It could be shown that the identification of HDO in treated pine sapwood (Pinus sylyestris L.) is relatively simple using this analytical technique. Quantification of this active ingredient can be carried out using the peak area of the specific mass fragment m/z 114. A calibration curve with a high correlation coefficient was obtained in the range from 40 to 550 mg HDO per kg timber. Furthermore it can be deduced that the results obtained are characterised by an excellent reproducibility with standard deviations ranging from 5 to 10% in general. For the chosen experimental set up a detection limit of 4 mg HDO per kg treated pine sapwood was calculated, although merely 20% of the active ingredient was desorbed.

First detection of HDO in the atmosphere of Venus at radio wavelengths - An estimate of the H2O vertical distribution

NASA Technical Reports Server (NTRS)

Encrenaz, T.; Lellouch, E.; Paubert, G.; Gulkis, S.

1991-01-01

The 225.9 GHz line of HDO has been detected in absorption in the atmosphere of Venus, with the 30-m IRAM antenna. This measurement gives information regarding the vertical distributions of HDO, and thus H2O, in this planet. The observations are consistent with an H2O vertical distribution strongly depleted by saturation at an altitude of 95 km, and, assuming a D/H enrichment of 120 with respect to the terrestrial value, with a mixing ratio of 3.5 (+ or - 2.0) ppm in the range 65-95 km.

Investigation of chemical modifications of micro- and macromolecules in bio-oil during hydrodeoxygenation with Pd/C catalyst in supercritical ethanol.

PubMed

Oh, Shinyoung; Hwang, Hyewon; Choi, Hang Seok; Choi, Joon Weon

2014-12-01

Miscanthus bio-oil was subjected to hydrodeoxygenation (HDO) with Pd/C at different temperatures (250, 300 and 350°C) and times (30, 45 and 60 min) to investigate the chemical modification of micro- and macromolecules in bio-oil. Four main products - char, gas and two immiscible oils (light and heavy oil) - were obtained from the HDO reaction. Yields of heavy oil as a targeting product of HDO varied from 60% to 13%, whereas those of gas and char were ranged from 7% to 36% and 6% to 17%, respectively. Water content was estimated to<1% and heating value was 26-31 MJ kg(-1). Reduction of unstable oxygen-containing compounds such as acids (2-hydroxy-butanoic acid), aldehydes (furfural), alcohols (butanedial) and sugars (levoglucosan) were characteristic in heavey oil. Apart from hydrogenation and deoxygenation, micromolecules in bio-oil were plausibly modified to stable ketones, esters and saturated components via demethoxylation, dealkylation, decarbonylation, dehydroxylation and ring opening. Macromolecular lignin fragments (referred to as pyrolytic lignins in bio-oil and phenol polymers in heavy oil) were extracted and subjected to several analyses. Approximately 60% of the pyrolytic lignins were decomposed into low molecular weight compounds during HDO reaction. Moreover, essential functional groups, OCH3 and phen-OH groups attached to pyrolytic lignin, were severely modified during HDO reaction. Copyright © 2014 Elsevier Ltd. All rights reserved.

Hydrodeoxygenation by deuterium gas--a powerful way to provide insight into the reaction mechanisms.

PubMed

Ben, Haoxi; Ferguson, Glen A; Mu, Wei; Pu, Yunqiao; Huang, Fang; Jarvis, Mark; Biddy, Mary; Deng, Yulin; Ragauskas, Arthur J

2013-11-28

This study demonstrates the use of isotopic labelling and NMR to study the HDO process. As far as we know, this is the first reported effort to trace the incorporation of hydrogen in the HDO process of lignin pyrolysis oil thereby providing key fundamental insight into its reaction mechanism.

A GREAT search for Deuterium in Comets

NASA Astrophysics Data System (ADS)

Mumma, Michael

2012-10-01

Comets are understood to be the most pristine bodies in the Solar System. Their compositions reflect the chemical state of materials at the very earliest evolutionary stages of the protosolar nebula and, as such, they provide detailed insight into the physical and chemical processes operating in planet-forming disks. Isotopic fractionation ratios of the molecular ices in the nucleus are regarded as signatures of formation processes. These ratios provide unique information on the natal heritage of those ices, and can also test the proposal that Earth's water and other volatiles were delivered by cometary bombardment. Measurement of deuterium fractionation ratios is thus a major goal in contemporary cometary science and the D/H ratio of water - the dominant volatile in comets - holds great promise for testing the formation history of cometary matter. The D/H ratio in cometary water has been measured in only seven comets. Six were from the Oort Cloud reservoir and the D/H ratio was about twice that of the Earth's oceans. However, the recent Herschel measurement of HDO/H2O in 103P/Hartley-2 (the first from the Kuiper Belt) was consistent with exogenous delivery of Earth's water by comets. Outstanding questions remain: are cometary HDO/H2O ratios consistent with current theories of nebular chemical evolution or with an interstellar origin? Does the HDO/H2O ratio vary substantially among comet populations? Hartley-2 is the only Kuiper Belt comet with measured HDO/H2O, are there comets with similar ratios in the Oort cloud? These questions can only be addressed by measuring HDO/H2O ratios in many more suitable bright comets. We therefore propose to measure the D/H ratio in water in a suitable target-of-opportunity comet by performing observations of HDO and OH with the GREAT spectrometer on SOFIA. A multi-wavelength, ground-based observing campaign will also be conducted in support of the airborne observations.

A GREAT search for Deuterium in Comets

NASA Astrophysics Data System (ADS)

Mumma, Michael

2013-10-01

Comets are understood to be the most pristine bodies in the Solar System. Their compositions reflect the chemical state of materials at the very earliest evolutionary stages of the protosolar nebula and, as such, they provide detailed insight into the physical and chemical processes operating in planet-forming disks. Isotopic fractionation ratios of the molecular ices in the nucleus are regarded as signatures of formation processes. These ratios provide unique information on the natal heritage of those ices, and can also test the proposal that Earth's water and other volatiles were delivered by cometary bombardment. Measurement of deuterium fractionation ratios is thus a major goal in contemporary cometary science and the D/H ratio of water - the dominant volatile in comets - holds great promise for testing the formation history of cometary matter. The D/H ratio in cometary water has been measured in only eight comets. Seven were from the Oort Cloud reservoir and the D/H ratio was about twice that of the Earth's oceans. However, the recent Herschel measurement of HDO/H2O in 103P/Hartley-2 (the first from the Kuiper Belt) was consistent with exogenous delivery of Earth's water by comets. Outstanding questions remain: are cometary HDO/H2O ratios consistent with current theories of nebular chemical evolution or with an interstellar origin? Does the HDO/H2O ratio vary substantially among comet populations? Hartley-2 is the only Kuiper Belt comet with measured HDO/H2O, are there comets with similar ratios in the Oort cloud? These questions can only be addressed by measuring HDO/H2O ratios in many more suitable bright comets. We therefore propose to measure the D/H ratio in water in a suitable target-of-opportunity comet by performing observations of HDO and OH with the GREAT spectrometer on SOFIA. A multi-wavelength, ground-based observing campaign will also be conducted in support of the airborne observations.

Water deuterium fractionation in the low-mass protostar NGC1333-IRAS2A

NASA Astrophysics Data System (ADS)

Liu, F.-C.; Parise, B.; Kristensen, L.; Visser, R.; van Dishoeck, E. F.; Güsten, R.

2011-03-01

Context. Although deuterium enrichment of water may provide an essential piece of information in the understanding of the formation of comets and protoplanetary systems, only a few studies up to now have aimed at deriving the HDO/H2O ratio in low-mass star forming regions. Previous studies of the molecular deuteration toward the solar-type class 0 protostar, IRAS 16293-2422, have shown that the D/H ratio of water is significantly lower than other grain-surface-formed molecules. It is not clear if this property is general or particular to this source. Aims: In order to see if the results toward IRAS 16293-2422 are particular, we aimed at studying water deuterium fractionation in a second low-mass solar-type protostar, NGC1333-IRAS2A. Methods: Using the 1-D radiative transfer code RATRAN, we analyzed five HDO transitions observed with the IRAM 30 m, JCMT, and APEX telescopes. We assumed that the abundance profile of HDO in the envelope is a step function, with two different values in the inner warm (T > 100 K) and outer cold (T < 100 K) regions of the protostellar envelope. Results: The inner and outer abundance of HDO is found to be well constrained at the 3σ level. The obtained HDO inner and outer fractional abundances are xHDO_in = 6.6 × 10-8-1.0 × 10-7(3σ) and x^{HDO}out=9×10-11= 9 × 10-11-1.0-1.8 × 10-9(3σ). These values are close to those in IRAS 16293-2422, which suggests that HDO may be formed by the same mechanisms in these two solar-type protostars. Taking into account the (rather poorly onstrained) H2O abundance profile deduced from Herschel observations, the derived HDO/H2O in the inner envelope is ≥1% and in the outer envelope it is 0.9%-18%. These values are more than one order of magnitude higher than what is measured in comets. If the same ratios apply to the protosolar nebula, this would imply that there is some efficient reprocessing of the material between the protostellar and cometary phases. Conclusions: The H2O inner fractional abundance could be further constrained by an analysis of newer observations of high-energy H_218O lines. These new observations would be required to understand water fractionation in more detail. Based on observations with the APEX telescope, the IRAM 30 m telescope and with the James Clerk Maxwell Telescope (JCMT). APEX is a collaboration between the Max-Planck-Institut für Radioastronomie, the European Southern Observatory, and the Onsala Space Observatory. IRAM is a European collaboration between the CNRS (Centre National de la Recherche Scientifique), the MPG (Max-Planck-Gesellschaft) and the Spanish IGN (Instituto Geográfico Nacional). The JCMT is operated by The Joint Astronomy Centre on behalf of the Particle Physics and Astronomy Research Council of the United Kingdom, the Netherlands Organization of Scientific Research, and the National Research Council of Canada.

Using polyfurfuryl alcohol to improve the hydrothermal stability of mesoporous oxides for reactions in the aqueous phase

USDA-ARS?s Scientific Manuscript database

Hydrodeoxygenation (HDO) of bio-oils derived from the pyrolysis of woody biomass is required to improve the stability and heating value of the liquid hydrocarbon products. Since pyrolysis produces bio-oils having up to 30 vol% water, HDO catalysts must not only be active and selective, but also sta...

Alkanes from Bioderived Furans by using Metal Triflates and Palladium-Catalyzed Hydrodeoxygenation of Cyclic Ethers.

PubMed

Song, Hai-Jie; Deng, Jin; Cui, Min-Shu; Li, Xing-Long; Liu, Xin-Xin; Zhu, Rui; Wu, Wei-Peng; Fu, Yao

2015-12-21

Using a metal triflate and Pd/C as catalysts, alkanes were prepared from bioderived furans in a one-pot hydrodeoxygenation (HDO) process. During the reaction, the metal triflate plays a crucial role in the ring-opening HDO of furan compounds. The entire reaction process has goes through two major phases: at low temperatures, saturation of the exocyclic double bond and furan ring are catalyzed by Pd/C; at high temperatures, the HDO of saturated furan compounds is catalyzed by the metal triflate. The reaction mechanism was verified by analyzing the changes of the intermediates during the reaction. In addition, different metal triflates, solvents, and catalyst recycling were also investigated. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Elucidation of reaction mechanism for m -cresol hydrodeoxygenation over Fe based catalysts: A kinetic study

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

Hong, Yongchun; Wang, Yong

Fe based catalysts are promising for hydrodeoxygenation (HDO) of lignin derived phenolics due to their high selectivity for aromatics. In this work, the reaction mechanism of m-cresol HDO on Fe catalysts and the kinetic consequence with Pd addition were elucidated by examining the effect of H2, H2O and m-cresol pressures on toluene formation rate on Fe and PdFe catalysts. A direct CO bond cleavage mechanism is proposed for HDO catalysis on both Fe and PdFe catalysts, while Pd provides a facilitated reaction pathway at the PdFe interface and therefore promotes the catalysis on Fe without changing the high selectivity towardsmore » aromatics.« less

Gradual collapse of nuclear wave functions regulated by frequency tuned X-ray scattering.

PubMed

Ignatova, Nina; Cruz, Vinícius V; Couto, Rafael C; Ertan, Emelie; Zimin, Andrey; Guimarães, Freddy F; Polyutov, Sergey; Ågren, Hans; Kimberg, Victor; Odelius, Michael; Gel'mukhanov, Faris

2017-03-07

As is well established, the symmetry breaking by isotope substitution in the water molecule results in localisation of the vibrations along one of the two bonds in the ground state. In this study we find that this localisation may be broken in excited electronic states. Contrary to the ground state, the stretching vibrations of HDO are delocalised in the bound core-excited state in spite of the mass difference between hydrogen and deuterium. The reason for this effect can be traced to the narrow "canyon-like" shape of the potential of the state along the symmetric stretching mode, which dominates over the localisation mass-difference effect. In contrast, the localisation of nuclear motion to one of the HDO bonds is preserved in the dissociative core-excited state . The dynamics of the delocalisation of nuclear motion in these core-excited states is studied using resonant inelastic X-ray scattering of the vibrationally excited HDO molecule. The results shed light on the process of a wave function collapse. After core-excitation into the state of HDO the initial wave packet collapses gradually, rather than instantaneously, to a single vibrational eigenstate.

Regular in situ measurements of HDO/H216O in the northern and southern hemispherical upper troposphere reveal tropospheric transport processes.

NASA Astrophysics Data System (ADS)

Christner, Emanuel; Dyroff, Christoph; Sanati, Shahrokh; Brenninkmeijer, Carl; Zahn, Andreas

2013-04-01

Atmospheric water in form of water vapor and clouds is an enormously crucial trace species. It is responsible for ~70 % of the natural greenhouse effect (Schmidt et al., JGR, 2010), carries huge amounts of latent heat, and is the major source of OH in the troposphere. The isotopic composition of water vapor is an elegant tracer for a better understanding and quantification of the extremely complex and variable hydrological cycle in Earth's atmosphere (evaporation, cloud condensation, rainout, re-evaporation, snow), which in turn is a prerequisite to improve climate modeling and predictions. In this context, water-isotopologues (here the isotope ratio HDO/H216O) can be used to study the atmospheric transport of water and in-cloud processes. As H216O and HDO differ in vapor pressure and molecular diffusion, fractionation occurs during condensation and rainout events. For that reason the ratio HDO/H216O preserves information about the transport and condensation history of an air mass. The tunable diode-laser absorption spectrometer ISOWAT was developed for airborne measurements of the water-isotopologue concentrations of H216O and HDO, probing fundamental rovibrational water-absorption lines at around 2.66 μm. Since April 2010 the spectrometer is regularly operated aboard the CARIBIC passenger aircraft (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container - Lufthansa, Airbus 340-600), which measures ~100 trace gases and aerosol components in the UTLS (9-12 km altitude) on four long-distance flights per month. During several flights across the equator (Africa) or close to the equator (Venezuela and Malaysia) an increase of HDO/H216O from the subtropics towards the tropics was measured (by more than 100 permil) at an altitude of ~12 km. This isotopic gradient can partly be attributed to differences in humidity. In addition there is a humidity independent latitudinal gradient (by more than 50 permil), revealing the strong influence of convection on the isotopic composition of water in the upper troposphere. This finding is consistent with the well-known regions of deep convection over Africa, Malaysia and South America.

Ion aggregation in high salt solutions. III. Computational vibrational spectroscopy of HDO in aqueous salt solutions

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

Choi, Jun-Ho; Lim, Sohee; Chon, Bonghwan

The vibrational frequency, frequency fluctuation dynamics, and transition dipole moment of the O—D stretch mode of HDO molecule in aqueous solutions are strongly dependent on its local electrostatic environment and hydrogen-bond network structure. Therefore, the time-resolved vibrational spectroscopy the O—D stretch mode has been particularly used to investigate specific ion effects on water structure. Despite prolonged efforts to understand the interplay of O—D vibrational dynamics with local water hydrogen-bond network and ion aggregate structures in high salt solutions, still there exists a gap between theory and experiment due to a lack of quantitative model for accurately describing O—D stretch frequencymore » in high salt solutions. To fill this gap, we have performed numerical simulations of Raman scattering and IR absorption spectra of the O—D stretch mode of HDO in highly concentrated NaCl and KSCN solutions and compared them with experimental results. Carrying out extensive quantum chemistry calculations on not only water clusters but also ion-water clusters, we first developed a distributed vibrational solvatochromic charge model for the O—D stretch mode in aqueous salt solutions. Furthermore, the non-Condon effect on the vibrational transition dipole moment of the O—D stretch mode was fully taken into consideration with the charge response kernel that is non-local polarizability density. From the fluctuating O—D stretch mode frequencies and transition dipole vectors obtained from the molecular dynamics simulations, the O—D stretch Raman scattering and IR absorption spectra of HDO in salt solutions could be calculated. The polarization effect on the transition dipole vector of the O—D stretch mode is shown to be important and the asymmetric line shapes of the O—D stretch Raman scattering and IR absorption spectra of HDO especially in highly concentrated NaCl and KSCN solutions are in quantitative agreement with experimental results. We anticipate that this computational approach will be of critical use in interpreting linear and nonlinear vibrational spectroscopies of HDO molecule that is considered as an excellent local probe for monitoring local electrostatic and hydrogen-bonding environment in not just salt but also other confined and crowded solutions.« less

Stratospheric Observations of CH3D and HDO from ATMOS Infrared Solar Spectra: Enrichments of Deuterium in Methane and Implications for HD

NASA Technical Reports Server (NTRS)

Irion, F. W.; Moyer, E. J.; Gunson, M. R.; Rinsland, C. P.; Yung, Y. L.; Michelsen, H. A.; Salawitch, R. J.; Chang, A. Y.; Newchurch, M. J.; Abbas, M. M.;

Ground-based Detection of Deuterated Water in Comet C/2014 Q2 (Lovejoy) at IR Wavelengths

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

Paganini, L.; Mumma, M. J.; Villanueva, G. L.

2017-02-20

We conducted a deep search for deuterated water (HDO) in the Oort Cloud comet C/2014 Q2 (Lovejoy), through infrared (IR) spectroscopy with NIRSPEC at the Keck Observatory. In this Letter, we present our detections of HDO and water (H{sub 2}O) in comet Lovejoy on 2015 February 4 (post-perihelion) after 1 hr integration on source. The IR observations allowed simultaneous detection of H{sub 2}O and HDO, yielding production rates of 5.9 ± 0.13 × 10{sup 29} and 3.6 ± 1.0 × 10{sup 26} molecules s{sup −1}, respectively. The simultaneous detection permitted accurate determination of the isotopic ratio (D/H) in water ofmore » 3.02 ± 0.87 × 10{sup −4}, i.e., larger than the value for water in terrestrial oceans (or Vienna Standard Mean Ocean Water, VSMOW) by a factor of 1.94 ± 0.56. This D/H ratio in water exceeds the value obtained independently at millimeter wavelengths (0.89 ± 0.25 VSMOW; pre-perihelion). We discuss these parameters in the context of origins and emphasize the need for contemporaneous measurements of HDO and H{sub 2}O.« less

CW EC-QCL-based sensor for simultaneous detection of H 2O, HDO, N 2O and CH 4 using multi-pass absorption spectroscopy

DOE PAGES

Yu, Yajun; Sanchez, Nancy P.; Griffin, Robert J.; ...

2016-05-03

A sensor system based on a continuous wave, external-cavity quantum-cascade laser (CW EC-QCL) was demonstrated for simultaneous detection of atmospheric H 2O, HDO, N 2O and CH 4 using a compact, dense pattern multi-pass gas cell with an effective path-length of 57.6 m. The EC-QCL with a mode-hop-free spectral range of 1225-1285 cm -1 operating at similar to 7.8 mu m was scanned covering four neighboring absorption lines, for H 2O at 1281.161 cm -1, HDO at 1281.455 cm -1, N 2O at 1281.53 cm -1 and CH 4 at 1281.61 cm -1. A first-harmonic-normalized wavelength modulation spectroscopy with second-harmonicmore » detection (WMS-2f/1f) strategy was employed for data processing. An Allan-Werle deviation analysis indicated that minimum detection limits of 1.77 ppmv for H 2O, 3.92 ppbv for HDO, 1.43 ppbv for N 2O, and 2.2 ppbv for CH 4 were achieved with integration times of 50-s, 50-s, 100-s and 129-s, respectively. In conclusion, experimental measurements of ambient air are also reported.« less

On the Utility (or Futility) of Using Stable Water Isotopes to Constrain the Bulk Properties of Tropical Convection

NASA Astrophysics Data System (ADS)

Duan, Suqin Q.; Wright, Jonathon S.; Romps, David M.

2018-02-01

Atmospheric water-vapor isotopes have been proposed as a potentially powerful constraint on convection, which plays a critical role in Earth's present and future climate. It is shown here, however, that the mean tropical profile of HDO in the free troposphere does not usefully constrain the mean convective entrainment rate or precipitation efficiency. This is demonstrated using a single-column analytical model of atmospheric water isotopes. The model has three parameters: the entrainment rate, the precipitation efficiency, and the distance that evaporating condensates fall. At a given relative humidity, the possible range of HDO is small: its range is comparable to both the measurement uncertainty in the mean tropical profile and the structural uncertainty of a single-column model. Therefore, the mean tropical HDO profile is unlikely to add information about convective processes in a bulk-plume framework that cannot already be learned from relative humidity alone.

Role of Deep Convection in Establishing the Isotopic Composition of Water Vapor in the Tropical Transition Layer

NASA Technical Reports Server (NTRS)

Smith, Jamison A.; Ackerman, Andrew S.; Jensen, Eric J.; Toon, Owen B.

2006-01-01

The transport of H2O and HDO within deep convection is investigated with 3-D large eddy simulations (LES) using bin microphysics. The lofting and sublimation of HDO-rich ice invalidate the Rayleigh fractionation model of isotopologue distribution within deep convection. Bootstrapping the correlation of the ratio of HDO to H2O (deltaD) to water vapor mixing ratio (q(sub v)) through a sequence of convective events produced non-Rayleigh correlations resembling observations. These results support two mechanisms for stratospheric entry. Deep convection can inject air with water vapor of stratospheric character directly into the tropical transition layer (TTL). Alternatively, moister air detraining from convection may be dehydrated via cirrus formation n the TTL to produce stratospheric water vapor. Significant production of subsaturated air in the TTL via convective dehydration is not observed in these simulations, nor is it necessary to resolve the stratospheric isotope paradox.

Hydrodeoxygenation of lignin-derived phenolic compounds to hydrocarbons over Ni/SiO2-ZrO2 catalysts.

PubMed

Zhang, Xinghua; Zhang, Qi; Wang, Tiejun; Ma, Longlong; Yu, Yuxiao; Chen, Lungang

2013-04-01

Inexpensive non-sulfided Ni-based catalysts were evaluated for hydrodeoxygenation (HDO) using guaiacol as model compound. SiO2-ZrO2 (SZ), a complex oxide synthesized by precipitation method with different ratio of Si/Zr, was impregnated with Ni(NO3)2·6H2O and calcined at 500°C. Conversion rates and product distribution for guaiacol HDO at 200-340°C were determined. Guaiacol conversion reached the maximum at 300°C in the presence of Ni/SZ-3. When HDO reaction was carried out with real lignin-derived phenolic compounds under the optimal conditions determined for guaiacol, the total yield of hydrocarbons was 62.81%. These hydrocarbons were comprised of cyclohexane, alkyl-substituted cyclohexane and alkyl-substituted benzene. They have high octane number, would be the most desirable components for fungible liquid transportation fuel. Copyright © 2013 Elsevier Ltd. All rights reserved.

Evaluation of 10 Jet Fuels in the Salmonella-Escherichia coli Mutagenicity Assay

DTIC Science & Technology

2016-09-07

4658), Valero 25% Aromatic JP8 (POSF 8457), KiOR Hydrotreated Kerosene/ Bio -Kerosene (POSF 10327), ARA ReadiJet (POSF 10328), Amyris Farnesane (POSF...JP8 (POSF 8457) * KiOR Hydrotreated Kerosene/ Bio -Kerosene (POSF 10327) * ARA ReadiJet (POSF 10328) * Amyris Farnesane (POSF 10329) * Virent HDO-SK...fuel/plate. Due to evidence of toxicity, KiOR Hydrotreated Kerosene/ Bio -Kerosene (POSF 10327) and Virent HDO-SK (POSF 10330) were used at

Understanding the Role of M/Pt(111) (M = Fe, Co, Ni, Cu) Bimetallic Surfaces for Selective Hydrodeoxygenation of Furfural

DOE PAGES

Jiang, Zhifeng; Wan, Weiming; Lin, Zhexi; ...

2017-07-24

Selectively cleaving the C=O bond of the aldehyde group in furfural is critical for converting this biomass-derived platform chemical to an important biofuel molecule, 2-methylfuran. This work combined density functional theory (DFT) calculations and temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) measurements to investigate the hydrodeoxygenation (HDO) activity of furfural on bimetallic surfaces prepared by modifying Pt(111) with 3d transition metals (Cu, Ni, Fe, and Co). The stronger binding energy of furfural and higher tilted degree of the furan ring on the Co-terminated bimetallic surface resulted in a higher activity for furfural HDO to produce 2-methylfuran inmore » comparison to that on either Pt(111) or Pt-terminated PtCoPt(111). The 3d-terminated bimetallic surfaces with strongly oxophilic 3d metals (Co and Fe) showed higher 2-methylfuran yield in comparison to those surfaces modified with weakly oxophilic 3d metals (Cu and Ni). The effect of oxygen on the HDO selectivity was also investigated on oxygen-modified bimetallic surfaces, revealing that the presence of surface oxygen resulted in a decrease in 2-methylfuran yield. Furthermore, the combined theoretical and experimental results presented here should provide useful guidance for designing Pt-based bimetallic HDO catalysts.« less

Airborne Measurements of Venus Cloud-top H2O and HDO from NASA’s SOFIA in the Mid-Infrared

NASA Astrophysics Data System (ADS)

Tsang, Constantine; Encrenaz, Therese; DeWitt, Curtis N.; Richter, Matthew; Irwin, Patrick

2017-10-01

The determination of the D/H ratio in Venus’s atmosphere using water (H2O) and light water (HDO) has been used as evidence for the loss of a global sized ocean in the distant past on paleo-Venus. Measurements of atmospheric water vapour at and above the cloud level is also important as water is a key ingredient in the production of the hydrated H2SO4 clouds that prevail globally on Venus. While variations in latitude and local solar time of H2O at the cloud tops has been most recently measured by ESA’s Venus Express spacecraft, the data is sporadic due to the limb sounding geometry needed to make these measurements.Here we present H2O and HDO measurements from January 2017 from NASA’s Stratospheric Observatory for Infrared Astronomy (SOFIA) using the EXES mid-infrared spectrometer flying at 40,000 ft where the relatively low telluric absorption makes detection of Venusian H2O possible. Two observation sequences were obtained that yielded spatially resolved maps of H2O and HDO at R~89,000 centered at 7.21 µm (1380 cm-1). We will also discuss the preliminary retrieved values of D/H ratios at the 65 km altitude probed at this wavelength.

Combination of haloperidol, dexamethasone, and ondansetron reduces nausea and pain intensity and morphine consumption after laparoscopic sleeve gastrectomy.

PubMed

Benevides, Márcio Luiz; Oliveira, Sérgio de Souza; Aguilar-Nascimento, José Eduardo

2013-01-01

Postoperative nausea and vomiting (PONV) occur frequently after laparoscopic bariatric surgery. The combination of haloperidol, dexamethasone, and ondansetron may reduce these undesirable events. The aim of this study was to evaluate the intensity of nausea and pain, the number of vomiting episodes, and morphine consumption in postoperative (PO) obese patients undergoing laparoscopic sleeve gastrectomy (LSG). A clinical, randomized, controlled, double-blind study conducted with 90 patients with body mass index ≥ 35 kg.cm-2. Patients were divided into three groups of 30 individuals to receive ondansetron 8 mg (Group O); ondansetron 8 mg and dexamethasone 8 mg (Group OD); and ondansetron 8 mg, dexamethasone 8 mg, and haloperidol 2 mg (Group HDO). We evaluated the intensity of nausea and pain using the verbal numeric scale, cumulative number of vomiting episodes, and morphine consumption in the period of 0-2, 2-12, 12-24, and 24-36 hours postoperatively. Nausea intensity was lower in Group HDO compared to Group O (p = 0.001), pain intensity was lower in Group HDO compared to Group O (p = 0.046), and morphine consumption was lower in Group HDO compared to Group O (p = 0.037). There was no difference between groups regarding the number of vomiting episodes (p = 0.052). The combination of haloperidol, ondansetron, and dexamethasone reduced nausea and pain intensity and morphine consumption in postoperative obese patients undergoing LSG.

Understanding the Role of M/Pt(111) (M = Fe, Co, Ni, Cu) Bimetallic Surfaces for Selective Hydrodeoxygenation of Furfural

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

Jiang, Zhifeng; Wan, Weiming; Lin, Zhexi

Selectively cleaving the C=O bond of the aldehyde group in furfural is critical for converting this biomass-derived platform chemical to an important biofuel molecule, 2-methylfuran. This work combined density functional theory (DFT) calculations and temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) measurements to investigate the hydrodeoxygenation (HDO) activity of furfural on bimetallic surfaces prepared by modifying Pt(111) with 3d transition metals (Cu, Ni, Fe, and Co). The stronger binding energy of furfural and higher tilted degree of the furan ring on the Co-terminated bimetallic surface resulted in a higher activity for furfural HDO to produce 2-methylfuran inmore » comparison to that on either Pt(111) or Pt-terminated PtCoPt(111). The 3d-terminated bimetallic surfaces with strongly oxophilic 3d metals (Co and Fe) showed higher 2-methylfuran yield in comparison to those surfaces modified with weakly oxophilic 3d metals (Cu and Ni). The effect of oxygen on the HDO selectivity was also investigated on oxygen-modified bimetallic surfaces, revealing that the presence of surface oxygen resulted in a decrease in 2-methylfuran yield. Furthermore, the combined theoretical and experimental results presented here should provide useful guidance for designing Pt-based bimetallic HDO catalysts.« less

Experimental and Ab Initio Studies of the HDO Absorption Spectrum in the 13165-13500 1/cm Spectral Region

NASA Technical Reports Server (NTRS)

Schwenke, David; Naumenko, Olga; Bertseva, Elena; Campargue, Alain; Arnold, James O. (Technical Monitor)

2000-01-01

The HDO absorption spectrum has been recorded in the 13165 - 13500 cm(exp-1) spectral region by Intracavity Laser Absorption Spectroscopy. The spectrum (615 lines), dominated by the 2n2 + 3n3 and n1+3n3 bands was assigned and modeled leading to the derivation of 196 accurate energy levels of the (103) and (023) vibrational states. Finally, 150 of these levels have been reproduced by an effective Hamiltonian involving two vibrational dark states interacting with the (023) and ( 103) bright states. The rms deviation achieved by variation of 28 parameters is 0.05-1 cm, compared to an averaged experimental uncertainty of 0.007-1 cm, indicating the limit of validity of the effective Hamiltonian approach for HDO at high vibrational excitation. The predictions of previous ab initio calculations of the HDO spectrum were extensively used in the assignment process. The particular spectral region under consideration has been used to test and discuss the improvements of new ab initio calculations recently performed on the basis of the same potential energy surface but with an improved dipole moment surface. The improvements concern both the energy levels and the line intensities. In particular, the strong hybrid character of the n1+3n3 band is very well accounted for by the the new ab initio calculations.

Detection of OD towards the low-mass protostar IRAS 16293-2422

NASA Astrophysics Data System (ADS)

Parise, B.; Du, F.; Liu, F.-C.; Belloche, A.; Wiesemeyer, H.; Güsten, R.; Menten, K. M.; Hübers, H.-W.; Klein, B.

2012-06-01

Context. Although water is an essential and widespread molecule in star-forming regions, its chemical formation pathways are still not very well constrained. Observing the level of deuterium fractionation of OH, a radical involved in the water chemical network, is a promising way to infer its chemical origin. Aims: We aim at understanding the formation mechanisms of water by investigating the origin of its deuterium fractionation. This can be achieved by observing the abundance of OD towards the low-mass protostar IRAS 16293-2422, where the HDO distribution is already known. Methods: Using the GREAT receiver on board SOFIA, we observed the ground-state OD transition at 1391.5 GHz towards the low-mass protostar IRAS 16293-2422. We also present the detection of the HDO 111-000 line using the APEX telescope. We compare the OD/HDO abundance ratio inferred from these observations with the predictions of chemical models. Results: The OD line is detected in absorption towards the source continuum. This is the first detection of OD outside the solar system. The SOFIA observation, coupled to the observation of the HDO 111-000 line, provides an estimate of the abundance ratio OD/HDO ~ 17-90 in the gas where the absorption takes place. This value is fairly high compared with model predictions. This may be reconciled if reprocessing in the gas by means of the dissociative recombination of H2DO+ further fractionates OH with respect to water. Conclusions: The present observation demonstrates the capability of the SOFIA/GREAT instrument to detect the ground transition of OD towards star-forming regions in a frequency range that was not accessible before. Dissociative recombination of H2DO+ may play an important role in setting a high OD abundance. Measuring the branching ratios of this reaction in the laboratory will be of great value for chemical models. Figure 5 is available in electronic form at http://www.aanda.org

Self- and CO2-broadened line shape parameters for infrared bands of HDO

NASA Astrophysics Data System (ADS)

Smith, Mary-Ann H.; Malathy Devi, V.; Benner, D. Chris; Sung, Keeyoon; Mantz, Arlan W.; Gamache, Robert R.; Villanueva, Geronimo L.

2015-11-01

Knowledge of CO2-broadened HDO line widths and their temperature dependence is required to interpret infrared spectra of the atmospheres of Mars and Venus. However, this information is currently absent in most spectroscopic databases. We have analyzed nine high-resolution, high signal-to-noise spectra of HDO and HDO+CO2 mixtures to obtain broadening coefficients and other line shape parameters for transitions of the ν2 and ν3 vibrational bands located at 7.13 and 2.70 μm, respectively. The gas samples were prepared by mixing equal amounts of high-purity distilled H2O and 99% enriched D2O. The spectra were recorded at different temperatures (255-296 K) using a 20.38 cm long coolable cell [1] installed in the sample compartment of the Bruker IFS125HR Fourier transform spectrometer at the Jet Propulsion Laboratory in Pasadena, CA. The retrieved HDO spectroscopic parameters include line positions, intensities, self- and CO2-broadened half-width and pressure-induced shift coefficients and the temperature dependences for CO2 broadening. These spectroscopic parameters were obtained by simultaneous multispectrum fitting [2] of the same interval in all nine spectra. A non-Voigt line shape with speed dependence was applied. Line mixing was also observed for several transition pairs. Preliminary results compare well with the few other measurements reported in the literature.[1] K. Sung et al., J. Mol. Spectrosc. 162, 124-134 (2010).[2] D. C. Benner et al., J. Quant. Spectrosc. Radiat Transfer 53, 705-721 (1995).The research performed at the College of William and Mary was supported by NASA’s Mars Fundamental Research Program (Grant NNX13AG66G). The research at Jet Propulsion Laboratory, California Institute of Technology, Connecticut College, Langley Research Center, and Goddard Space Flight Center was conducted under contracts and cooperative agreements with the National Aeronautics and Space Administration. RRG is pleased to acknowledge support of this study by the National Science Foundation through Grant No. AGS-1156862.

Mechanistic Investigation of Molybdate-Catalysed Transfer Hydrodeoxygenation.

PubMed

Larsen, Daniel B; Petersen, Allan R; Dethlefsen, Johannes R; Teshome, Ayele; Fristrup, Peter

2016-11-07

The molybdate-catalysed transfer hydrodeoxygenation (HDO) of benzyl alcohol to toluene driven by oxidation of the solvent isopropyl alcohol to acetone has been investigated by using a combination of experimental and computational methods. A Hammett study that compared the relative rates for the transfer HDO of five para-substituted benzylic alcohols was carried out. Density-functional theory (DFT) calculations suggest a transition state with significant loss of aromaticity contributes to the lack of linearity observed in the Hammett study. The transfer HDO could also be carried out in neat PhCH 2 OH at 175 °C. Under these conditions, PhCH 2 OH underwent disproportionation to yield benzaldehyde, toluene, and significant amounts of bibenzyl. Isotopic-labelling experiments (using PhCH 2 OD and PhCD 2 OH) showed that incorporation of deuterium into the resultant toluene originated from the α position of benzyl alcohol, which is in line with the mechanism suggested by the DFT study. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

First In-situ Measurements of the HDO/H2O Isotopic Ratio in the Asian Summer Monsoon

NASA Astrophysics Data System (ADS)

Clouser, B.; Sarkozy, L.; Gaeta, D. C.; Singer, C. E.; Moyer, E. J.

2017-12-01

The Asian monsoon is one of the world's largest weather systems, and forms one of the main pathways by which water vapor enters the UT/LS. Satellite measurements of the HDO/H2O ratio of UT/LS water, a strong tracer of convective origin, have suggested significant differences in transport behavior between the Asian and North American monsoons, with strong UT/LS enhancement occurring only over North America. We report here the first in-situ measurements of the HDO/H2O ratio in the Asian monsoon, that help resolve this discrepancy. The Chicago Water Isotope Spectrometer (Chi-WIS) participated in the July/August 2017 StratoClim campaign, measuring water vapor and its isotopic composition between 12 and 20 kilometers. We use these measurements to diagnose the importance of overshooting convection in water transport by the Asian monsoon, and to characterize the extent to which convection-driven water vapor perturbations propagate to higher altitudes and contribute to the overall stratospheric water budget.

CW EC-QCL-based sensor for simultaneous detection of H₂O, HDO, N₂O and CH₄ using multi-pass absorption spectroscopy.

PubMed

Yu, Yajun; Sanchez, Nancy P; Griffin, Robert J; Tittel, Frank K

2016-05-16

A sensor system based on a continuous wave, external-cavity quantum-cascade laser (CW EC-QCL) was demonstrated for simultaneous detection of atmospheric H₂O, HDO, N₂O and CH₄ using a compact, dense pattern multi-pass gas cell with an effective path-length of 57.6 m. The EC-QCL with a mode-hop-free spectral range of 1225-1285 cm^-1 operating at ~7.8 µm was scanned covering four neighboring absorption lines, for H₂O at 1281.161 cm^-1, HDO at 1281.455 cm^-1, N₂O at 1281.53 cm^-1 and CH₄ at 1281.61 cm^-1. A first-harmonic-normalized wavelength modulation spectroscopy with second-harmonic detection (WMS-2f/1f) strategy was employed for data processing. An Allan-Werle deviation analysis indicated that minimum detection limits of 1.77 ppmv for H₂O, 3.92 ppbv for HDO, 1.43 ppbv for N₂O, and 2.2 ppbv for CH₄ were achieved with integration times of 50-s, 50-s, 100-s and 129-s, respectively. Experimental measurements of ambient air are also reported.

Selective hydrodeoxygenation of biomass-derived oxygenates to unsaturated hydrocarbons using molybdenum carbide catalysts.

PubMed

Ren, Hui; Yu, Weiting; Salciccioli, Michael; Chen, Ying; Huang, Yulin; Xiong, Ke; Vlachos, Dionisios G; Chen, Jingguang G

2013-05-01

Which cleavage do you prefer? With a combination of density functional theory (DFT) calculations, surface science studies, and reactor evaluations, Mo(2)C is identified as a highly selective HDO catalyst to selectively convert biomass-derived oxygenates to unsaturated hydrocarbons through selective C-O bond scissions without C-C bond cleavage. This provides high-value HDO products for utilization as feedstocks for chemicals and fuels; this also reduces the overall consumption of H2 . Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Seasonal, synoptic and diurnal variation of atmospheric water-isotopologues in the boundary layer of Southwestern Germany caused by plant transpiration, cold-front passages and dewfall.

NASA Astrophysics Data System (ADS)

Christner, Emanuel; Dyroff, Christoph; Kohler, Martin; Zahn, Andreas; Gonzales, Yenny; Schneider, Matthias

2013-04-01

Atmospheric water is an enormously crucial trace gas. It is responsible for ~70 % of the natural greenhouse effect (Schmidt et al., JGR, 2010) and carries huge amounts of latent heat. The isotopic composition of water vapor is an elegant tracer for a better understanding and quantification of the extremely complex and variable hydrological cycle in Earth's atmosphere (evaporation, cloud condensation, rainout, re-evaporation, snow), which in turn is a prerequisite to improve climate modeling and predictions. As H216O, H218O and HDO differ in vapor pressure and mass, isotope fractionation occurs due to condensation, evaporation and diffusion processes. In contrast to that, plants are able to transpire water with almost no isotope fractionation. For that reason the ratio of isotopologue concentrations in the boundary layer (BL) provides, compared to humidity measurements alone, independent and additional constraints for quantifying the strength of evaporation and transpiration. Furthermore the isotope ratios contain information about transport history of an air mass and microphysical processes, that is not accessible by humidity measurements. Within the project MUSICA (MUlti-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water) a commercial Picarro Analyzer L2120-i is operated at Karlsruhe in Southwestern Germany, which is continuously measuring the isotopologues H216O, HDO and H218O of atmospheric water vapor since January 2012. A one year record of H216O, HDO and H218O shows clear seasonal, synoptic and diurnal characteristics and reveals the main driving processes affecting the isotopic composition of water vapor in the Middle European BL. Changes in continental plant transpiration and evaporation throughout the year lead to a slow seasonal HDO/H216O-variation, that cannot be explained by pure Rayleigh condensation. Furthermore, cold-front passages from NW lead to fast and pronounced depletion of the HDO/H216O-ratio within minutes. Superimposed to these variations are local diurnal processes like dewfall, which cause a diurnal pattern captured by the deuterium excess.

Nitrogen-Doped Ordered Mesoporous Carbon Supported Bimetallic PtCo Nanoparticles for Upgrading of Biophenolics.

PubMed

Wang, Guang-Hui; Cao, Zhengwen; Gu, Dong; Pfänder, Norbert; Swertz, Ann-Christin; Spliethoff, Bernd; Bongard, Hans-Josef; Weidenthaler, Claudia; Schmidt, Wolfgang; Rinaldi, Roberto; Schüth, Ferdi

2016-07-25

Hydrodeoxygenation (HDO) is an attractive route for the upgrading of bio-oils produced from lignocellulose. Current catalysts require harsh conditions to effect HDO, decreasing the process efficiency in terms of energy and carbon balance. Herein we report a novel and facile method for synthesizing bimetallic PtCo nanoparticle catalysts (ca. 1.5 nm) highly dispersed in the framework of nitrogen-doped ordered mesoporous carbon (NOMC) for this reaction. We demonstrate that NOMC with either 2D hexagonal (p6m) or 3D cubic (Im3‾ m) structure can be easily synthesized by simply adjusting the polymerization temperature. We also demonstrate that PtCo/NOMC (metal loading: Pt 9.90 wt %; Co 3.31 wt %) is a highly effective catalyst for HDO of phenolic compounds and "real-world" biomass-derived phenolic streams. In the presence of PtCo/NOMC, full deoxygenation of phenolic compounds and a biomass-derived phenolic stream is achieved under conditions of low severity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Yu, Zhiquan; Wang, Anjie; Liu, Shan

SiO 2, HZSM-5 and Al 2O 3 were used to support nickel phosphides to prepare hydrodeoxygenation (HDO) catalysts. The nickel loading was kept at 20 wt% while the Ni/P molar ratio was varied among 3, 2, and 1 in the preparation by incipient wetness impregnation. XRD characterization revealed that Ni 3P, Ni 12P 5, and Ni 2P as the major crystal phases were obtained at Ni/P ratio of 3, 2, and 1, respectively, on SiO 2 and HZSM-5. When Al 2O 3 was used as the support, nickel metal rather than nickel phosphides was generated. Among SiO 2-supported nickel phosphides,more » Ni 3P exhibited highest hydrogenation activity and catalytic performance in phenol HDO. Ni 3P/HZSM-5 showed the high catalytic performance in HDO of phenol as well as catechol and o-cresol, with Ni 3P as the hydrogenation site and the acid sites in HZSM-5 zeolite as the dehydration site. In conclusion, the strong acidity in HZSM-5 also facilitated the isomerization of cycloalkanes at elevated temperatures.« less

Influence of Solvent on Liquid Phase Hydrodeoxygenation of Furfural-Acetone Condensation Adduct using Ni/Al2O3-ZrO2 Catalysts

NASA Astrophysics Data System (ADS)

Ulfa, S. M.; Mahfud, A.; Nabilah, S.; Rahman, M. F.

2017-02-01

Influence of water and acidic protic solvent on hydrodeoxygenation (HDO) of the furfural-acetone adduct (FAA) over Ni/Al2O3-ZrO2 (NiAZ) catalysts were investigated. The HDO of FAA was carried out in a batch reactor at 150°C for 8 hours. The NiAZ catalysts were home-made catalysts which were prepared by wet impregnation method with 10 and 20% nickel loading. The HDO reaction of FAA using 10NiAZ in water at 150°C gave alkane and oxygenated hydrocarbons at 31.41% with selectivity over tridecane (C13) in 6.67%. On the other hand, a reaction using acetic acid:water (1:19 v/v) in similar reaction condition gave only oxygenated compounds and hydrocracking product (C8-C10). The formation of tridecane (C13) was proposed by hydrogenation of C=O and C=C followed by decarboxylation without hydrocracking process. The presence of water facilitated decarboxylation mechanism by stabilized dehydrogenated derivatives of FAA.

Low-temperature chemistry between water and hydroxyl radicals: H/D isotopic effects

NASA Astrophysics Data System (ADS)

Lamberts, T.; Fedoseev, G.; Puletti, F.; Ioppolo, S.; Cuppen, H. M.; Linnartz, H.

2016-01-01

Sets of systematic laboratory experiments are presented - combining Ultra High Vacuum cryogenic and plasma-line deposition techniques - that allow us to compare H/D isotopic effects in the reaction of H2O (D2O) ice with the hydroxyl radical OD (OH). The latter is known to play a key role as intermediate species in the solid-state formation of water on icy grains in space. The main finding of our work is that the reaction H2O + OD → OH + HDO occurs and that this may affect the HDO/H2O abundances in space. The opposite reaction D2O + OH → OD + HDO is much less effective, and also given the lower D2O abundances in space not expected to be of astronomical relevance. The experimental results are extended to the other four possible reactions between hydroxyl and water isotopes and are subsequently used as input for Kinetic Monte Carlo simulations. This way we interpret our findings in an astronomical context, qualitatively testing the influence of the reaction rates.

U.S. Marine 3rd Tank Battalion Lubrication Evaluation under Hot Ambient Temperatures at Twenty-Nine Palms, California

DTIC Science & Technology

1988-09-01

designed to compare the performance of grade 15W-40 (OE/HDO- 15/40), grade 40 (OE/HDO-40), and SAE -50 grade lubricants in M60 battle tanks and to verify...throughout the test period. Company A was to continue to use SAE -50 grade oil, Company B was to receive an OEIHDO-l3I40 oil, and Company C was to be...Company A procured the SAE -nO grade oil thdrough normal supply channels. 2 Each tank company was to follow regularly scheduled training cycles so that by

Influence of oxalate ligand functionalization on Co/ZSM-5 activity in Fischer Tropsch synthesis and hydrodeoxygenation of oleic acid into hydrocarbon fuels.

PubMed

Ayodele, Olumide Bolarinwa

2017-08-30

Achieving high degree of active metal dispersions at the highest possible metal loading and high reducibility of the metal remains a challenge in Fischer Tropsch synthesis (FTS) as well as in hydrogeoxygenation (HDO).This study therefore reports the influence of oxalic acid (OxA) functionalization on the metal dispersion, reducibility and activity of Co supported ZSM-5 catalyst in FTS and HDO of oleic acid into paraffin biofuel. The Brunauer-Emmett-Teller (BET) results showed that cobalt oxalate supported ZSM-5 catalyst (CoOx/ZSM-5) synthesized from the incorporation of freshly prepared cobalt oxalate complex into ZSM-5 displayed increase in surface area, pore volume and average pore size while the nonfunctionalized cobalt supported on ZSM-5 (Co/ZSM-5) catalyst showed reduction in those properties. Furthermore, both XRD and XPS confirmed the presence of Co° formed from the decomposition of CoOx during calcination of CoOx/ZSM-5 under inert atmosphere. The HRTEM showed that Co species average particle sizes were smaller in CoOx/ZSM-5 than in Co/ZSM-5, and in addition, CoOx/ZSM-5 shows a clear higher degree of active metal dispersion. The FTS result showed that at CO conversion over Co/ZSM-5 and CoOx/ZSM-5 catalysts were 74.28% and 94.23% and their selectivity to C 5+ HC production were 63.15% and 75.4%, respectively at 4 h TOS. The HDO result also showed that the CoOx/ZSM-5 has higher OA conversion of 92% compared to 59% over Co/ZSM-5. In addition CoOx/ZSM-5 showed higher HDO and isomerization activities compared to Co/ZSM-5.

Influence of convection on the diffusive transport and sieving of water and small solutes across the peritoneal membrane.

PubMed

Asghar, Ramzana B; Diskin, Ann M; Spanel, Patrik; Smith, David; Davies, Simon J

2005-02-01

The three-pore model of peritoneal membrane physiology predicts sieving of small solutes as a result of the presence of a water-exclusive pathway. The purpose of this study was to measure the diffusive and convective components of small solute transport, including water, under differing convection. Triplicate studies were performed in eight stable individuals using 2-L exchanges of bicarbonate buffered 1.36 or 3.86% glucose and icodextrin. Diffusion of water was estimated by establishing an artificial gradient of deuterated water (HDO) between blood/body water and the dialysate. (125)RISA (radio-iodinated serum albumin) was used as an intraperitoneal volume marker to determine the net ultrafiltration and reabsorption of fluid. The mass transfer area coefficient (MTAC) for HDO and solutes was estimated using the Garred and Waniewski equations. The MTAC of HDO calculated for 1.36% glucose and icodextrin were similar (36.8 versus 39.7 ml/min; P = 0.3), whereas for other solutes, values obtained using icodextrin were consistently higher (P < 0.05). A significant increase in the MTAC of HDO was demonstrated with an increase in the convective flow of water when using 3.86% glucose (mean value, 49.5 ml/min; P < 0.05). MTAC for urea was also increased with 3.86% glucose. The identical MTAC for water using 1.36% glucose and icodextrin indicates that diffusion is predominantly through small pores, whereas the difference in MTAC for the remaining solutes is a reflection of their sieving. The increase in the MTAC of water and urea associated with an increase in convection is most likely due to increased mixing within the interstitium.

Laser spectroscopic visualization of hydrogen bond motions in liquid water

NASA Astrophysics Data System (ADS)

Bratos, S.; Leicknam, J.-Cl.; Pommeret, S.; Gallot, G.

2004-12-01

Ultrafast pump-probe experiments are described permitting a visualization of molecular motions in diluted HDO/D 2O solutions. The experiments were realized in the mid-infrared spectral region with a time resolution of 150 fs. They were interpreted by a careful theoretical analysis, based on the correlation function approach of statistical mechanics. Combining experiment and theory, stretching motions of the OH⋯O bonds as well as HDO rotations were 'filmed' in real time. It was found that molecular rotations are the principal agent of hydrogen bond breaking and making in water. Recent literatures covering the subject, including molecular dynamics simulations, are reviewed in detail.

Hydrodeoxygenation of phenolic compounds to cycloalkanes over supported nickel phosphides

DOE PAGES

Yu, Zhiquan; Wang, Anjie; Liu, Shan; ...

2018-05-07

SiO 2, HZSM-5 and Al 2O 3 were used to support nickel phosphides to prepare hydrodeoxygenation (HDO) catalysts. The nickel loading was kept at 20 wt% while the Ni/P molar ratio was varied among 3, 2, and 1 in the preparation by incipient wetness impregnation. XRD characterization revealed that Ni 3P, Ni 12P 5, and Ni 2P as the major crystal phases were obtained at Ni/P ratio of 3, 2, and 1, respectively, on SiO 2 and HZSM-5. When Al 2O 3 was used as the support, nickel metal rather than nickel phosphides was generated. Among SiO 2-supported nickel phosphides,more » Ni 3P exhibited highest hydrogenation activity and catalytic performance in phenol HDO. Ni 3P/HZSM-5 showed the high catalytic performance in HDO of phenol as well as catechol and o-cresol, with Ni 3P as the hydrogenation site and the acid sites in HZSM-5 zeolite as the dehydration site. In conclusion, the strong acidity in HZSM-5 also facilitated the isomerization of cycloalkanes at elevated temperatures.« less

One-Pot Process for Hydrodeoxygenation of Lignin to Alkanes Using Ru-Based Bimetallic and Bifunctional Catalysts Supported on Zeolite Y.

PubMed

Wang, Hongliang; Ruan, Hao; Feng, Maoqi; Qin, Yuling; Job, Heather; Luo, Langli; Wang, Chongmin; Engelhard, Mark H; Kuhn, Erik; Chen, Xiaowen; Tucker, Melvin P; Yang, Bin

2017-04-22

The synthesis of high-efficiency and low-cost catalysts for hydrodeoxygenation (HDO) of waste lignin to advanced biofuels is crucial for enhancing current biorefinery processes. Inexpensive transition metals, including Fe, Ni, Cu, and Zn, were severally co-loaded with Ru on HY zeolite to form bimetallic and bifunctional catalysts. These catalysts were subsequently tested for HDO conversion of softwood lignin and several lignin model compounds. Results indicated that the inexpensive earth-abundant metals could modulate the hydrogenolysis activity of Ru and decrease the yield of low-molecular-weight gaseous products. Among these catalysts, Ru-Cu/HY showed the best HDO performance, affording the highest selectivity to hydrocarbon products. The improved catalytic performance of Ru-Cu/HY was probably a result of the following three factors: (1) high total and strong acid sites, (2) good dispersion of metal species and limited segregation, and (3) high adsorption capacity for polar fractions, including hydroxyl groups and ether bonds. Moreover, all bifunctional catalysts proved to be superior over the combination catalysts of Ru/Al 2 O 3 and HY zeolite. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Production of bio-hydrogenated diesel by catalytic hydrotreating of palm oil over NiMoS2/γ-Al2O3 catalyst.

PubMed

Srifa, Atthapon; Faungnawakij, Kajornsak; Itthibenchapong, Vorranutch; Viriya-Empikul, Nawin; Charinpanitkul, Tawatchai; Assabumrungrat, Suttichai

2014-04-01

Catalytic hydrotreating of palm oil (refined palm olein type) to produce bio-hydrogenated diesel (BHD) was carried out in a continuous-flow fixed-bed reactor over NiMoS2/γ-Al2O3 catalyst. Effects of dominant hydrotreating parameters: temperature: 270-420°C; H2 pressure: 15-80 bar; LHSV: 0.25-5.0 h(-1); and H2/oil ratio: 250-2000 N(cm(3)/cm(3)) on the conversion, product yield, and a contribution of hydrodeoxygenation (HDO) and decarbonylation/decarboxylation (DCO/DCO2) were investigated to find the optimal hydrotreating conditions. All calculations including product yield and the contribution of HDO and DCO/DCO2 were extremely estimated based on mole balance corresponding to the fatty acid composition in feed to fully understand deoxygenation behaviors at different conditions. These analyses demonstrated that HDO, DCO, and DCO2 reactions competitively occurred at each condition, and had different optimal and limiting conditions. The differences in the hydrotreating reactions, liquid product compositions, and gas product composition were also discussed. Copyright © 2014 Elsevier Ltd. All rights reserved.

One-pot process for hydrodeoxygenation of lignin to alkanes using Ru-based bimetallic and bifunctional catalysts supported on zeolite Y

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

Wang, Hongliang; Ruan, Hao; Feng, Maoqi

2017-02-22

Here, the synthesis of high-efficiency and low-cost catalysts for hydrodeoxygenation (HDO) of waste lignin to advanced biofuels is crucial for enhancing current biorefinery processes. Inexpensive transition metals, including Fe, Ni, Cu, and Zn, were severally co-loaded with Ru on HY zeolite to form bimetallic and bifunctional catalysts. These catalysts were subsequently tested for HDO conversion of softwood lignin and several lignin model compounds. Results indicated that the inexpensive earth-abundant metals could modulate the hydrogenolysis activity of Ru and decrease the yield of low-molecular-weight gaseous products. Among these catalysts, Ru-Cu/HY showed the best HDO performance, affording the highest selectivity to hydrocarbonmore » products. The improved catalytic performance of Ru-Cu/HY was probably a result of the following three factors: (1) high total and strong acid sites, (2) good dispersion of metal species and limited segregation, and (3) high adsorption capacity for polar fractions, including hydroxyl groups and ether bonds. Moreover, all bifunctional catalysts proved to be superior over the combination catalysts of Ru/Al 2O 3 and HY zeolite.« less

Synergistic Catalysis between Pd and Fe in Gas Phase Hydrodeoxygenation of m-Cresol

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

Hong, Yongchun; Zhang, He; Sun, Junming

2014-10-31

In this work, a series of Pd/Fe2O3 catalysts were synthesized, characterized, and evaluated for the hydrodeoxygenation (HDO) of m-cresol. It was found that the addition of Pd remarkably promotes the catalytic activity of Fe while the product distributions resemble that of monometallic Fe catalyst, showing high selectivity towards the production of toluene (C-O cleavage without saturation of aromatic ring and C-C cleavage). Reduced catalysts featured with Pd patches on the top of reduced Fe nanoparticle surface, and the interaction between Pd and Fe was further confirmed using X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM) and X-ray absorption nearmore » edge fine structure (XANES). A possible mechanism, including Pd assisted H2 dissociation and Pd facilitated stabilization of metallic Fe surface as well as Pd enhanced product desorption, is proposed to be responsible for the high activity and HDO selectivity in Pd-Fe catalysts. The synergic catalysis derived from Pd-Fe interaction found in this work was proved to be applicable to other precious metal promoted Fe catalysts, providing a promising strategy for future design of highly active and selective HDO catalysts.« less

Hydrodeoxygenation of coal using organometallic catalyst precursors

NASA Astrophysics Data System (ADS)

Kirby, Stephen R.

2002-04-01

The objective of this dissertation was to determine the desirability of organometallic compounds for the hydrodeoxygenation (HDO) of coal during liquefaction. The primary focus of this study was the removal of phenol-like compounds from coal liquids for the production of a thermally stable jet fuel. Investigation of the HDO ability of an organometallic compound containing both cobalt and molybdenum (CoMo-T2) was achieved using a combination of model compound and coal experiments. Model compounds were chosen representing four oxygen functional groups present in a range of coals. Electron density and bond order calculations were performed for anthrone, dinaphthyl ether, xanthene, di-t-butylmethylphenol, and some of their derivatives to ascertain a potential order of hydrogenolysis and hydrogenation reactivity for these compounds. The four model compounds were then reacted with CoMo-T2, as well as ammonium tetrathiomolybdate (ATTM). Products of reaction were grouped as compounds that had undergone deoxygenation, those that had aromatic rings reduced, those that were products of both reaction pathways, and those produced through other routes. ATTM had an affinity for both reaction types. Its reaction order for the four model compounds with respect to deoxygenated compounds was the same as that estimated from electron density calculations for hydrogenolysis reactivity. CoMo-T2 appeared to show a preference toward hydrogenation, although deoxygenated products were still achieved in similar, or greater, yields, for almost all the model compounds. The reactivity order achieved for the four compounds with CoMo-T2 was similar to that estimated from bond order calculations for hydrogenation reactivity. Three coals were selected representing a range of coal ranks and oxygen contents. DECS-26 (Wyodak), DECS-24 (Illinois #6), and DECS-23 (Pittsburgh #8) were analyzed by CPMAS 13C NMR and pyrolysis-GC-MS to determine the functional groups comprising the oxygen content of these coals. Trends within the data were similar to those reported by other authors. Based on the conclusions from both the model compound studies and the coal analysis, predictions were made of the catalyst precursors' performance in the HDO of the three selected coals. It was concluded that CoMo-T2 is a desirable catalyst precursor for the HDO of coals (particularly low-rank coals), but that an optimum set of conditions must be determined to take full advantage of its HDO ability. (Abstract shortened by UMI.)

Deuterated Water in Comet C/1996 B2 (Hyakutake) and its Implications for the Origin of Comets

NASA Technical Reports Server (NTRS)

Bockelee-Morvan, D.; Gautier, D.; Lis, D. C.; Young, K.; Keene, J.; Phillips, T. G.; Owen, T.; Crovisier, J.; Goldsmith, P. F.; Bergin, E. A.;

Instrumentation and signal processing for the detection of heavy water using off axis-integrated cavity output spectroscopy technique

NASA Astrophysics Data System (ADS)

Gupta, A.; Singh, P. J.; Gaikwad, D. Y.; Udupa, D. V.; Topkar, A.; Sahoo, N. K.

2018-02-01

An experimental setup is developed for the trace level detection of heavy water (HDO) using the off axis-integrated cavity output spectroscopy technique. The absorption spectrum of water samples is recorded in the spectral range of 7190.7 cm-1-7191.5 cm-1 with the diode laser as the light source. From the recorded water vapor absorption spectrum, the heavy water concentration is determined from the HDO and water line. The effect of cavity gain nonlinearity with per pass absorption is studied. The signal processing and data fitting procedure is devised to obtain linear calibration curves by including nonlinear cavity gain effects into the calculation. Initial calibration of mirror reflectivity is performed by measurements on the natural water sample. The signal processing and data fitting method has been validated by the measurement of the HDO concentration in water samples over a wide range from 20 ppm to 2280 ppm showing a linear calibration curve. The average measurement time is about 30 s. The experimental technique presented in this paper could be applied for the development of a portable instrument for the fast measurement of water isotopic composition in heavy water plants and for the detection of heavy water leak in pressurized heavy water reactors.

Carbon-supported bimetallic Pd–Fe catalysts for vapor-phase hydrodeoxygenation of guaiacol

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

Sun, Junming; Karim, Ayman M.; Zhang, He

2013-10-01

Abstract Carbon supported metal catalysts (Cu/C, Fe/C, Pd/C, Pt/C, PdFe/C and Ru/C) have been prepared, characterized and tested for vapor-phase hydrodeoxygenation (HDO) of guaiacol (GUA) at atmospheric pressure. Phenol was the major intermediate on all catalysts. Over the noble metal catalysts saturation of the aromatic ring was the major pathway observed at low temperature (250 °C), forming predominantly cyclohexanone and cyclohexanol. Substantial ring opening reaction was observed on Pt/C and Ru/C at higher reaction temperatures (e.g., 350 °C). Base metal catalysts, especially Fe/C, were found to exhibit high HDO activity without ring-saturation or ring-opening with the main products being benzene,more » phenol along with small amounts of cresol, toluene and trimethylbenzene (TMB). A substantial enhancement in HDO activity was observed on the PdFe/C catalysts. Compared with Fe/C, the yield to oxygen-free aromatic products (i.e., benzene/toluene/TMB) on PdFe/C increased by a factor of four at 350 °C, and by approximately a factor of two (83.2% versus 43.3%) at 450 °C. The enhanced activity of PdFe/C is attributed to the formation of PdFe alloy as evidenced by STEM, EDS and TPR.« less

One-Pot Process for Hydrodeoxygenation of Lignin to Alkanes Using Ru-Based Bimetallic and Bifunctional Catalysts Supported on Zeolite Y

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

Wang, Hongliang; Ruan, Hao; Feng, Maoqi

2017-03-16

The synthesis of high-efficiency and low-cost multifunctional catalysts for hydrodeoxygenation (HDO) of waste lignin into advanced biofuels is crucial for enhancing current biorefinery processes. Inexpensive transition metals, including Fe, Ni, Cu, Zn, were severally co-loaded with Ru on HY zeolite to form bimetallic and bifunctional catalysts. These catalysts were subsequently tested for HDO conversion of softwood lignin and several lignin model compounds. Results indicated that the inexpensive earth abundant metals could modulate the hydrogenolysis activity of Ru and decrease the yield of low molecular weight gaseous side-products. Among all the prepared catalysts, Ru-Cu/HY showed the best HDO performance, giving themore » highest selectivity to hydrocarbon products. The improved catalytic performance of Ru-Cu/HY was probably due to the following three factors: (1) high total and strong acid sites, (2) good dispersion of metal species and limited segregation, (3) high adsorption capacity for polar fractions, including hydroxyl groups and ether bonds. Moreover, all the bifunctional catalysts were proven to be superior over the combination catalysts of Ru/Al2O3 and HY zeolite, and this could be attributed to the “intimacy criterion”. The practical use of the designed catalysts would be promising in lignin valorization.« less

Deuterated water in low-mass protostars

NASA Astrophysics Data System (ADS)

Coutens, Audrey; Vastel, Charlotte; Chess Collaboration; Wish Collaboration; Hexos Collaboration

2013-07-01

In addition to its dominant role in the cooling of warm gas and in the oxygen chemistry, water is a primordial species in the emergence of life, and comets may have brought a large fraction to Earth to form the oceans. Observations of deuterated water are an important complement for studies of H2O to understand how water forms and how it has evolved from cold prestellar cores to protoplanetary disks and consequently oceans for the Earth's specific, but probably not isolated, case. Several deuterated water transitions were observed with the Herschel/HIFI (Heterodyne Instrument for Far Infrared) instrument towards three low-mass protostars: IRAS 16293-2422, NGC1333 IRAS4A and NGC1333 IRAS4B. In the first source, both HDO and D2O lines are detected, thanks to the unbiased spectral survey carried out by the CHESS key program (Vastel et al. 2010, Coutens et al. 2013a). In the framework of a collaboration between the CHESS, WISH and HEXOS programs, two HDO key lines were observed towards the two other protostars. In addition, complementary observations were carried out with several ground-based single-dish telescopes (IRAM-30m, JCMT, APEX). We used the non-LTE RATRAN spherical model (Hogerheijde & van der Tak 2000) to determine the HDO abundance distribution throughout the protostellar envelope. An abundance jump at 100 K is required to reproduce the line profiles. Indeed, water molecules trapped in the icy grain mantles thermally desorb in the hot corinos, the inner warm regions of the protostellar envelopes. We also obtain that it is necessary to add a water-rich external absorbing layer to reproduce the absorbing components of the HDO and D2O fundamental transitions in all sources (Coutens et al. 2012, 2013a,b). The results derived for the different sources will be then presented and discussed.

COMPARISON OF HIGH-DEFINITION OSCILLOMETRIC AND DIRECT ARTERIAL BLOOD PRESSURE MEASUREMENT IN ANESTHETIZED CHEETAHS (ACINONYX JUBATUS).

PubMed

Sant Cassia, Emma V; Boswood, Adrian; Tordiffe, Adrian S W

2015-09-01

Blood pressure measurement reveals important insights into the health of conscious and anesthetized individuals. This is of particular interest in cheetahs (Acinonyx jubatus), which in captivity are known to suffer from chronic diseases that may be associated with hypertension and which often require immobilization for transport or veterinary treatment. Invasive testing methods are considered the gold standard but are not practical in many settings. Consequently, it is important to evaluate the use of noninvasive methods in this species. Measurements for systolic, diastolic, and mean arterial pressure obtained using high-definition oscillometry (HDO) at the coccygeal artery were compared to simultaneous direct measurements obtained via catheterization of the femoral or dorsal pedal artery in eight anesthetized captive cheetahs during nine anesthetic events. Overall, HDO and direct measurements agreed most closely for mean arterial pressure, and the poorest agreement was observed for systolic pressure. There was a tendency for low diastolic pressures to be underestimated and for high diastolic pressures to be overestimated. Across all three parameters, HDO measurements from the tail overestimated directly measured pressures in the femoral artery and underestimated those in the dorsal pedal artery. HDO agreed most closely with directly measured dorsal pedal pressures. Mean arterial pressure showed the greatest precision (standard deviation of 10.2 mm Hg) and lowest bias (-1.2 mm Hg), with 75.9% of readings within 10 mm Hg of the direct dorsal pedal pressure. Agreement with systolic pressure was hindered by a high bias (-10.4 mm Hg), but if a correction factor of +10 mm Hg was applied to all systolic measurements, agreement was improved and 65.7% of readings were within 10 mm Hg of the direct pressure. When compared to criteria defined by the American College of Veterinary Internal Medicine for validation of blood pressure devices, results were favorable, but a limited sample size prevented formal validation.

Development of Bio-Oil Commodity Fuel as a Refinery Feedstock from High Impact Algae Biomass

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

Kastner, James; Mani, Sudhagar; Das, K. C.

A two-stage hydrothermal liquefaction (HTL) process was developed to 1) reduce nitrogen levels in algal oil, 2) generate a nitrogen rich stream with limited inhibitors for recycle and algae cultivation, and 3) improve downstream catalytic hydrodenitrogenation and hydrodeoxygenation of the algal oil to refinery intermediates. In the first stage, low temperature HTL was conducted at 125, 175, and 225°C at holding times ranging from 1 to 30 min (time at reaction temperature). A consortium of three algal strains, namely Chlorella sorokiniana, Chlorella minutissima, and Scenedesmus bijuga were used to grow and harvest biomass in a raceway system – this consortiummore » is called the UGA Raceway strain throughout the report. Subsequent analysis of the final harvested product indicated that only two strains predominated in the final harvest - Chlorella sorokiniana and Scenedesmus bijuga. Two additional strains representing a high protein (Spirulina platensis) and high lipid algae (Nannochloropsis) strains were also used in this study. These strains were purchased from suppliers. S. platensis biomass was provided by Earthrise Nutritionals LLC (Calipatria, CA) in dry powder form with defined properties, and was stored in airtight packages at 4°C prior to use. A Nannochloropsis paste from Reed Mariculture was purchased and used in the two-stage HTL/HDO experiments. The solids and liquids from this low temperature HTL pretreatment step were separated and analyzed, leading to the following conclusions. Overall, these results indicate that low temperature HTL (200-250°C) at short residence times (5-15 min) can be used to lyse algae cells and remove/separate protein and nitrogen before subsequent higher temperature HTL (for lipid and other polymer hydrolysis) and HDO. The significant reduction in nitrogen when coupled with low protein/high lipid algae cultivation methods at scale could significantly improve downstream catalytic HDO results. However, significant barriers and knowledge gaps exist that must be overcome and understood. The ability of the separated protein/nitrogen rich aqueous stream to support algae cultivation needs to be verified (and the kinetics of growth measured). The kinetics of algae hydrothermal liquefaction on a mechanistic basis needs to be measured and understood. A better understanding of Maillard reactions during algae HTL is needed. And the impact of Maillard reaction products and incompletely hydrolyzed cell wall components on catalyst deactivation during HDO needs to be understood. Finally, an inexpensive HDO process and associated catalyst capable of converting the algal oil to hydrocarbons needs to be developed.« less

Selective Hydrodeoxygenation of Alkyl Lactates to Alkyl Propionates with Fe-based Bimetallic Supported Catalysts.

PubMed

Khokarale, Santosh Govind; He, Jian; Schill, Leonhard; Yang, Song; Riisager, Anders; Saravanamurugan, Shunmugavel

2018-02-22

Hydrodeoxygenation (HDO) of methyl lactate (ML) to methyl propionate (MP) was performed with various base-metal supported catalysts. A high yield of 77 % MP was obtained with bimetallic Fe-Ni/ZrO 2 in methanol at 220 °C and 50 bar H 2 . A synergistic effect of Ni increased the yield of MP significantly when using Fe-Ni/ZrO 2 instead of Fe/ZrO 2 alone. Moreover, the ZrO 2 support contributed to improve the yield as a phase transition of ZrO 2 from tetragonal to monoclinic occurred after metal doping giving rise to fine dispersion of the Fe and Ni on the ZrO 2 , resulting in a higher catalytic activity of the material. Interestingly, it was observed that Fe-Ni/ZrO 2 also effectively catalyzed methanol reforming to produce H 2 in situ, followed by HDO of ML, yielding 60 % MP at 220 °C with 50 bar N 2 instead of H 2 . Fe-Ni/ZrO 2 also catalyzed HDO of other short-chain alkyl lactates to the corresponding alkyl propionates in high yields around 70 %. No loss of activity of Fe-Ni/ZrO 2 occurred in five consecutive reaction runs demonstrating the high durability of the catalyst system. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Water Planetary and Cometary Atmospheres: H2O/HDO Transmittance and Fluorescence Models

NASA Technical Reports Server (NTRS)

Villanueva, G. L.; Mumma, M. J.; Bonev, B. P.; Novak, R. E.; Barber, R. J.; DiSanti, M. A.

2012-01-01

We developed a modern methodology to retrieve water (H2O) and deuterated water (HDO) in planetary and cometary atmospheres, and constructed an accurate spectral database that combines theoretical and empirical results. Based on a greatly expanded set of spectroscopic parameters, we built a full non-resonance cascade fluorescence model and computed fluorescence efficiencies for H2O (500 million lines) and HDO (700 million lines). The new line list was also integrated into an advanced terrestrial radiative transfer code (LBLRTM) and adapted to the CO2 rich atmosphere of Mars, for which we adopted the complex Robert-Bonamy formalism for line shapes. We then retrieved water and D/H in the atmospheres of Mars, comet C/2007 WI, and Earth by applying the new formalism to spectra obtained with the high-resolution spectrograph NIRSPEC/Keck II atop Mauna Kea (Hawaii). The new model accurately describes the complex morphology of the water bands and greatly increases the accuracy of the retrieved abundances (and the D/H ratio in water) with respect to previously available models. The new model provides improved agreement of predicted and measured intensities for many H2O lines already identified in comets, and it identifies several unassigned cometary emission lines as new emission lines of H2O. The improved spectral accuracy permits retrieval of more accurate rotational temperatures and production rates for cometary water.

Nano-catalysts for upgrading bio-oil: Catalytic decarboxylation and hydrodeoxygenation

NASA Astrophysics Data System (ADS)

Uemura, Yoshimitsu; Tran, Nga T. T.; Naqvi, Salman Raza; Nishiyama, Norikazu

2017-09-01

Bio-oil is a mixture of oxygenated chemicals produced by fast pyrolysis of lignocellulose, and has attracted much attention recently because the raw material is renewable. Primarily, bio-oil can be used as a replacement of heavy oil. But it is not highly recommended due to bio-oil's inferior properties: high acidity and short shelf life. Upgrading of bio-oil is therefore one of the important technologies nowadays, and is categorized into the two: (A) decrarboxylation/decarbonylation by solid acid catalysts and (B) hydrodeoxygenation (HDO) by metallic catalysts. In our research group, decarboxylation of bio-oil by zeolites and HDO of guaiacol (a model compound of bio-oil) have been investigated. In this paper, recent developments of these upgrading reactions in our research group will be introduced.

Property distribution of drug-related chemical databases*

NASA Astrophysics Data System (ADS)

Oprea, Tudor I.

2000-04-01

The process of compound selection and prioritization is crucial for both combinatorial chemistry (CBC) and high throughput screening (HTS). Compound libraries have to be screened for unwanted chemical structures, as well as for unwanted chemical properties. Property extrema can be eliminated by using property filters, in accordance with their actual distribution. Property distribution was examined in the following compound databases: MACCS-II Drug Data Report (MDDR), Current Patents Fast-alert, Comprehensive Medicinal Chemistry, Physician Desk Reference, New Chemical Entities, and the Available Chemical Directory (ACD). The ACDF and MDDRF subsets were created by removing reactive functionalities from the ACD and MDDR databases, respectively. The ACDF subset was further filtered by keeping only molecules with a `drug-like' score [Ajay et al., J. Med. Chem., 41 (1998) 3314; Sadowski and Kubinyi, J. Med. Chem., 41 (1998) 3325] below 0.8. The following properties were examined: molecular weight (MW), the calculated octanol/water partition coefficient (CLOGP), the number of rotatable (RTB) and rigid bonds (RGB), the number of rings (RNG), and the number of hydrogen bond donors (HDO) and acceptors (HAC). Of these, MW and CLOGP follow a Gaussian distribution, whereas all other descriptors have an asymmetric (truncated Gaussian) distribution. Four out of five compounds in ACDF and MDDRF pass the `rule of 5' test, a probability scheme that estimates oral absorption proposed by Lipinski et al. [Adv. Drug Deliv. Rev., 23 (1997) 3]. Because property distributions of HDO, HAC, MW and CLOGP (used in the `rule of 5' test) do not differ significantly between these datasets, the `rule of 5' does not distinguish `drugs' from `nondrugs'. Therefore, Pareto analyses were performed to examine skewed distributions in all compound collections. Seventy percent of the `drug-like' compounds were found between the following limits: 0 ≤ HDO ≤ 2, 2 ≤ HAC ≤ 9, 2 ≤ RTB ≤ 8, and 1 ≤ RNG ≤ 4, respectively. The number of launched drugs in MDDR having 0 ≤ HDO ≤ 2 is 4.8 times higher than the number of drugs having 3 ≤ HDO ≤ 5. Skewed distributions can be exploited to focus on the `drug-like space': 62.68% of ACDF (`nondrug-like') compounds have 0 ≤ RNG ≤ 2, and RGB ≤ 17, while 28.88% of ACDF compounds have 3 ≤ RNG ≤ 13, and 18 ≤ RGB ≤ 56. By contrast, 61.22% of MDDRF compounds have RNG ≥ 3, and RGB ≥ 18, and only 24.73% of MDDRF compounds have 0 ≤ RNG ≤ 2 rings, and RGB ≤ 17. The probability of identifying `drug-like' structures increases with molecular complexity.

Warm water deuterium fractionation in IRAS 16293-2422. The high-resolution ALMA and SMA view

NASA Astrophysics Data System (ADS)

Persson, M. V.; Jørgensen, J. K.; van Dishoeck, E. F.

2013-01-01

Context. Measuring the water deuterium fractionation in the inner warm regions of low-mass protostars has so far been hampered by poor angular resolution obtainable with single-dish ground- and space-based telescopes. Observations of water isotopologues using (sub)millimeter wavelength interferometers have the potential to shed light on this matter. Aims: To measure the water deuterium fractionation in the warm gas of the deeply-embedded protostellar binary IRAS 16293-2422. Methods: Observations toward IRAS 16293-2422 of the 53,2 - 44,1 transition of H218O at 692.07914 GHz from Atacama Large Millimeter/submillimeter Array (ALMA) as well as the 31,3 - 22,0 of H218O at 203.40752 GHz and the 31,2 - 22,1 transition of HDO at 225.89672 GHz from the Submillimeter Array (SMA) are presented. Results: The 692 GHz H218O line is seen toward both components of the binary protostar. Toward one of the components, "source B", the line is seen in absorption toward the continuum, slightly red-shifted from the systemic velocity, whereas emission is seen off-source at the systemic velocity. Toward the other component, "source A", the two HDO and H218O lines are detected as well with the SMA. From the H218O transitions the excitation temperature is estimated at 124 ± 12 K. The calculated HDO/H2O ratio is (9.2 ± 2.6) × 10-4 - significantly lower than previous estimates in the warm gas close to the source. It is also lower by a factor of ~5 than the ratio deduced in the outer envelope. Conclusions: Our observations reveal the physical and chemical structure of water vapor close to the protostars on solar-system scales. The red-shifted absorption detected toward source B is indicative of infall. The excitation temperature is consistent with the picture of water ice evaporation close to the protostar. The low HDO/H2O ratio deduced here suggests that the differences between the inner regions of the protostars and the Earth's oceans and comets are smaller than previously thought. Appendix A is available in electronic form at http://www.aanda.org

Pyrolysis bio-oil upgrading to renewable fuels.

DOT National Transportation Integrated Search

2014-01-01

This study aims to upgrade woody biomass pyrolysis bio-oil into transportation fuels by catalytic hydrodeoxygenation : (HDO) using nanospring (NS) supported catalyst via the following research objectives: (1) develop nanospring-based : catalysts (nan...

Final Technical Report: Tandem and Bimetallic Catalysts for Oxidative Dehydrogenation of Light Hydrocarbon with Renewable Feedstock

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

Abu-Omar, Mahdi

2017-01-06

An estimated 490 million metric tons of lignocellulosic biomass is available annually from U.S. agriculture and forestry. With continuing concerns over greenhouse gas emission, the development of efficient catalytic processes for conversion of biomass derived compounds is an important area of research. Since carbohydrates and polyols are rich in oxygen, approximately one oxygen atom per carbon, removal of hydroxyl groups via deoxygenation is needed. The necessary hydrogen required for hydrodeoxygenation (HDO) would either come from reforming biomass itself or from steam reforming of natural gas. Both processes contribute to global CO2 emission. The hope is that eventually renewable sources suchmore » as wind and solar for hydrogen production will become more viable and economic in the future. In the meantime, unconventional natural gas production in North America has boomed. As a result, light hydrocarbons present an opportunity when coupled with biomass derived oxygenates to generate valuable products from both streams without co-production of carbon dioxide. This concept is the focus of our current funding period. The objective of the project requires coupling two different types of catalysis, HDO and dehydrogenation. Our hypothesis was formulated around our success in establishing oxorhenium catalysts for polyol HDO reactions and known literature precedence for the use of iridium hydrides in alkane dehydrogenation. To examine our hypothesis we set out to investigate the reaction chemistry of binuclear complexes of oxorhenium and iridium hydride.« less

Influence of H 2O and H 2S on the composition, activity, and stability of sulfided Mo, CoMo, and NiMo supported on MgAl 2O 4 for hydrodeoxygenation of ethylene glycol

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

Dabros, Trine Marie Hartmann; Gaur, Abhijeet; Pintos, Delfina Garcia

Here in this work, density functional theory (DFT), catalytic activity tests, and in-situ X-ray absorption spectroscopy (XAS) was performed to gain detailed insights into the activity and stability of MoS 2, Ni-MoS 2, and Co-MoS 2 catalysts used for hydrodeoxygenation (HDO) of ethylene glycol upon variation of the partial pressures of H 2O and H 2S. The results show high water tolerance of the catalysts and highlight the importance of promotion and H 2S level during HDO. DFT calculations unraveled that the active edge of MoS 2 could be stabilized against SO exchanges by increasing the partial pressure of Hmore » 2S or by promotion with either Ni or Co. The Mo, NiMo, and CoMo catalysts of the present study were all active and fairly selective for ethylene glycol HDO at 400 °C, 27 bar H 2, and 550–2200 ppm H 2S, and conversions of ≈50–100%. The unpromoted Mo/MgAl 2O 4 catalyst had a lower stability and activity per gram catalyst than the promoted analogues. The NiMo and CoMo catalysts produced ethane, ethylene, and C1 cracking products with a C 2/C 1 ratio of 1.5–2.0 at 550 ppm H 2S. This ratio of HDO to cracking could be increased to ≈2 at 2200 ppm H 2S which also stabilized the activity. Removing H 2S from the feed caused severe catalyst deactivation. Both DFT and catalytic activity tests indicated that increasing the H 2S concentration increased the concentration of SH groups on the catalyst, which correspondingly activated and stabilized the catalytic HDO performance. In-situ XAS further supported that the catalysts were tolerant towards water when exposed to increasing water concentration with H2O/H2S ratios up to 300 at 400–450 °C. Raman spectroscopy and XAS showed that MoS2 was present in the prepared catalysts as small and highly dispersed particles, probably owing to a strong interaction with the support. Linear combination fitting (LCF) analysis of the X-ray absorption near edge structure (XANES) spectra obtained during in-situ sulfidation showed that Ni was sulfided faster than Mo and CoMo, and that Mo was sulfided faster when promoted with Ni. Extended X-ray absorption fine structure (EXAFS) results showed the presence of MoS 2 in all sulfided catalysts. Lastly, sulfided CoMo was present as a mixture of CoMoS and Co 9S 8, whereas sulfided NiMo was present as NiMoS.« less

Influence of H 2O and H 2S on the composition, activity, and stability of sulfided Mo, CoMo, and NiMo supported on MgAl 2O 4 for hydrodeoxygenation of ethylene glycol

DOE PAGES

Dabros, Trine Marie Hartmann; Gaur, Abhijeet; Pintos, Delfina Garcia; ...

2017-12-10

Here in this work, density functional theory (DFT), catalytic activity tests, and in-situ X-ray absorption spectroscopy (XAS) was performed to gain detailed insights into the activity and stability of MoS 2, Ni-MoS 2, and Co-MoS 2 catalysts used for hydrodeoxygenation (HDO) of ethylene glycol upon variation of the partial pressures of H 2O and H 2S. The results show high water tolerance of the catalysts and highlight the importance of promotion and H 2S level during HDO. DFT calculations unraveled that the active edge of MoS 2 could be stabilized against SO exchanges by increasing the partial pressure of Hmore » 2S or by promotion with either Ni or Co. The Mo, NiMo, and CoMo catalysts of the present study were all active and fairly selective for ethylene glycol HDO at 400 °C, 27 bar H 2, and 550–2200 ppm H 2S, and conversions of ≈50–100%. The unpromoted Mo/MgAl 2O 4 catalyst had a lower stability and activity per gram catalyst than the promoted analogues. The NiMo and CoMo catalysts produced ethane, ethylene, and C1 cracking products with a C 2/C 1 ratio of 1.5–2.0 at 550 ppm H 2S. This ratio of HDO to cracking could be increased to ≈2 at 2200 ppm H 2S which also stabilized the activity. Removing H 2S from the feed caused severe catalyst deactivation. Both DFT and catalytic activity tests indicated that increasing the H 2S concentration increased the concentration of SH groups on the catalyst, which correspondingly activated and stabilized the catalytic HDO performance. In-situ XAS further supported that the catalysts were tolerant towards water when exposed to increasing water concentration with H2O/H2S ratios up to 300 at 400–450 °C. Raman spectroscopy and XAS showed that MoS2 was present in the prepared catalysts as small and highly dispersed particles, probably owing to a strong interaction with the support. Linear combination fitting (LCF) analysis of the X-ray absorption near edge structure (XANES) spectra obtained during in-situ sulfidation showed that Ni was sulfided faster than Mo and CoMo, and that Mo was sulfided faster when promoted with Ni. Extended X-ray absorption fine structure (EXAFS) results showed the presence of MoS 2 in all sulfided catalysts. Lastly, sulfided CoMo was present as a mixture of CoMoS and Co 9S 8, whereas sulfided NiMo was present as NiMoS.« less

Validation of SCIAMACHY HDO/H2O measurements using the TCCON and NDACC-MUSICA networks

NASA Astrophysics Data System (ADS)

Scheepmaker, R. A.; Frankenberg, C.; Deutscher, N. M.; Schneider, M.; Barthlott, S.; Blumenstock, T.; Garcia, O. E.; Hase, F.; Jones, N.; Mahieu, E.; Notholt, J.; Velazco, V.; Landgraf, J.; Aben, I.

2015-04-01

Measurements of the atmospheric HDO/H2O ratio help us to better understand the hydrological cycle and improve models to correctly simulate tropospheric humidity and therefore climate change. We present an updated version of the column-averaged HDO/H2O ratio data set from the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY). The data set is extended with 2 additional years, now covering 2003-2007, and is validated against co-located ground-based total column δD measurements from Fourier transform spectrometers (FTS) of the Total Carbon Column Observing Network (TCCON) and the Network for the Detection of Atmospheric Composition Change (NDACC, produced within the framework of the MUSICA project). Even though the time overlap among the available data is not yet ideal, we determined a mean negative bias in SCIAMACHY δD of -35 ± 30‰ compared to TCCON and -69 ± 15‰ compared to MUSICA (the uncertainty indicating the station-to-station standard deviation). The bias shows a latitudinal dependency, being largest (∼ -60 to -80‰) at the highest latitudes and smallest (∼ -20 to -30‰) at the lowest latitudes. We have tested the impact of an offset correction to the SCIAMACHY HDO and H2O columns. This correction leads to a humidity- and latitude-dependent shift in δD and an improvement of the bias by 27‰, although it does not lead to an improved correlation with the FTS measurements nor to a strong reduction of the latitudinal dependency of the bias. The correction might be an improvement for dry, high-altitude areas, such as the Tibetan Plateau and the Andes region. For these areas, however, validation is currently impossible due to a lack of ground stations. The mean standard deviation of single-sounding SCIAMACHY-FTS differences is ∼ 115‰, which is reduced by a factor ∼ 2 when we consider monthly means. When we relax the strict matching of individual measurements and focus on the mean seasonalities using all available FTS data, we find that the correlation coefficients between SCIAMACHY and the FTS networks improve from 0.2 to 0.7-0.8. Certain ground stations show a clear asymmetry in δD during the transition from the dry to the wet season and back, which is also detected by SCIAMACHY. This asymmetry points to a transition in the source region temperature or location of the water vapour and shows the added information that HDO/H2O measurements provide when used in combination with variations in humidity.

Validation of SCIAMACHY HDO/H2O measurements using the TCCON and NDACC-MUSICA networks

NASA Astrophysics Data System (ADS)

Scheepmaker, R. A.; Frankenberg, C.; Deutscher, N. M.; Schneider, M.; Barthlott, S.; Blumenstock, T.; Garcia, O. E.; Hase, F.; Jones, N.; Mahieu, E.; Notholt, J.; Velazco, V.; Landgraf, J.; Aben, I.

2014-11-01

Measurements of the atmospheric HDO/H2O ratio help us to better understand the hydrological cycle and improve models to correctly simulate tropospheric humidity and therefore climate change. We present an updated version of the column-averaged HDO/H2O ratio dataset from the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY). The dataset is extended with two additional years, now covering 2003-2007, and is validated against co-located ground-based total column δD measurements from Fourier-Transform Spectrometers (FTS) of the Total Carbon Column Observing Network (TCCON) and the Network for the Detection of Atmospheric Composition Change (NDACC, produced within the framework of the MUSICA project). Even though the time overlap between the available data is not yet ideal, we determined a mean negative bias in SCIAMACHY δD of -35±30‰ compared to TCCON and -69±15‰ compared to MUSICA (the uncertainty indicating the station-to-station standard deviation). The bias shows a latitudinal dependency, being largest (∼ -60 to -80‰) at the highest latitudes and smallest (∼ -20 to -30‰) at the lowest latitudes. We have tested the impact of an offset correction to the SCIAMACHY HDO and H2O columns. This correction leads to a humidity and latitude dependent shift in δD and an improvement of the bias by 27‰, although it does not lead to an improved correlation with the FTS measurements nor to a strong reduction of the latitudinal dependency of the bias. The correction might be an improvement for dry, high-altitude areas, such as the Tibetan Plateau and the Andes region. For these areas, however, validation is currently impossible due to a lack of ground stations. The mean standard deviation of single-sounding SCIAMACHY-FTS differences is ∼ 115‰, which is reduced by a factor ∼ 2 when we consider monthly means. When we relax the strict matching of individual measurements and focus on the mean seasonalities using all available FTS data, we find that the correlation coefficients between SCIAMACHY and the FTS networks improve from 0.2 to 0.7-0.8. Certain ground stations show a clear asymmetry in δD during the transition from the dry to the wet season and back, which is also detected by SCIAMACHY. This asymmetry points to a transition in the source region temperature or location of the water vapor, and shows the added information that HDO/H2O measurements provide, if used in combination with variations in humidity.

Hydrodeoxygenation of Guaiacol Over Pt/Al-SBA-15 Catalysts.

PubMed

Yu, Mi Jin; Park, Sung Hoon; Jeon, Jong-Ki; Ryu, Changkook; Sohn, Jung Min; Kim, Sang Chai; Park, Young-Kwon

2015-01-01

Upgrading of bio-oil through catalytic hydrodeoxygenation (HDO) reaction was investigated for guaiacol as a model compound. A batch reactor was used for the reaction condition of 40 bar and 250 degrees C. The target product was cyclohexane. Pt/Al-SBA-15 with the Si/Al ratios of 20, 40, and 80 and Pt/HZSM-5 were used as the catalyst. The SBA-15 catalysts were characterized by N2 adsorption-desorption, X-ray diffraction analysis, and temperature programmed desorption of ammonia. The order of cyclohexane yield was Pt/Al-SBA-15 (Si/Al = 20) > Pt/Al-SBA-15(40) > Pt/Al-SBA-15 (80), indicating that the quantity of acid sites plays an important role in the HDO reaction. On the other hand, Pt/HZSM-5 led to a very low cyclohexane yield, in spite of its abundant strong acid sites, due to its small pore size.

Physical Properties and Seasonal Behavior of H2O, HDO, CO2 and Trace Gases on Mars: Quantitative Mapping from Earth-Based Observatories

NASA Technical Reports Server (NTRS)

Novak, Robert E.; Mumma, Michael J.

2011-01-01

Since 1997, we have used high-resolution (R greater than 40000) spectrometers on ground based-telescopes to study molecules that have astrobiological significance in Mars' atmosphere. We have used the NASA-IRTF, Keck II, and VLT telescopes in the 1.0-5.0 micron range. The spectrometer is set at a wavelength to detect specific molecules. Spectral/spatial images are produced. Extracts from these images provide column densities centered at latitude/longitude locations (resolution 400km at sub-Earth point). We have mapped the O2 singlet-Delta emission (a proxy for ozone), HDO, and H2O for seasonal dates throughout the Martian year. Previously undiscovered isotopic bands of CO2 have been identified along with isotopic forms of CO. We are searching for other molecules that have astrobiological importance and have successfully measured methane in Mars' atmosphere.

Hydrodeoxygenation of prairie cordgrass bio-oil over Ni based activated carbon synergistic catalysts combined with different metals.

PubMed

Cheng, Shouyun; Wei, Lin; Zhao, Xianhui; Kadis, Ethan; Cao, Yuhe; Julson, James; Gu, Zhengrong

2016-06-25

Bio-oil can be upgraded through hydrodeoxygenation (HDO). Low-cost and effective catalysts are crucial for the HDO process. In this study, four inexpensive combinations of Ni based activated carbon synergistic catalysts including Ni/AC, Ni-Fe/AC, Ni-Mo/AC and Ni-Cu/AC were evaluated for HDO of prairie cordgrass (PCG) bio-oil. The tests were carried out in the autoclave under mild operating conditions with 500psig of H2 pressure and 350°C temperature. The catalysts were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) and transmission electron microscope (TEM). The results show that all synergistic catalysts had significant improvements on the physicochemical properties (water content, pH, oxygen content, higher heating value and chemical compositions) of the upgraded PCG bio-oil. The higher heating value of the upgraded bio-oil (ranging from 29.65MJ/kg to 31.61MJ/kg) improved significantly in comparison with the raw bio-oil (11.33MJ/kg), while the oxygen content reduced to only 21.70-25.88% from 68.81% of the raw bio-oil. Compared to raw bio-oil (8.78% hydrocarbons and no alkyl-phenols), the Ni/AC catalysts produced the highest content of gasoline range hydrocarbons (C6-C12) at 32.63% in the upgraded bio-oil, while Ni-Mo/AC generated the upgraded bio-oil with the highest content of gasoline blending alkyl-phenols at 38.41%. Copyright © 2016 Elsevier B.V. All rights reserved.

Inconsistency in Reporting Abstention and Heavy Drinking Frequency: Associations with Sex and Socioeconomic Status, and Potential Impacts

PubMed Central

Kydd, Robyn M.; Connor, Jennie

2015-01-01

Aims: To describe inconsistencies in reporting past-year drinking status and heavy drinking occasions (HDOs) on single questions from two different instruments, and to identify associated characteristics and impacts. Methods: We compared computer-presented Alcohol Use Disorder Identification Test-Consumption (AUDIT-C) with categorical response options, and mental health interview (MHI) with open-ended consumption questions, completed on the same day. Participants were 464 men and 459 women aged 38 (91.7% of surviving birth cohort members). Differences in dichotomous single-item measures of abstention and HDO frequency, associations of inconsistent reporting with sex, socioeconomic status (SES) and survey order, and impacts of instrument choice on associations of alcohol with sex and SES were examined. Results: The AUDIT-C drinking frequency question estimated higher past-year abstention prevalence (AUDIT = 7.6%, MHI = 5.4%), with one-third of AUDIT-C abstainers being MHI drinkers. Only AUDIT-C produced significant sex differences in abstainer prevalence. Inconsistencies in HDO classifications were bidirectional, but with fewer HDOs reported on the MHI than AUDIT-C question. Lower SES was associated with inconsistency in abstention and weekly+ HDOs. Abstention and higher HDO frequency were associated with lower SES overall, but sex-specific associations differed by instrument. Conclusions: In this context, data collection method affected findings, with inconsistencies in abstention reports having most impact. Future studies should: (a) confirm self-reported abstention; (b) consider piloting data collection methods in target populations; (c) expect impacts of sex and SES on measurements and analyses. PMID:25648932

OT1_ebergin_5: A Systematic Survery of the Water D to H Ratio in Hot Molecular Cores

NASA Astrophysics Data System (ADS)

Bergin, E.

2010-07-01

The D/H ratio of water and the enrichment of HDO relative to H2O in comets, oceans, and interstellar water vapor, has been posited as one of the primary links between chemistry in the cold (T = 10-20 K) dense interstellar medium (ISM) and chemistry in the Solar Nebula. However, there are only ~10 measurements of HDO/H2O, even in hot (T > 100 K) molecular cores, which have the most favorable chemistry (due to fossil evaporation of D-enriched ices) and excitation. In addition the existing measurements have a wide range of uncertainty, making it impossible to discern the presence of source-to-source variations, which could hint at the origin of deuterium enrichments in the dense ISM. We propose here to change this statistic with a systematic survey of HDO and H2O in a sample of 20 hot molecular cores spanning a two order of magnitude range in mass and luminosity. This will increase the number of known water D/H ratios by ~200%. This program is unique in scope for Herschel and requires the uniformity in calibration and high spectral resolution offered by the HIFI instrument. With the stability of HIFI we will be able to derive D/H ratios with significantly less uncertainty. Our observations will be combined with theoretical chemical models to explore the statistics offered by this sample. By looking at a large number of objects with a range of conditions we aim to unlock the secrets of water deuteration in the interstellar space.

Upgrading biomass pyrolysis bio-oil to renewable fuels.

DOT National Transportation Integrated Search

2015-01-01

Fast pyrolysis is a process that can convert woody biomass to a crude bio-oil (pyrolysis oil). However, some of these compounds : contribute to bio-oil shelf life instability and difficulty in refining. Catalytic hydrodeoxygenation (HDO) of the bio-o...

Axle Lubricant Efficiency

DTIC Science & Technology

2014-05-09

state or reflect those of the United States Government or the DoA, and shall not be used for advertising or product endorsement purposes...Engine Control Module FMTV Family of Medium Tactical Vehicles GO Gear Oil GPS Global Positioning System GVW Gross Vehicle Weight HDO Heavy Duty Oil

Glucose- and Cellulose-Derived Ni/C-SO3H Catalysts for Liquid Phase Phenol Hydrodeoxygenation

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

Kasakov, Stanislav; Zhao, Chen; Barath, Eszter

2015-01-19

Sulfonated carbons were explored as functionalized supports for Ni nanoparticles to hydrodeoxygenate (HDO) phenol. Both hexadecane and water were used as solvents. The dual-functional Ni catalysts supported on sulfonated carbon (Ni/C-SO3H) showed high rates for phenol hydrodeoxygenation in liquid hexadecane, but not in water. Glucose and cellulose were precursors to the carbon supports. Changes in the carbons resulting from sulfonation of the carbons resulted in variations of carbon sheet structures, morphologies and the surface concentrations of acid sites. While the C-SO3H supports were active for cyclohexanol dehydration in hexadecane and water, Ni/C-SO3H only catalyzed the reduction of phenol to cyclohexanolmore » in water. The state of 3 – 5 nm grafted Ni particles was analyzed by in situ X-ray absorption spectroscopy. The results show that the metallic Ni was rapidly formed in situ without detectable leaching to the aqueous phase, suggesting that just the acid functions on Ni/C-SO3H are inhibited in presence of water. Using in situ IR spectroscopy, it was shown that even in hexadecane, phenol HDO is limited by the dehydration step. Thus, phenol HDO catalysis was further improved by physically admixing C-SO3H with the Ni/C-SO3H catalyst to balance the two catalytic functions. The minimum addition of 7 wt.% C-SO3H to the most active of the Ni/C-SO3H catalysts enabled nearly quantitative conversion of phenol and the highest selectivity (90%) towards cyclohexane in 6 h, at temperatures as low as 473 K, suggesting that the proximity to Ni limits the acid properties of the support.« less

Submillimeter mapping of mesospheric minor species on Venus with ALMA

NASA Astrophysics Data System (ADS)

Encrenaz, Therese; Moreno, Raphael; Moullet, Arielle; Lellouch, Emmanuel; Fouchet, Thierry

2014-05-01

ALMA offers a unique opportunity to map mesospheric species on Venus. During Cycle 0, we have observed Venus on November 14 and 15, 2011, using the compact configuration of ALMA. The diameter of Venus was 11 arcsec and the illumination factor was about 90 percent. Maps of CO, SO, SO2, and HDO have been built from transitions recorded in the 335-347 GHz frequency range. The mesospheric thermal profile has been inferred using the CO transition at 345.795 GHz. From the integrated spectrum of SO recorded on Nov. 14 at 346.528 GHz, we find that the best fit is obtained with a cut-off in the SO vertical distribution at about 88 km and a mean mixing ratio of about 8.0 ppb above this level. In the case of SO2, as for SO, we find that the best fit is obtained with a cut-off at about 88 km; the SO2 mixing ratio above this level is about 12 ppb. The map of HDO is retrieved from the 335.395 GHz transition. Assuming a typical D/H ratio of 200 times the terrestrial value in the mesosphere of Venus, we find that the disk averaged HDO spectrum is consistent with a H2O mixing ratio of about 2.5 ppm, constant with altitude. Our results are in good agreement with previous single dish submillimeter observations (Sandor and Clancy, Icarus 177, 129, 2005; Gurwell et al. Icarus 188, 288, 2007; Sandor et al. Icarus 208, 49, 2010; Icarus 217, 836, 2012), as well as with the predictions of photochemical models (Zhang et al. Icarus 217, 714, 2012).

Glucose- and cellulose-derived Ni/C-SO3H catalysts for liquid phase phenol hydrodeoxygenation.

PubMed

Kasakov, Stanislav; Zhao, Chen; Baráth, Eszter; Chase, Zizwe A; Fulton, John L; Camaioni, Donald M; Vjunov, Aleksei; Shi, Hui; Lercher, Johannes A

2015-01-19

Sulfonated carbons were explored as functionalized supports for Ni nanoparticles to hydrodeoxygenate (HDO) phenol. Both hexadecane and water were used as solvents. The dual-functional Ni catalysts supported on sulfonated carbon (Ni/C-SO3H) showed high rates for phenol hydrodeoxygenation in liquid hexadecane, but not in water. Glucose and cellulose were precursors to the carbon supports. Changes in the carbons resulting from sulfonation of the carbons resulted in variations of carbon sheet structures, morphologies and the surface concentrations of acid sites. While the C-SO3H supports were active for cyclohexanol dehydration in hexadecane and water, Ni/C-SO3H only catalysed the reduction of phenol to cyclohexanol in water. The state of 3-5 nm grafted Ni particles was analysed by in situ X-ray absorption spectroscopy. The results show that the metallic Ni was rapidly formed in situ without detectable leaching to the aqueous phase, suggesting that just the acid functions on Ni/C-SO3H are inhibited in the presence of water. Using in situ IR spectroscopy, it was shown that even in hexadecane, phenol HDO is limited by the dehydration step. Thus, phenol HDO catalysis was further improved by physically admixing C-SO3H with the Ni/C-SO3H catalyst to balance the two catalytic functions. The minimum addition of 7 wt % C-SO3H to the most active of the Ni/C-SO3H catalysts enabled nearly quantitative conversion of phenol and the highest selectivity (90%) towards cyclohexane in 6 h, at temperatures as low as 473 K, suggesting that the proximity to Ni limits the acid properties of the support. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fundamental studies of catalytic processing of synthetic liquids. Final report

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

Watson, P.R.

1994-06-15

Liquids derived from coal contain relatively high amounts of oxygenated organic compounds, mainly in the form of phenols and furans that are deleterious to the stability and quality of these liquids as fuels. Hydrodeoxygenation (HDO) using Mo/W sulfide catalysts is a promising method to accomplish this removal, but our understanding of the reactions occurring on the catalyst surface during HDO is very limited. Rather than attempting to examine the complexities of real liquids and catalysts we have adopted an approach here using model systems amenable to surface-sensitive techniques that enable us to probe in detail the fundamental processes occurring duringmore » HDO at the surfaces of well-defined model catalysts. The results of this work may lead to the development of more efficient, selective and stable catalysts. Above a S/Mo ratio of about 0.5 ML, furan does not adsorb on sulfided Mo surfaces; as the sulfur coverage is lowered increasing amounts of furan can be adsorbed. Temperature-programmed reaction spectroscopy (TPRS) reveals that C-H, C-C and C-O bond scission occurs on these surfaces. Auger spectra show characteristic changes in the nature and amount of surface carbon. Comparisons with experiments carried out with CO, H{sub 2} and alkenes show that reaction pathways include -- direct abstraction of CO at low temperatures; cracking and release of hydrogen below its normal desorption temperature; dehydrogenatin of adsorbed hydrocarbon fragments; recombination of C and O atoms and dissolution of carbon into the bulk at high temperatures. Performing the adsorption or thermal reaction in 10{sup {minus}5} torr of hydrogen does not change the mode of reaction significantly.« less

Methane measurement by the Pioneer Venus large probe neutral mass spectrometer

NASA Technical Reports Server (NTRS)

Donahue, T. M.; Hodges, R. R., Jr.

1992-01-01

The Pioneer Venus Large Probe Mass Spectrometer detected a large quantity of methane as it descended below 20 km in the atmosphere of Venus. Terrestrial methane and Xe-136, both originating in the same container and flowing through the same plumbing, were deliberately released inside the mass spectrometer for instrumental reasons. However, the Xe-136 did not exhibit behavior similar to methane during Venus entry, nor did CH4 in laboratory simulations. The CH4 was deuterium poor compared to Venus water and hydrogen. While the inlet to the mass spectrometer was clogged with sulfuric acid droplets, significant deuteration of CH4 and its H2 progeny was observed. Since the only source of deuterium identifiable was water from sulfuric acid, we have concluded that we should correct the HDO/H2O ratio in Venus water from 3.2 x 10(exp -2) to (5 plus or minus 0.7) x 10(exp -2). When the probe was in the lower atmosphere, transfer of deuterium from Venus HDO and HD to CH4 can account quantitatively for the deficiencies recorded in HDO and HD below 10 km, and consequently, the mysterious gradients in water vapor and hydrogen mixing ratios we have reported. The revision in the D/H ratio reduces the mixing ratio of water vapor (and H2) reported previously by a factor of 3.2/5. We are not yet able to say whether the methane detected was atmospheric or an instrumental artifact. If it was atmospheric, its release must have been episodic and highly localized. Otherwise, the large D/H ratio in Venus water and hydrogen could not be maintained.

Methane measurement by the Pioneer Venus large probe neutral mass spectrometer

NASA Astrophysics Data System (ADS)

Donahue, T. M.; Hodges, R. R., Jr.

1992-12-01

The Pioneer Venus Large Probe Mass Spectrometer detected a large quantity of methane as it descended below 20 km in the atmosphere of Venus. Terrestrial methane and Xe-136, both originating in the same container and flowing through the same plumbing, were deliberately released inside the mass spectrometer for instrumental reasons. However, the Xe-136 did not exhibit behavior similar to methane during Venus entry, nor did CH4 in laboratory simulations. The CH4 was deuterium poor compared to Venus water and hydrogen. While the inlet to the mass spectrometer was clogged with sulfuric acid droplets, significant deuteration of CH4 and its H2 progeny was observed. Since the only source of deuterium identifiable was water from sulfuric acid, we have concluded that we should correct the HDO/H2O ratio in Venus water from 3.2 x 10-2 to (5 plus or minus 0.7) x 10-2. When the probe was in the lower atmosphere, transfer of deuterium from Venus HDO and HD to CH4 can account quantitatively for the deficiencies recorded in HDO and HD below 10 km, and consequently, the mysterious gradients in water vapor and hydrogen mixing ratios we have reported. The revision in the D/H ratio reduces the mixing ratio of water vapor (and H2) reported previously by a factor of 3.2/5. We are not yet able to say whether the methane detected was atmospheric or an instrumental artifact. If it was atmospheric, its release must have been episodic and highly localized. Otherwise, the large D/H ratio in Venus water and hydrogen could not be maintained.

Simulations of the HDO and H2O-18 atmospheric cycles using the NASA GISS general circulation model - Sensitivity experiments for present-day conditions

NASA Technical Reports Server (NTRS)

Jouzel, Jean; Koster, R. D.; Suozzo, R. J.; Russell, G. L.; White, J. W. C.

1991-01-01

Incorporating the full geochemical cycles of stable water isotopes (HDO and H2O-18) into an atmospheric general circulation model (GCM) allows an improved understanding of global delta-D and delta-O-18 distributions and might even allow an analysis of the GCM's hydrological cycle. A detailed sensitivity analysis using the NASA/Goddard Institute for Space Studies (GISS) model II GCM is presented that examines the nature of isotope modeling. The tests indicate that delta-D and delta-O-18 values in nonpolar regions are not strongly sensitive to details in the model precipitation parameterizations. This result, while implying that isotope modeling has limited potential use in the calibration of GCM convection schemes, also suggests that certain necessarily arbitrary aspects of these schemes are adequate for many isotope studies. Deuterium excess, a second-order variable, does show some sensitivity to precipitation parameterization and thus may be more useful for GCM calibration.

Guaiacol hydrodeoxygenation mechanism on Pt(111): insights from density functional theory and linear free energy relations.

PubMed

Lee, Kyungtae; Gu, Geun Ho; Mullen, Charles A; Boateng, Akwasi A; Vlachos, Dionisios G

2015-01-01

Density functional theory is used to study the adsorption of guaiacol and its initial hydrodeoxygenation (HDO) reactions on Pt(111). Previous Brønsted-Evans-Polanyi (BEP) correlations for small open-chain molecules are inadequate in estimating the reaction barriers of phenolic compounds except for the side group (methoxy) carbon-dehydrogenation. New BEP relations are established using a select group of phenolic compounds. These relations are applied to construct a potential-energy surface of guaiacol-HDO to catechol. Analysis shows that catechol is mainly produced via dehydrogenation of the methoxy functional group followed by the CHx (x<3) removal of the functional group and hydrogenation of the ring carbon, in contrast to a hypothesis of a direct demethylation path. Dehydroxylation and demethoxylation are slow, implying that phenol is likely produced from catechol but not through its direct dehydroxylation followed by aromatic carbon-ring hydrogenation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bio-oil from fast pyrolysis of lignin: Effects of process and upgrading parameters.

PubMed

Fan, Liangliang; Zhang, Yaning; Liu, Shiyu; Zhou, Nan; Chen, Paul; Cheng, Yanling; Addy, Min; Lu, Qian; Omar, Muhammad Mubashar; Liu, Yuhuan; Wang, Yunpu; Dai, Leilei; Anderson, Erik; Peng, Peng; Lei, Hanwu; Ruan, Roger

2017-10-01

Effects of process parameters on the yield and chemical profile of bio-oil from fast pyrolysis of lignin and the processes for lignin-derived bio-oil upgrading were reviewed. Various process parameters including pyrolysis temperature, reactor types, lignin characteristics, residence time, and feeding rate were discussed and the optimal parameter conditions for improved bio-oil yield and quality were concluded. In terms of lignin-derived bio-oil upgrading, three routes including pretreatment of lignin, catalytic upgrading, and co-pyrolysis of hydrogen-rich materials have been investigated. Zeolite cracking and hydrodeoxygenation (HDO) treatment are two main methods for catalytic upgrading of lignin-derived bio-oil. Factors affecting zeolite activity and the main zeolite catalytic mechanisms for lignin conversion were analyzed. Noble metal-based catalysts and metal sulfide catalysts are normally used as the HDO catalysts and the conversion mechanisms associated with a series of reactions have been proposed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Deoxygenation of glycolaldehyde and furfural on Mo2C/Mo(100)

NASA Astrophysics Data System (ADS)

McManus, Jesse R.; Vohs, John M.

2014-12-01

The desire to produce fuels and chemicals in an energy conscious, environmentally sympathetic approach has motivated considerable research on the use of cellulosic biomass feedstocks. One of the major challenges facing the utilization of biomass is finding effective catalysts for the efficient and selective removal of oxygen from the highly-oxygenated, biomass-derived platform molecules. Herein, a study of the reaction pathways for the biomass-derived platform molecule furfural and biomass-derived sugar model compound glycolaldehyde provides insight into the mechanisms of hydrodeoxygenation (HDO) on a model molybdenum carbide catalyst, Mo2C/Mo(100). Using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS), it was found that the Mo2C/Mo(100) catalyst was active for selective deoxygenation of the aldehyde carbonyl by facilitating adsorption of the aldehyde in an η2(C,O) bonding configuration. Furthermore, the catalyst showed no appreciable activity for furanic ring hydrogenation, highlighting the promise of relatively inexpensive Mo2C catalysts for selective HDO chemistry.

Synthesis of high density aviation fuel with cyclopentanol derived from lignocellulose

NASA Astrophysics Data System (ADS)

Sheng, Xueru; Li, Ning; Li, Guangyi; Wang, Wentao; Yang, Jinfan; Cong, Yu; Wang, Aiqin; Wang, Xiaodong; Zhang, Tao

2015-03-01

For the first time, renewable high density aviation fuels were synthesized at high overall yield (95.6%) by the Guerbet reaction of cyclopentanol which can be derived from lignocellulose, followed by the hydrodeoxygenation (HDO). The solvent-free Guerbet reaction of cyclopentanol was carried out under the co-catalysis of solid bases and Raney metals. Among the investigated catalyst systems, the combinations of magnesium-aluminium hydrotalcite (MgAl-HT) and Raney Ni (or Raney Co) exhibited the best performances. Over them, high carbon yield (96.7%) of C10 and C15 oxygenates was achieved. The Guerbet reaction products were further hydrodeoxygenated to bi(cyclopentane) and tri(cyclopentane) over a series of Ni catalysts. These alkanes have high densities (0.86 g mL-1 and 0.91 g mL-1) and can be used as high density aviation fuels or additives to bio-jet fuel. Among the investigated HDO catalysts, the 35 wt.% Ni-SiO2-DP prepared by deposition-precipitation method exhibited the highest activity.

Synthesis of high density aviation fuel with cyclopentanol derived from lignocellulose.

PubMed

Sheng, Xueru; Li, Ning; Li, Guangyi; Wang, Wentao; Yang, Jinfan; Cong, Yu; Wang, Aiqin; Wang, Xiaodong; Zhang, Tao

2015-03-31

For the first time, renewable high density aviation fuels were synthesized at high overall yield (95.6%) by the Guerbet reaction of cyclopentanol which can be derived from lignocellulose, followed by the hydrodeoxygenation (HDO). The solvent-free Guerbet reaction of cyclopentanol was carried out under the co-catalysis of solid bases and Raney metals. Among the investigated catalyst systems, the combinations of magnesium-aluminium hydrotalcite (MgAl-HT) and Raney Ni (or Raney Co) exhibited the best performances. Over them, high carbon yield (96.7%) of C10 and C15 oxygenates was achieved. The Guerbet reaction products were further hydrodeoxygenated to bi(cyclopentane) and tri(cyclopentane) over a series of Ni catalysts. These alkanes have high densities (0.86 g mL(-1) and 0.91 g mL(-1)) and can be used as high density aviation fuels or additives to bio-jet fuel. Among the investigated HDO catalysts, the 35 wt.% Ni-SiO2-DP prepared by deposition-precipitation method exhibited the highest activity.

Biobased alkylphenols from lignins via a two-step pyrolysis - Hydrodeoxygenation approach.

PubMed

de Wild, P J; Huijgen, W J J; Kloekhorst, A; Chowdari, R K; Heeres, H J

2017-04-01

Five technical lignins (three organosolv, Kraft and soda lignin) were depolymerised to produce monomeric biobased aromatics, particularly alkylphenols, by a new two-stage thermochemical approach consisting of dedicated pyrolysis followed by catalytic hydrodeoxygenation (HDO) of the resulting pyrolysis oils. Pyrolysis yielded a mixture of guaiacols, catechols and, optionally, syringols in addition to alkylphenols. HDO with heterogeneous catalysts (Ru/C, CoMo/alumina, phosphided NiMO/C) effectively directed the product mixture towards alkylphenols by, among others, demethoxylation. Up to 15wt% monomeric aromatics of which 11wt% alkylphenols was obtained (on the lignin intake) with limited solid formation (<3wt% on lignin oil intake). For comparison, solid Kraft lignin was also directly hydrotreated for simultaneous depolymerisation and deoxygenation resulting in two times more alkylphenols. However, the alkylphenols concentration in the product oil is higher for the two-stage approach. Future research should compare direct hydrotreatment and the two-stage approach in more detail by techno-economic assessments. Copyright © 2017 Elsevier Ltd. All rights reserved.

Highly Selective Relaxation of the OH Stretching Overtones in Isolated HDO Molecules Observed by Infrared Pump-Repump-Probe Spectroscopy.

PubMed

Hutzler, Daniel; Werhahn, Jasper C; Heider, Rupert; Bradler, Maximilian; Kienberger, Reinhard; Riedle, Eberhard; Iglev, Hristo

2015-07-02

A quantitative investigation of the relaxation dynamics of higher-lying vibrational states is afforded by a novel method of infrared pump-repump-probe spectroscopy. The technique is used to study the dynamics of OH stretching overtones in NaClO4·HDO monohydrate. We observe a continuous decrease of the energy separation for the first four states, i.e. v01 = 3575 cm(-1), v12 = 3370 cm(-1), and v23 = 3170 cm(-1), respectively. The population lifetime of the first excited state is 7.2 ps, while the one of the second excited state is largely reduced to 1.4 ps. The relaxation of the v = 2 state proceeds nearly quantitatively to the v = 1 state. The new information on the OH stretching overtones demands improved theoretical potentials and modeling of the H bond interactions. This work shows the potential of the new technique for the precise study of complex vibrational relaxation pathways.

Catalytic cracking of fast and tail gas reactive pyrolysis bio-oils over HZSM-5

USDA-ARS?s Scientific Manuscript database

While hydrodeoxygenation (HDO) of pyrolysis oil is well understood as an upgrading method, the high processing pressures associated with it alone justify the exploration of alternative upgrading solutions, especially those that could adapt pyrolysis oils into the existing refinery infrastructure. Ca...

Anomalous Centrifugal Distortion in HDO and Spectroscopic Data Bases

NASA Astrophysics Data System (ADS)

Coudert, L. H.

2015-06-01

The HDO molecule is important from the atmospheric point of view as it can be used to study the water cycle in the earth atmosphere. It is also interesting from the spectroscopic point of view as it displays an anomalous centrifugal distortion similar to that of the normal species H_2O. A model developed to treat the anomalous distortion in HDO should account for the fact that it lacks a two-fold axis of symmetry. A new treatment aimed at the calculation of the rovibrational energy of the HDO molecule and allowing for anomalous centrifugal distortion effects has been developed. It is based on an effective Hamiltonian in which the large amplitude bending ν_2 mode and the overall rotation of the molecule are treated simultaneously. Due to the lack of a two-fold axis of symmetry, this effective Hamiltonian contains terms arising from the non-diagonal component of the inertia tensor and from the Coriolis-coupling between the large amplitude bending ν_2 mode and the overall rotation of the molecule. This new treatment has been used to perform a line position analysis of a large body of infrared, microwave, and hot water vapor data involving the ground and (010) states up to J=22. For these 4413 data, a unitless standard deviation of 1.1 was achieved. A line intensity analysis was also carried out and allowed us to reproduce the strength of 1316 transitions^c with a unitless standard deviation of 1.1. In the talk, the new theoretical approach will be presented. The results of both analyses will be discussed and compared with those of a previous investigation. The new spectroscopic data base built will be compared with HITRAN 2012. Herbin et al., Atmos. Chem. Phys.~9 (2009) 9433; and Schneider and Hase, Atmos. Chem. Phys.~ 11 (2011) 11207. Coudert, Wagner, Birk, Baranov, Lafferty, and Flaud, J. Molec. Spectrosc.~251 (2008) 339. Johns, J. Opt. Soc. Am. B~2 (1985) 1340 Toth, J. Molec. Spectrosc.~162 (1993) 20 Paso and Horneman, J. Opt. Soc. Am. B~12 (1995) 1813 Toth, J. Molec. Spectrosc.~195 (1999) 73. Messer, De Lucia, and Helminger, J. Molec. Spectrosc.~105 (1984) 139; and Baskakov et al., Opt. Spectrosc.~63 (1987) 1016. Parekunnel et al., J. Molec. Spectrosc.~210 (2001) 28 Janca et al., J. Molec. Specrosc.~219 (2003) 132. Tennyson et al., J. Quant. Spectrosc. Radiat. Transfer~111 (2010) 2160. Rothman et al., J. Quant. Spectrosc. Radiat. Transfer~130 (2013) 4.

A Low-cost, High-yield Process for the Direct Productin of High Energy Density Liquid Fuel from Biomass

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

Agrawal, Rakesh; Delgass, W. N.; Ribeiro, F.

2013-08-31

The primary objective and outcome of this project was the development and validation of a novel, low-cost, high-pressure fast-hydropyrolysis/hydrodeoxygenation (HDO) process (H 2Bioil) using supplementary hydrogen (H 2) to produce liquid hydrocarbons from biomass. The research efforts under the various tasks of the project have culminated in the first experimental demonstration of the H 2Bioil process, producing 100% deoxygenated >C4+ hydrocarbons containing 36-40% of the carbon in the feed of pyrolysis products from biomass. The demonstrated H{sub 2}Bioil process technology (i.e. reactor, catalyst, and downstream product recovery) is scalable to a commercial level and is estimated to be economically competitivemore » for the cases when supplementary H 2 is sourced from coal, natural gas, or nuclear. Additionally, energy systems modeling has revealed several process integration options based on the H 2Bioilprocess for energy and carbon efficient liquid fuel production. All project tasks and milestones were completed or exceeded. Novel, commercially-scalable, high-pressure reactors for both fast-hydropyrolysis and hydrodeoxygenation were constructed, completing Task A. These reactors were capable of operation under a wide-range of conditions; enabling process studies that lead to identification of optimum process conditions. Model compounds representing biomass pyrolysis products were studied, completing Task B. These studies were critical in identifying and developing HDO catalysts to target specific oxygen functional groups. These process and model compound catalyst studies enabled identification of catalysts that achieved 100% deoxygenation of the real biomass feedstock, sorghum, to form hydrocarbons in high yields as part of Task C. The work completed during this grant has identified and validated the novel and commercially scalable H 2Bioil process for production of hydrocarbon fuels from biomass. Studies on model compounds as well as real biomass feedstocks were utilized to identify optimized process conditions and selective HDO catalyst for high yield production of hydrocarbons from biomass. In addition to these experimental efforts, in Tasks D and E, we have developed a mathematical optimization framework to identify carbon and energy efficient biomass-to-liquid fuel process designs that integrate the use of different primary energy sources along with biomass (e.g. solar, coal or natural gas) for liquid fuel production. Using this tool, we have identified augmented biomass-to-liquid fuel configurations based on the fast-hydropyrolysis/HDO pathway, which was experimentally studied in this project. The computational approach used for screening alternative process configurations represents a unique contribution to the field of biomass processing for liquid fuel production.« less

Mechanism of dehydration of phenols on nobel metals using first-principles micokinetic modeling

USDA-ARS?s Scientific Manuscript database

Phenolic compounds constitute a sizable fraction of depolymerized biomass and are an ideal feedstock for the production of chemicals such as benzene and toluene. However, these compounds require catalytic upgrade via hydrodeoxygenation (HDO), a process whereby oxygen is removed as water by adding hy...

Long-term series of tropospheric water vapour amounts and HDO/H2O ratio profiles above Jungfraujoch.

NASA Astrophysics Data System (ADS)

Lejeune, B.; Mahieu, E.; Schneider, M.; Hase, F.; Servais, C.; Demoulin, P.

2012-04-01

Water vapour is a crucial climate variable involved in many processes which widely determine the energy budget of our planet. In particular, water vapour is the dominant greenhouse gas in the Earth's atmosphere and its radiative forcing is maximum in the middle and upper troposphere. Because of the extremely high variability of water vapour concentration in time and space, it is challenging for the available relevant measurement techniques to provide a consistent data set useful for trend analyses and climate studies. Schneider et al. (2006a) showed that ground-based Fourier Transform Infrared (FTIR) spectroscopy, performed from mountain observatories, allows for the detection of H2O variabilities up to the tropopause. Furthermore, the FTIR measurements allow the retrieval of HDO amounts and therefore the monitoring of HDO/H2O ratio profiles whose variations act as markers for the source and history of the atmospheric water vapour. In the framework of the MUSICA European project (Multi-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water, http://www.imk-asf.kit.edu/english/musica.php), a new approach has been developed and optimized by M. Schneider and F. Hase, using the PROFFIT algorithm, to consistently retrieve tropospheric water vapour profiles from high-resolution ground-based infrared solar spectra and so taking benefit from available long-term data sets of ground-based observations. The retrieval of the water isotopologues is performed on a logarithmic scale from 14 micro-windows located in the 2600-3100 cm-1 region. Other important features of this new retrieval strategy are: a speed dependant Voigt line shape model, a joint temperature profile retrieval and an interspecies constraint for the HDO/H2O profiles. In this contribution, we will combine the quality of the MUSICA strategy and of our observations, which are recorded on a regular basis with FTIR spectrometers, under clear-sky conditions, at the NDACC site (Network for the Detection of Atmospheric Composition Change, http://www.ndacc.org) of the Jungfraujoch International Scientific Station (Swiss Alps, 46.5° N, 8.0° E, 3580m asl). Information content analysis of the retrieved H2O products allows us to produce a long-term trend from 1996 to 2011 for different tropospheric levels. We will compare the annual cycle of tropospheric HDO/H2O ratio profiles with those already produced at other sites (Schneider et al., 2010). We will also focus on the diurnal variability of water vapour to determine a time limit in the inter-comparison of different water vapour measurement techniques. Acknowledgments The University of Liège involvement has primarily been supported by the PRODEX program funded by the Belgian Federal Science Policy Office, Brussels and by the Swiss GAW-CH program. The FRS-FNRS and the Fédération Wallonie-Bruxelles are further acknowledged for observational activities support. We thank the International Foundation High Altitude Research Stations Jungfraujoch and Gornergrat (HFSJG, Bern) for supporting the facilities needed to perform the observations. MUSICA is funded by the European Research Council under the European Community's Seventh Framework Programme (FP7/2007-2013) / ERC Grant agreement n° 256961.

Guaiacol hydrodeoxygenation mechanism on Pt(111): Insights from density functional theory and linear free energy relations

USDA-ARS?s Scientific Manuscript database

In this study density functional theory (DFT) was used to study the adsorption of guaiacol and its initial hydrodeoxygenation (HDO) reactions on Pt(111). Previously reported Brønsted–Evans–Polanyi (BEP) correlations for small open chain molecules are found to be inadequate in estimating the reaction...

Stable Water Isotope Climate Archives in Springs from the Olympic Mountains, Washington

EPA Science Inventory

The ¹⁸O and ²H (HDO) compositions are summarized for sampled springs (n = 81) within the Elwha watershed (≈ 692 km²) on the northern Olympic Peninsula. Samples, collected during 2001–2009, of springs (n = 158), precipitation (n = 520), streams (n...

Saturation Transfer Difference NMR as an Analytical Tool for Detection and Differentiation of Plastic Explosives on the Basis of Minor Plasticizer Composition

DTIC Science & Technology

2015-05-01

HMX ); ethylene glycol dinitrate (EGDN); ammonium nitrate (AN); and nitrocellulose (NC).1–4 Alternatively, in one recent study,5 fluorescence-based...saturation transfer difference AN ammonium nitrate BSA bovine serum albumin EGDN ethylene glycol dinitrate HDO partially deuterated water HMX

Measurement of the Isotopic Signatures of Water on Mars: Implications for Studying Methane

NASA Technical Reports Server (NTRS)

Novak, R. E.; Mumma, M. J.; Villanueva, G. L.

2010-01-01

The recent discovery of methane on Mars has led to much discussion concerning its origin. On Earth, the isotopic signatures of methane vary with the nature of its production. Specifically, the ratios among 12CH4, 13CH4, and 12CH3D differ for biotic and abiotic origins. On Mars, measuring these ratios would provide insights into the origins of methane and measurements of water isotopologues co-released with methane would assist in testing their chemical relationship. Since 1997, we have been measuring HDO and H2O in Mars atmosphere and comparing their ratio to that in Earth s oceans. We recently incorporated a line-by-line radiative transfer model (LBLRTM) into our analysis. Here, we present a map for [HDO]/[H2O] along the central meridian (1541W) for Ls 501. From these results, we constructed models to determine the observational conditions needed to quantify the isotopic ratios of methane in Mars atmosphere. Current ground-based instruments lack the spectral resolution and sensitivity needed to make these measurements. Measurements of the isotopologues of methane will likely require in situ sampling.

Synthesis of high density aviation fuel with cyclopentanol derived from lignocellulose

PubMed Central

Sheng, Xueru; Li, Ning; Li, Guangyi; Wang, Wentao; Yang, Jinfan; Cong, Yu; Wang, Aiqin; Wang, Xiaodong; Zhang, Tao

2015-01-01

For the first time, renewable high density aviation fuels were synthesized at high overall yield (95.6%) by the Guerbet reaction of cyclopentanol which can be derived from lignocellulose, followed by the hydrodeoxygenation (HDO). The solvent-free Guerbet reaction of cyclopentanol was carried out under the co-catalysis of solid bases and Raney metals. Among the investigated catalyst systems, the combinations of magnesium-aluminium hydrotalcite (MgAl-HT) and Raney Ni (or Raney Co) exhibited the best performances. Over them, high carbon yield (96.7%) of C10 and C15 oxygenates was achieved. The Guerbet reaction products were further hydrodeoxygenated to bi(cyclopentane) and tri(cyclopentane) over a series of Ni catalysts. These alkanes have high densities (0.86 g mL−1 and 0.91 g mL−1) and can be used as high density aviation fuels or additives to bio-jet fuel. Among the investigated HDO catalysts, the 35 wt.% Ni-SiO2-DP prepared by deposition-precipitation method exhibited the highest activity. PMID:25826744

A full-mission data set of H2O and HDO columns from SCIAMACHY 2.3 µm reflectance measurements

NASA Astrophysics Data System (ADS)

Schneider, Andreas; Borsdorff, Tobias; aan de Brugh, Joost; Hu, Haili; Landgraf, Jochen

2018-06-01

A new data set of vertical column densities of the water vapour isotopologues H2O and HDO from the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) instrument for the whole of the mission period from January 2003 to April 2012 is presented. The data are retrieved from reflectance measurements in the spectral range 2339 to 2383 nm with the Shortwave Infrared CO Retrieval (SICOR) algorithm, ignoring atmospheric light scattering in the measurement simulation. The retrievals are validated with ground-based Fourier transform infrared measurements obtained within the Multi-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water (MUSICA) project. A good agreement for low-altitude stations is found with an average bias of -3.6×1021 for H2O and -1.0×1018 molec cm-2 for HDO. The a posteriori computed δD shows an average bias of -8 ‰, even though polar stations have a larger negative bias. The latter is due to the large amount of sensor noise in SCIAMACHY in combination with low albedo and high solar zenith angles. To demonstrate the benefit of accounting for light scattering in the retrieval, the quality of the data product fitting effective cloud parameters simultaneously with trace gas columns is evaluated in a dedicated case study for measurements round high-altitude stations. Due to a large altitude difference between the satellite ground pixel and the mountain station, clear-sky scenes yield a large bias, resulting in a δD bias of 125 ‰. When selecting scenes with optically thick clouds within 1000 m above or below the station altitude, the bias in a posteriori δD is reduced from 125 to 44 ‰. The insights from the present study will also benefit the analysis of the data from the new Sentinel-5 Precursor mission.

Bifunctional Molybdenum Polyoxometalates for the Combined Hydrodeoxygenation and Alkylation of Lignin-Derived Model Phenolics.

PubMed

Anderson, Eric; Crisci, Anthony; Murugappan, Karthick; Román-Leshkov, Yuriy

2017-05-22

Reductive catalytic fractionation of biomass has recently emerged as a powerful lignin extraction and depolymerization method to produce monomeric aromatic oxygenates in high yields. Here, bifunctional molybdenum-based polyoxometalates supported on titania (POM/TiO 2 ) are shown to promote tandem hydrodeoxygenation (HDO) and alkylation reactions, converting lignin-derived oxygenated aromatics into alkylated benzenes and alkylated phenols in high yields. In particular, anisole and 4-propylguaiacol were used as model compounds for this gas-phase study using a packed-bed flow reactor. For anisole, 30 % selectivity for alkylated aromatic compounds (54 % C-alkylation of the methoxy groups by methyl balance) with an overall 72 % selectivity for HDO at 82 % anisole conversion was observed over H 3 PMo 12 O 40 /TiO 2 at 7 h on stream. Under similar conditions, 4-propylguaiacol was mainly converted into 4-propylphenol and alkylated 4-propylphenols with a selectivity to alkylated 4-propylphenols of 42 % (77 % C-alkylation) with a total HDO selectivity to 4-propylbenzene and alkylated 4-propylbenzenes of 4 % at 92 % conversion (7 h on stream). Higher catalyst loadings pushed the 4-propylguaiacol conversion to 100 % and resulted in a higher selectivity to propylbenzene of 41 %, alkylated aromatics of 21 % and alkylated phenols of 17 % (51 % C-alkylation). The reactivity studies coupled with catalyst characterization revealed that Lewis acid sites act synergistically with neighboring Brønsted acid sites to simultaneously promote alkylation and hydrodeoxygenation activity. A reaction mechanism is proposed involving activation of the ether bond on a Lewis acid site, followed by methyl transfer and C-alkylation. Mo-based POMs represent a versatile catalytic platform to simultaneously upgrade lignin-derived oxygenated aromatics into alkylated arenes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental Results of Fractionation of HDO and H2O with simulated Martian Dust: Implications for the interpretation of past climate on Mars

NASA Astrophysics Data System (ADS)

Moores, J. E.; Smith, P.; Brown, R.; Lauretta, D.; Boynton, W.

2009-05-01

Climate change on Mars has been greatly debated in recent years. This has been motivated by the results from the Mars Reconnaissance Orbiter, Phoenix Lander and ground-based spectroscopic studies which have found mounting evidence that not only may Mars have had a wet and warm past, but those conditions inclement to life may also have been present more recently. On Mars, this is largely a story of water transport and, as on the Earth, isotopic analysis presents a key to understanding and decoding the Martian paleoclimate. For Mars, the major fractionation observed is in HDO, analogous to the Oxygen-18 cycle on Earth, and observations have shown that the D/H ratio of the planet is enriched by a factor of 5 to 6 from comparable terrestrial values. The conventional explanation is that a great deal of water has been lost to space over geologic time. However, previous studies have not taken into account the ability of present-day Mars to fractionate water as it moves from the polar caps to the polar layered deposits through the atmosphere, potentially masking any climate signal which may exist. In this presentation, we shall report on a series of Mars analogue experiments completed at the relevant ranges of pressure and temperature. Two different scenarios were simulated: the sublimation of dusty water ice and the sublimation of clean water ice through a simulated regolith/dust lag. In both cases, we have found that the system is dominated by adsorption of water. However, the simulant dust (JSC-1) appears to be an extremely efficient vehicle for fractionating water at cold temperatures, as different desorption rates have been recorded for HDO and H2O. This, when coupled with the relatively small amount of water exchanging today implies heavy fractionations in the current Mars system without requiring significant water losses to space.

Spectroscopy of Mars Atmosphere from Orbiting and Ground-based Observatories: Recent Results and Implications for Evolution

NASA Astrophysics Data System (ADS)

Krasnopolsky, V. A.

2003-07-01

This is a review of the ground-based and Earth-orbiting studies of Mars atmosphere in the last decade that resulted in the detections of HDO, D, H2, He, and detailed mapping of O3, O2(delta), and CO. These studies provide new insights on the history of volatiles and climate on Mars.

Synergy in Lignin Upgrading by a Combination of Cu-Based Mixed Oxide and Ni-Phosphide Catalysts in Supercritical Ethanol

PubMed Central

2017-01-01

The depolymerization of lignin to bioaromatics usually requires a hydrodeoxygenation (HDO) step to lower the oxygen content. A mixed Cu–Mg–Al oxide (CuMgAlOx) is an effective catalyst for the depolymerization of lignin in supercritical ethanol. We explored the use of Ni-based cocatalysts, i.e. Ni/SiO2, Ni2P/SiO2, and Ni/ASA (ASA = amorphous silica alumina), with the aim of combining lignin depolymerization and HDO in a single reaction step. While the silica-supported catalysts were themselves hardly active in lignin upgrading, Ni/ASA displayed comparable lignin monomer yield as CuMgAlOx. A drawback of using an acidic support is extensive dehydration of the ethanol solvent. Instead, combining CuMgAlOx with Ni/SiO2 and especially Ni2P/SiO2 proved to be effective in increasing the lignin monomer yield, while at the same time reducing the oxygen content of the products. With Ni2P/SiO2, the lignin monomer yield was 53 wt %, leading to nearly complete deoxygenation of the aromatic products. PMID:28405528

Legacy Effect of Amazonian Drought Delays the Season Transition from Dry to Wet

NASA Astrophysics Data System (ADS)

Shi, M.; Liu, J.; Wong, S.; Worden, J. R.; Fisher, J.; Frankenberg, C.

2017-12-01

The long-term drought effect on forest coverage, so-called legacy effect, has been observed in ground and remote sensing measurements. Drought and forest loss may amplify each other through vegetation-atmosphere feedbacks. In this study, we investigate the impact of the reduced growth of southern Amazonian forest from the 2005 drought on dry-to-wet season transition and its variations in 2005 and 2006. We quantified the vegetation-atmosphere feedbacks with the Community Atmosphere Model version 5 (CAM5) with a control and a sensitivity experiments. We further investigate the mechanism of vegetation-atmosphere feedbacks with data-constrained evapotranspiration (ET) and HDO/H2O observations from the Scanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) and from the Tropospheric Emission Spectrometer (TES). Our results show that the dry season end (DSE) in southern Amazonian forest was delayed by 15 days in 2005 and by 25 days in 2006 with drought induced leaf carbon pool reduction. The postponed DSE is triggered by the reduced evapotranspiration (ET), but amplified by change of large-scale circulation. The reduction of ET and its delaying effect on dry-wet season transition is further confirmed with SCIAMACHY and TES HDO/H2O measurements.

Novel Fast Pyrolysis/Catalytic Technology for the Production of Stable Upgraded Liquids

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

Oyama, Ted; Agblevor, Foster; Battaglia, Francine

The objective of the proposed research is the demonstration and development of a novel biomass pyrolysis technology for the production of a stable bio-oil. The approach is to carry out catalytic hydrodeoxygenation (HDO) and upgrading together with pyrolysis in a single fluidized bed reactor with a unique two-level design that permits the physical separation of the two processes. The hydrogen required for the HDO will be generated in the catalytic section by the water-gas shift reaction employing recycled CO produced from the pyrolysis reaction itself. Thus, the use of a reactive recycle stream is another innovation in this technology. Themore » catalysts will be designed in collaboration with BASF Catalysts LLC (formerly Engelhard Corporation), a leader in the manufacture of attrition-resistant cracking catalysts. The proposed work will include reactor modeling with state-of-the-art computational fluid dynamics in a supercomputer, and advanced kinetic analysis for optimization of bio-oil production. The stability of the bio-oil will be determined by viscosity, oxygen content, and acidity determinations in real and accelerated measurements. A multi-faceted team has been assembled to handle laboratory demonstration studies and computational analysis for optimization and scaleup.« less

Synergy in Lignin Upgrading by a Combination of Cu-Based Mixed Oxide and Ni-Phosphide Catalysts in Supercritical Ethanol.

PubMed

Korányi, Tamás I; Huang, Xiaoming; Coumans, Alessandro E; Hensen, Emiel J M

2017-04-03

The depolymerization of lignin to bioaromatics usually requires a hydrodeoxygenation (HDO) step to lower the oxygen content. A mixed Cu-Mg-Al oxide (CuMgAlO x ) is an effective catalyst for the depolymerization of lignin in supercritical ethanol. We explored the use of Ni-based cocatalysts, i.e. Ni/SiO 2 , Ni 2 P/SiO 2 , and Ni/ASA (ASA = amorphous silica alumina), with the aim of combining lignin depolymerization and HDO in a single reaction step. While the silica-supported catalysts were themselves hardly active in lignin upgrading, Ni/ASA displayed comparable lignin monomer yield as CuMgAlO x . A drawback of using an acidic support is extensive dehydration of the ethanol solvent. Instead, combining CuMgAlO x with Ni/SiO 2 and especially Ni 2 P/SiO 2 proved to be effective in increasing the lignin monomer yield, while at the same time reducing the oxygen content of the products. With Ni 2 P/SiO 2 , the lignin monomer yield was 53 wt %, leading to nearly complete deoxygenation of the aromatic products.

Hydrogen/deuterium (H/D) exchange of gelatinized starch studied by two-dimensional (2D) near-infrared (NIR) correlation spectroscopy

NASA Astrophysics Data System (ADS)

Shinzawa, Hideyuki; Mizukado, Junji

2018-05-01

Hydrogen/deuterium (H/D) exchange of gelatinized starch was probed by in-situ near-infrared (NIR) monitoring coupled with two-dimensional (2D) correlation spectroscopy. Gelatinized starch undergoes spontaneous H/D exchange in D2O. During the substitution, the exchange rate essentially becomes different depending on solvent accessibility of various parts of the molecule. Thus, by analyzing the change in the NIR feature observed during the substitution, it becomes possible to sort out local structure and dynamics of the system. 2D correlation analysis of the time-dependent NIR spectra reveals the presence of different local structure of the starch, each having different solvent accessibility. For example, during the H/D exchange, the D2O is first absorbed by starch molecules especially around the surface area between the starch and water, where the water molecules are weakly interacted with the starch molecules. This absorption is quickly followed by the development of HDO species. Further absorption of the D2O results in the penetration of the molecules inside the starch and eventually develops the relatively strong interaction between the HDO and starch molecules because of the presence of dominant starch molecules.

Off-axis Integrated Cavity Output Spectrometer measurements of HDO/H2O ratio for understanding water transport in the Asian Summer Monsoon

NASA Astrophysics Data System (ADS)

Clouser, B.; Moyer, E. J.; Sarkozy, L.

2016-12-01

The Asian monsoon is one of the main pathways by which water vapor enters the stratosphere. However, the pathways by which water is carried to the upper troposphere/lower stratosphere (UTLS) region and the monsoon contributions to the total stratospheric water budget are not well constrained. We describe here a new instrument for measuring the isotopic composition of water vapor in this region, a useful tracer of the convective and microphysical history of air parcels, and show preliminary results from studies of monsoon outflow in summer 2016. The Chicago Water Isotope Spectrometer (Chi-WIS) is an absorption spectroscopy instrument for measurements of HDO and H2O at 2.65 microns by integrated cavity output spectroscopy (ICOS), designed to sample the 14-21 km range from the M55 Geophysica aircraft. The instrument is rebuilt specifically for the StratoClim campaign to study the Asian monsoon effect on the UTLS region in 2016-2017. We discuss steps taken to maximize signal in this extremely cold and dry environment, explore the instrument's sensitivity limits, and discuss data from test flights sampling monsoon outflow.

Water D/H Ratio In Low-Mass Protostars

NASA Astrophysics Data System (ADS)

Persson, Magnus V.; Jørgensen, Jes K.; van Dishoeck, Ewine F.; Harsono, Daniel

2013-07-01

Water is an important molecule for our life on Earth, but its way from formation on the surfaces of dust grains to planets and the accompanying chemical processing are not well understood. Through evaporation in the warm inner regions of protostars, water brings complex organics and other species previously locked up in the ice into the gas phase. The water deuterium fractionation (HDO/H2O abundance ratio) has traditionally been used to infer the amount of water that was brought to the Earth by comets. Deducing this ratio in the warm gas of deeply-embedded low-mass protostars allows to extend the discussion of the origin of Earth's water to earlier evolutionary stages. This poster present high-angular resolution, ground based interferometric observations of both HDO and H2(18)O water isotopologues toward several Class~0 low-mass protostars. The emission is compact, and stems from the inner few 100 AU in all sources. The derived amount of deuterium fractionation in water, obtained assuming LTE and optically thin emission, is the same within the uncertainties in all sources and shows only small enhancements compared with Earth's oceans and solar system's comets.

Observations of tropospheric trace gases from GOSAT thermal infrared spectra

NASA Astrophysics Data System (ADS)

Ohyama, Hirofumi; Shiomi, Kei; Kawakami, Shuji; Nakajima, Masakatsu; Maki, Takashi; Deushi, Makoto

2013-04-01

Thermal And Near infrared Sensor for carbon Observation-Fourier Transform Spectrometer (TANSO-FTS), which is one of the sensors onboard the Greenhouse gases Observing SATellite (GOSAT), measures the sunlight backscattered by the Earth's surface and atmosphere as well as the thermal radiance emitted from the Earth. Atmospheric trace gases such as ozone (O3), water vapor (H2O and HDO), methanol (CH3OH) and ammonia (NH3) are derived from the thermal infrared spectral radiance recorded with the TANSO-FTS by an optimal estimation retrieval approach. TANSO-FTS total ozone columns are compared with Dobson spectrophotometer and Ozone Monitoring Instrument (OMI) data. The TANSO-FTS total ozone retrievals exhibit a positive bias of 3-4% with a root-mean-square difference of 2-6% compared to the Dobson and OMI measurements. We compare TANSO-FTS tropospheric ozone columns to those from ozonesonde data as well as from a three-dimensional chemical-climate model (MRI-CCM2). The TANSO-FTS data have high correlations with the ozonesonde data. The seasonal trends of the retrieved tropospheric ozone are consistent with those of the ozonesonde data. The spatial distribution of the tropospheric ozone from the TANSO-FTS and MRI-CCM2 shows good agreement, especially in the high-level tropospheric ozone regions. We also retrieve tropospheric H2O and HDO profiles simultaneously, accounting for the cross correlations between the water isotopes. The joint retrieval results in precise estimation of the isotope ratio by partial cancellation of systematic errors common to both H2O and HDO. The retrieved profiles and columns are compared with radiosonde, GPS, and ground-based high-resolution FTS data. The temporal and spatial variations of the precipitable water and the isotope ratio are consistent with those of the validation data. Finally, air pollutants such as CH3OH and NH3 are retrieved using the retrieved ozone and water vapor. We present the latitudinal and seasonal variations of CH3OH related to plant growth and biomass burning, and the high-level NH3 in the hot spot areas.

Temperature-dependent kinetic measurements and quasi-classical trajectory studies for the OH(+) + H2/D2 → H2O(+)/HDO(+) + H/D reactions.

PubMed

Martinez, Oscar; Ard, Shaun G; Li, Anyang; Shuman, Nicholas S; Guo, Hua; Viggiano, Albert A

2015-09-21

We have measured the temperature-dependent kinetics for the reactions of OH(+) with H2 and D2 using a selected ion flow tube apparatus. Reaction occurs via atom abstraction to result in H2O(+)/HDO(+) + H/D. Room temperature rate coefficients are in agreement with prior measurements and resulting temperature dependences are T(0.11) for the hydrogen and T(0.25) for the deuterated reactions. This work is prompted in part by recent theoretical work that mapped a full-dimensional global potential energy surface of H3O(+) for the OH(+) + H2 → H + H2O(+) reaction [A. Li and H. Guo, J. Phys. Chem. A 118, 11168 (2014)], and reported results of quasi-classical trajectory calculations, which are extended to a wider temperature range and initial rotational state specification here. Our experimental results are in excellent agreement with these calculations which accurately predict the isotope effect in addition to an enhancement of the reaction rate constant due to the molecular rotation of OH(+). The title reaction is of high importance to astrophysical models, and the temperature dependence of the rate coefficients determined here should now allow for better understanding of this reaction at temperatures more relevant to the interstellar medium.

Influence of oxygen-, nitrogen-, and sulfur-containing compounds on the hydrodeoxygenation of phenols over sulfided CoMo/[gamma]-Al[sub 2]O[sub 3] and NiMo/[gamma]-Al[sub 2]O[sub 3] catalysts

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

Laurent, E.; Delmon, B.

1993-11-01

The hydrodeoxygenation (HDO) of phenols is a key reaction of the hydroprocessing of bio-oils, because phenolic molecules represent an important part of these oils and they are among the most difficult to deoxygenate. This reaction is also a very good reaction test for the characterization of the hydrogenation and hydrogenolysis functions of hydrotreating catalysts. In this work, the influence of competitors on the activity and selectivity of 4-methylphenol HDO over conventional CoMo and NiMo hydrotreating catalysts was evaluated in batch reaction tests. The inhibiting strength followed the order H[sub 2]O << 2-ethylphenol < H[sub 2]S < NH[sub 3]. In allmore » cases, the hydrogenolysis path was more inhibited than the hydrogenation path, indicating a higher adsorption strength and electrophilicity of associated sites. The inhibition was quantified according to a Langmuir adsorption concept. The deviations from this model were attributed to a distribution of the adsorption strength. As opposed to other competitors, hydrogen sulfide slightly promotes the hydrogenation activity of CoMo but not of NiMo. These observations were interpreted as the result of an interconversion of the hydrogenolysis and hydrogenation active sites.« less

Deuterium on Venus: Observations from Earth

NASA Technical Reports Server (NTRS)

Lutz, Barry L.; Debergh, C.; Bezard, B.; Owen, T.; Crisp, D.; Maillard, J.-P.

1991-01-01

In view of the importance of the deuterium-to-hydrogen ratio in understanding the evolutionary scenario of planetary atmospheres and its relationship to understanding the evolution of our own Earth, we undertook a series of observations designed to resolve previous observational conflicts. We observed the dark side of Venus in the 2.3 micron spectral region in search of both H2O and HDO, which would provide us with the D/H ratio in Venus' atmosphere. We identified a large number of molecular lines in the region, belonging to both molecules, and, using synthetic spectral techniques, obtained mixing ratios of 34 plus or minus 10 ppm and 1.3 plus or minus 0.2 ppm for H2O and HDO, respectively. These mixing ratios yield a D/H ratio for Venus of D/H equals 1.9 plus or minus 0.6 times 10 (exp 12) and 120 plus or minus 40 times the telluric ratio. Although the detailed interpretation is difficult, our observations confirm that the Pioneer Venus Orbiter results and establish that indeed Venus had a period in its early history in which it was very wet, perhaps not unlike the early wet period that seems to have been present on Mars, and that, in contrast to Earth, lost much of its water over geologic time.

Historical Orthoimagery of the Lake Tahoe Basin

USGS Publications Warehouse

Soulard, Christopher E.; Raumann, Christian G.

2008-01-01

The U.S. Geological Survey (USGS) Western Geographic Science Center has developed a series of historical digital orthoimagery (HDO) datasets covering part or all of the Lake Tahoe Basin. Three datasets are available: (A) 1940 HDOs for the southern Lake Tahoe Basin, (B) 1969 HDOs for the entire Lake Tahoe Basin, and (C) 1987 HDOs for the southern Lake Tahoe Basin. The HDOs (for 1940, 1969, and 1987) were compiled photogrammically from aerial photography with varying scales, camera characteristics, image quality, and capture dates. The resulting datasets have a 1-meter horizontal resolution. Precision-corrected Ikonos multispectral satellite imagery was used as a substitute for HDOs/DOQs for the 2002 imagery date, but these data are not available for download in this series due to licensing restrictions. The projection of the HDO data is set to UTM Zone 10, NAD 1983. The data for each of the three available dates are clipped into files that spatially approximate the 3.75-minute USGS quarter quadrangles (roughly 3,000 to 4,000 hectares), and have roughly 100 pixels (or 100 meters) of overlap to facilitate combining the files into larger regions without data gaps. The files are named after 3.75-minute USGS quarter quadrangles that cover the same general spatial extent. These files are available in the ERDAS Imagine (.img) format.

High-pressure vapor-phase hydrodeoxygenation of lignin-derived oxygenates to hydrocarbons by a PtMo bimetallic catalyst: Product selectivity, reaction pathway, and structural characterization

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

Yohe, Sara L.; Choudhari, Harshavardhan J.; Mehta, Dhairya D.

2016-12-01

High-pressure, vapor-phase, hydrodeoxygenation (HDO) reactions of dihydroeugenol (2-methoxy-4-propylphenol), as well as other phenolic, lignin-derived compounds, were investigated over a bimetallic platinum and molybdenum catalyst supported on multi-walled carbon nanotubes (5%Pt2.5%Mo/MWCNT). Hydrocarbons were obtained in 100% yield from dihydroeugenol, including 98% yield of the hydrocarbon propylcyclohexane. The final hydrocarbon distribution was shown to be a strong function of hydrogen partial pressure. Kinetic analysis showed three main dihydroeugenol reaction pathways: HDO, hydrogenation, and alkylation. The major pathway occurred via Pt catalyzed hydrogenation of the aromatic ring and methoxy group cleavage to form 4-propylcyclohexanol, then Mo catalyzed removal of the hydroxyl group bymore » dehydration to form propylcyclohexene, followed by hydrogenation of propylcyclohexene on either the Pt or Mo to form the propylcyclohexane. Transalkylation by the methoxy group occurred as a minor side reaction. Catalyst characterization techniques including chemisorption, scanning transmission electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy were employed to characterize the catalyst structure. Catalyst components identified were Pt particles, bimetallic PtMo particles, a Mo carbide-like phase, and Mo oxide phases.« less

Hydration of amino acids: FTIR spectra and molecular dynamics studies.

PubMed

Panuszko, Aneta; Adamczak, Beata; Czub, Jacek; Gojło, Emilia; Stangret, Janusz

2015-11-01

The hydration of selected amino acids, alanine, glycine, proline, valine, isoleucine and phenylalanine, has been studied in aqueous solutions by means of FTIR spectra of HDO isotopically diluted in H2O. The difference spectra procedure and the chemometric method have been applied to remove the contribution of bulk water and thus to separate the spectra of solute-affected HDO. To support interpretation of obtained spectral results, molecular dynamics simulations of amino acids were performed. The structural-energetic characteristic of these solute-affected water molecules shows that, on average, water affected by amino acids forms stronger and shorter H-bonds than those in pure water. Differences in the influence of amino acids on water structure have been noticed. The effect of the hydrophobic side chain of an amino acid on the solvent interactions seems to be enhanced because of the specific cooperative coupling of water strong H-bond chain, connecting the carboxyl and amino groups, with the clathrate-like H-bond network surrounding the hydrocarbon side chain. The parameter derived from the spectral data, which corresponds to the contributions of the population of weak hydrogen bonds of water molecules which have been substituted by the stronger ones in the hydration sphere of amino acids, correlated well with the amino acid hydrophobicity indexes.

Submillimeter mapping of mesospheric minor species on Venus with ALMA

NASA Astrophysics Data System (ADS)

Encrenaz, T.; Moreno, R.; Moullet, A.; Lellouch, E.; Fouchet, T.

2015-08-01

Millimeter and submillimeter heterodyne spectroscopy offers the possibility of probing the mesosphere of Venus and monitoring minor species and winds. ALMA presents a unique opportunity to map mesospheric species of Venus. During Cycle 0, we have observed Venus on November 14 and 15, 2011, using the compact configuration of ALMA. The diameter of Venus was 11″ and the illumination factor was about 90%. Maps of CO, SO, SO2 and HDO have been built from transitions recorded in the 335-347 GHz frequency range. A mean mesospheric thermal profile has been inferred from the analysis of the CO transition at the disk center, to be used in support of minor species retrieval. Maps of SO and SO2 abundance show significant local variations over the disk and contrast variations by as much as a factor 4. In the case of SO2, the spatial distribution appears more "patchy", i.e. shows short-scale structures apparently disconnected from day-side and latitudinal variations. For both molecules, significant changes occur over a timescale of one day. From the disk averaged spectrum of SO recorded on November 14 at 346.528 GHz, we find that the best fit is obtained with a cutoff in the SO vertical distribution at 88±2 km and a uniform mixing ratio of 8.0±2.0 ppb above this level. The SO2 map of November 14, derived from the weaker transition at 346.652 GHz, shows a clear maximum in the morning side at low latitudes, which is less visible in the map of November 15. We find that the best fit for SO2 is obtained for a cutoff in the vertical distribution at 88±3 km and a uniform mixing ratio of 12.0±3.5 ppb above this level. The HDO maps retrieved from the 335.395 GHz show some enhancement in the northern hemisphere, but less contrasted variations than for the sulfur species maps, with little change between November 14 and 15. Assuming a typical D/H ratio of 200 times the terrestrial value in the mesosphere of Venus, we find that the disk averaged HDO spectrum is best fitted with a uniform H2O mixing ratio of 2.5±0.6 ppm (corresponding to a HDO mixing ratio of 0.165±0.040 ppm). We note that our spectrum is also compatible with a H2O mixing ratio of 1.5 ppm in the 80-90 km altitude range, and a mixing ratio of 3 ppm outside this range, as suggested by the photochemical model of Zhang et al. (2012, Icarus, vol. 217, pp. 714-739). Our results are in good general agreement with previous single dish submillimeter observations of Sandor and Clancy (2005, Icarus, vol. 177, pp. 129-143), Gurwell et al. (2007, Icarus, vol. 188, p. 288), and Sandor et al. (2010, Icarus, vol. 208, pp. 49-60; 2012, Icarus, vol. 217, pp. 839-844) and with SPICAV/Venus Express results of Fedorova et al. (2008, J. Geophys. Res., vol. 113, p. E00B25) and Belyaev et al. (2012).

Synthesis of jet fuel range branched cycloalkanes with mesityl oxide and 2-methylfuran from lignocellulose

NASA Astrophysics Data System (ADS)

Li, Shanshan; Li, Ning; Wang, Wentao; Li, Lin; Wang, Aiqin; Wang, Xiaodong; Zhang, Tao

2016-09-01

Jet fuel range branched cycloalkanes with high density (0.82 g mL-1) and low freezing point (217-219 K) was first prepared by the solvent-free intramolecular aldol condensation of the trione from the hydrolysis of the alkylation product of mesityl oxide and 2-methylfuran (or the one-pot reaction of mesityl oxide, 2-methylfuran and water), followed by hydrodeoxygenation (HDO).

Synthesis of jet fuel range branched cycloalkanes with mesityl oxide and 2-methylfuran from lignocellulose.

PubMed

Li, Shanshan; Li, Ning; Wang, Wentao; Li, Lin; Wang, Aiqin; Wang, Xiaodong; Zhang, Tao

2016-09-01

Jet fuel range branched cycloalkanes with high density (0.82 g mL(-1)) and low freezing point (217-219 K) was first prepared by the solvent-free intramolecular aldol condensation of the trione from the hydrolysis of the alkylation product of mesityl oxide and 2-methylfuran (or the one-pot reaction of mesityl oxide, 2-methylfuran and water), followed by hydrodeoxygenation (HDO).

Synthesis of jet fuel range branched cycloalkanes with mesityl oxide and 2-methylfuran from lignocellulose

PubMed Central

Li, Shanshan; Li, Ning; Wang, Wentao; Li, Lin; Wang, Aiqin; Wang, Xiaodong; Zhang, Tao

2016-01-01

Jet fuel range branched cycloalkanes with high density (0.82 g mL−1) and low freezing point (217–219 K) was first prepared by the solvent-free intramolecular aldol condensation of the trione from the hydrolysis of the alkylation product of mesityl oxide and 2-methylfuran (or the one-pot reaction of mesityl oxide, 2-methylfuran and water), followed by hydrodeoxygenation (HDO). PMID:27582417

Isotopic Exchange of Deuterium Between Hydrogen and Water in Vapor Phase. Report No. 56; INTERCAMBIO ISOTOPICO DE DEUTERIO ENTRE EL HIDROGENO Y EL AGUA EN FASE VAPOR. INFORME NO. 56

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

Baran, W.J.; Cretella, R.F.

1961-01-01

The design is described of a device for the measurement of catalytic activities of the isotopic exchange reaction, H/sub 2/O (v) + HD in equilibrium HDO (v) + H/sub 2/, and to determine experimentally the kinetics for the interpretation of the results for the optimum conditions for the reaction. (tr- auth)

Effects of insolation on habitability and the isotopic history of Martian water

NASA Astrophysics Data System (ADS)

Moores, John

Three aspects of the Habitability of the Northern Plains of Mars to organics and terrestrial-like microbial life were assessed. (1) Protection offered by small surface features and; (2) the breakdown of rocks to form soils were examined using a radiative transfer computer model. Two separate sublimation experiments provided a basis to improve; (3) estimates of the amount of available water today and in the past by determining the fractionation of HDO between present-day reservoirs. (1) UV radiation sterilizes the hardiest of terrestrial organisms within minutes on the Martian surface. Small surface features including pits, trenches, flat faces and overhangs may create "safe havens" for organisms by blocking much of the UV flux. In the most favorable cases, this flux is sufficiently reduced such that organic in-fall could accumulate beneath overhanging surfaces and in pits and cracks while terrestrial microorganisms could persist for several tens of martian years. (2) The production of soils on the surface is considered by analogy with the arid US Southwest. Here differential insolation of incipient cracks of random orientations predicts crack orientation distributions consistent with field observations by assuming that only crack orientations which shield their interiors, minimizing their water loss, can grow, eventually disrupting the clast. (3) Disaggregated water ice to simulate the polar caps was produced by flash freezing in liquid nitrogen and crushing. When dust was added to the mixtures, the D/H ratio of the sublimate gas was seen to decrease with time from the bulk ratio. The more dust was added to the mixture, the more pronounced was this effect. The largest fractionation factor observed during these experiments was 2.5. Clean ice was also prepared and overlain by dust to simulate ground ice. Here, the movement of water vapor was modeled using an effective diffusivity that incorporated both adsorption on grains and diffusion. For low temperatures (<-55°C) a significant difference between the diffusivities of H 2 O and HDO was observed. This suggests adsorptive-control within the regolith as energies of interaction are 60-70kJmol -1 . This ability of the martian regolith to preferentially adsorb HDO decouples the ice table and polar caps from the atmosphere and allows for geographic variations in the D/H ratio on Mars.

Zinc-assisted hydrodeoxygenation of biomass-derived 5-hydroxymethylfurfural to 2,5-dimethylfuran.

PubMed

Saha, Basudeb; Bohn, Christine M; Abu-Omar, Mahdi M

2014-11-01

2,5-Dimethylfuran (DMF), a promising cellulosic biofuel candidate from biomass derived intermediates, has received significant attention because of its low oxygen content, high energy density, and high octane value. A bimetallic catalyst combination containing a Lewis-acidic Zn(II) and Pd/C components is effective for 5-hydroxymethylfurfural (HMF) hydrodeoxygenation (HDO) to DMF with high conversion (99%) and selectivity (85% DMF). Control experiments for evaluating the roles of zinc and palladium revealed that ZnCl2 alone did not catalyze the reaction, whereas Pd/C produced 60% less DMF than the combination of both metals. The presence of Lewis acidic component (Zn) was also found to be beneficial for HMF HDO with Ru/C catalyst, but the synergistic effect between the two metal components is more pronounced for the Pd/Zn system than the Ru/Zn. A comparative analysis of the Pd/Zn/C catalyst to previously reported catalytic systems show that the Pd/Zn system containing at least four times less precious metal than the reported catalysts gives comparable or better DMF yields. The catalyst shows excellent recyclability up to 4 cycles, followed by a deactivation, which could be due to coke formation on the catalyst surface. The effectiveness of this combined bimetallic catalyst has also been tested for one-pot conversion of fructose to DMF. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dynamics of a bistable Miura-origami structure

NASA Astrophysics Data System (ADS)

Fang, Hongbin; Li, Suyi; Ji, Huimin; Wang, K. W.

2017-05-01

Origami-inspired structures and materials have shown extraordinary properties and performances originating from the intricate geometries of folding. However, current state of the art studies have mostly focused on static and quasistatic characteristics. This research performs a comprehensive experimental and analytical study on the dynamics of origami folding through investigating a stacked Miura-Ori (SMO) structure with intrinsic bistability. We fabricate and experimentally investigated a bistable SMO prototype with rigid facets and flexible crease lines. Under harmonic base excitation, the SMO exhibits both intrawell and interwell oscillations. Spectrum analyses reveal that the dominant nonlinearities of SMO are quadratic and cubic, which generate rich dynamics including subharmonic and chaotic oscillations. The identified nonlinearities indicate that a third-order polynomial can be employed to approximate the measured force-displacement relationship. Such an approximation is validated via numerical study by qualitatively reproducing the phenomena observed in the experiments. The dynamic characteristics of the bistable SMO resemble those of a Helmholtz-Duffing oscillator (HDO); this suggests the possibility of applying the established tools and insights of HDO to predict origami dynamics. We also show that the bistability of SMO can be programmed within a large design space via tailoring the crease stiffness and initial stress-free configurations. The results of this research offer a wealth of fundamental insights into the dynamics of origami folding, and provide a solid foundation for developing foldable and deployable structures and materials with embedded dynamic functionalities.

Preparation, Characterization, and Catalytic Activity of MoCo/USY Catalyst on Hydrodeoxygenation Reaction of Anisole

NASA Astrophysics Data System (ADS)

Nugrahaningtyas, K. D.; Suharbiansah, R. S. R.; Rahmawati, F.

2018-03-01

This research aims to prepare, characterize, and study the catalytic activity of Molybdenum (Mo) and Cobalt (Co) metal with supporting material Ultra Stable Y-Zeolite (USY), to produce catalysts with activity in hydrotreatment reaction and in order to eliminate impurities compounds that containing unwanted groups heteroatoms. The bimetallic catalysts MoCo/USY were prepared by wet impregnation method with weight variation of Co metal 0%, 2%, 4%, 6%, 8%, and Mo metal 8% (w/w), respectively. Activation method of the catalyst included calcination, oxidation, reduction and the crystallinity was characterized using X-ray diffraction (XRD), the acidity of the catalyst was analyzed using Fourier Transform Infrared Spectroscopy (FT-IR) and gravimetry method, minerals present in the catalyst was analyzed using X-Ray Fluorescence (XRF), and surface of the catalyst was analyzed using Surface Area Analyzer (SAA). Catalytic activity test (benzene yield product) of MoCo/USY on hydrodeoxigenation reaction of anisole aimed to determine the effect of Mo-Co/USY for catalytic activity in the reaction hydrodeoxigenation (HDO) anisole. Based on characterization and test of catalytic activity, it is known that catalytic of MoCo/USY 2% (catalyst B) shows best activities with acidity of 10.209 mmol/g, specific area of catalyst of 426.295 m2/g, pore average of 14.135 Å, total pore volume 0.318 cc/g, and total yield of HDO products 6.06%.

Femtosecond spectroscopic study of the solvation of amphiphilic molecules by water

NASA Astrophysics Data System (ADS)

Rezus, Y. L. A.; Bakker, H. J.

2008-06-01

We use polarization-resolved mid-infrared pump-probe spectroscopy to study the aqueous solvation of proline and N-methylacetamide. These molecules serve as models to study the solvation of proteins. We monitor the orientational dynamics of partly deuterated water molecules (HDO) that are present at a low concentration in the water. We find that the OD vibration of HDO relaxes via an intermediate level, that is characterized by a hydrogen-bond that is stronger than in the ground state. With increasing concentration the lifetime of the excited state increases from 1.8 ps to 2.4 ps and the lifetime of the intermediate level from 0.6 ps to 1.0 ps. Regarding the orientational dynamics we observe biexponential behavior, which finds its origin in the presence of two classes of water molecules. There is a fraction of water molecules that has bulk-like orientational dynamics ( τrot = 2.5 ps) and a fraction of immobilized water molecules ( τrot > 10 ps). The relative abundance of the two fractions is determined by the nature and concentration of the solute. We find that the hydrophobic solute groups are responsible for the immobilization of water molecules. Every methyl group causes the immobilization of approximately 4 water OH groups. The hydrophilic solute groups, on the other hand, do not hinder the reorientation and the water molecules solvating them reorient with the same rate as in the bulk liquid.

Field Evaluation of All-Season Tactical Engine Oil OE/HDO-15/40 at Ft. Knox, Kentucky and Ft. Bliss, Texas

DTIC Science & Technology

1986-07-01

qualified lubricants were employed in the test, one product at each of the test locations. The test lubricants were used in all equipment components...Overall, the grade 15W-40 products demonstrated satisfactory and equivalent performance to single-graded oils. The oil was well received by both...operators and maintenance personnel who noted that the grade 15W-40 products significantly reduced logistics burden by having only one grade product to

Hydrodeoxygenation of p -Cresol over Pt/Al 2 O 3 Catalyst Promoted by ZrO 2 , CeO 2 , and CeO 2 –ZrO 2

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

Wang, Weiyan; Wu, Kui; Liu, Pengli

2016-07-20

ZrO 2-Al 2O 3 and CeO 2-Al 2O 3 were prepared by a co-precipitation method and selected as supports for Pt catalysts. The effects of CeO 2 and ZrO 2 on the surface area and Brønsted acidity of Pt/Al 2O 3 were studied. In the hydrodeoxygenation (HDO) of p-cresol, the addition of ZrO 2 promoted the direct deoxygenation activity on Pt/ZrOO 2-Al 2O 3 via Caromatic-O bond scission without benzene ring saturation. Pt/CeOO 2-Al 2O 3 exhibited higher deoxygenation extent than Pt/Al 2O 3 due to the fact that Brønsted acid sites on the catalyst surface favored the adsorption ofmore » p-cresol. With the advantages of CeO 2 and ZrO 2 taken into consideration, CeO 2-ZrOO 2-Al 2O 3 was prepared, leading to the highest HDO activity of Pt/CeO 2-ZrOO 2-Al 2O 3. The deoxygenation extent for Pt/CeO 2-ZrOO 2-Al 2O 3 was 48.4% and 14.5% higher than that for Pt/ZrO2O 2-Al 2O 3 and Pt/CeOO 2-Al 2O 3, respectively.« less

An Accurate Potential Energy Surface for H2O

NASA Technical Reports Server (NTRS)

Schwenke, David W.; Partridge, Harry; Langhoff, Stephen R. (Technical Monitor)

1997-01-01

We have carried out extensive high quality ab initio electronic structure calculations of the ground state potential energy surface (PES) and dipole moment function (DMF) for H2O. A small adjustment is made to the PES to improve the agreement of line positions from theory and experiment. The theoretical line positions are obtained from variational ro-vibrational calculations using the exact kinetic energy operator. For the lines being fitted, the root-mean-square error was reduced from 6.9 to 0.08 /cm. We were then able to match 30,092 of the 30,117 lines from the HITRAN 96 data base to theoretical lines, and 80% of the line positions differed less than 0.1 /cm. About 3% of the line positions in the experimental data base appear to be incorrect. Theory predicts the existence of many additional weak lines with intensities above the cutoff used in the data base. To obtain results of similar accuracy for HDO, a mass dependent correction to the PH is introduced and is parameterized by simultaneously fitting line positions for HDO and D2O. The mass dependent PH has good predictive value for T2O and HTO. Nonadiabatic effects are not explicitly included. Line strengths for vibrational bands summed over rotational levels usually agree well between theory and experiment, but individual line strengths can differ greatly. A high temperature line list containing about 380 million lines has been generated using the present PES and DMF

Hydrodeoxygenation of phenol over zirconia supported Pd bimetallic catalysts. The effect of second metal on catalyst performance

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

Resende, Karen A.; Teles, Camila A.; Jacobs, Gary

Here, this work investigated the effect of the addition of a second metal (Cu, Ag, Zn, Sn) on the performance of Pd/ZrO 2 catalyst for HDO of phenol at 573 K in the gas phase. The incorporation of dopants resulted in the formation of Pd–X (Cu, Ag, Zn) alloys, which reduced the reaction rate for HDO and increased the selectivity to hydrogenation products (cyclohexanone and cyclohexanol). The lower activity of the bimetallic catalysts was due to the segregation of the second metal on the surface of the Pd particle. For PdSn/ZrO 2, alloying was also observed but tin oxide wasmore » still present on the surface after reduction at 773 K. For Pd and PdSn/ZrO 2, the oxophilic sites represented by Zr and Sn cations promotes the hydrogenation of the carbonyl group of the keto-tautomer intermediate formed, producing benzene as the main product. All catalysts significantly deactivated during the reaction but the deactivation degree depended on the type of the metal. Pd/ZrO 2 and PdZn/ZrO 2 and PdAg/ZrO 2 exhibited approximately the same deactivation degree. However, the loss of activity was less pronounced for PdSn/ZrO2 catalyst. Finally, Pd dispersion significantly decreased during the reaction, indicating that the sintering of Pd particles is one of the causes for catalyst deactivation.« less

Hydrodeoxygenation of phenol over zirconia supported Pd bimetallic catalysts. The effect of second metal on catalyst performance

DOE PAGES

Resende, Karen A.; Teles, Camila A.; Jacobs, Gary; ...

2018-03-21

Here, this work investigated the effect of the addition of a second metal (Cu, Ag, Zn, Sn) on the performance of Pd/ZrO 2 catalyst for HDO of phenol at 573 K in the gas phase. The incorporation of dopants resulted in the formation of Pd–X (Cu, Ag, Zn) alloys, which reduced the reaction rate for HDO and increased the selectivity to hydrogenation products (cyclohexanone and cyclohexanol). The lower activity of the bimetallic catalysts was due to the segregation of the second metal on the surface of the Pd particle. For PdSn/ZrO 2, alloying was also observed but tin oxide wasmore » still present on the surface after reduction at 773 K. For Pd and PdSn/ZrO 2, the oxophilic sites represented by Zr and Sn cations promotes the hydrogenation of the carbonyl group of the keto-tautomer intermediate formed, producing benzene as the main product. All catalysts significantly deactivated during the reaction but the deactivation degree depended on the type of the metal. Pd/ZrO 2 and PdZn/ZrO 2 and PdAg/ZrO 2 exhibited approximately the same deactivation degree. However, the loss of activity was less pronounced for PdSn/ZrO2 catalyst. Finally, Pd dispersion significantly decreased during the reaction, indicating that the sintering of Pd particles is one of the causes for catalyst deactivation.« less

Tritium Separation from High Volume Dilute Aqueous Streams- Milestone Report for M3FT-15OR0302092

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

Bhave, Ramesh R.; Jubin, Robert Thomas; Spencer, Barry B.

2016-02-29

This report describes the synthesis and evaluation of molecular sieve zeolite membranes to separate and concentrate tritiated water (HTO) from dilute HTO-bearing aqueous streams. Several silico alumino phosphate (SAPO-34) molecular sieve zeolite membranes were synthesized and characterized with gas and vapor permeation measurements. The pervaporation process performance was evaluated for the separation and concentration of tritiated water. Experiments were performed over a range of tritiated water concentration covering the range of concentration anticipated in nuclear fuel processing where potentially both acid and water streams are recycled. The permeate was recovered under vacuum. The tritium concentration ranged from 0.5 to 1more » mCi/mL which is about 0.1 mg/L or 0.1 ppm. The HTO concentration was three orders of magnitude lower than experiments performed with simulated feed containing HDO (>100 ppm) using deuterated water where high separation factors (>10) were obtained using SAPO membranes. Separation factor calculated from the measured tritium concentrations ranged from 0.83-0.98. Although the membrane performance characterization results were lower than expected, they can be explained on the basis of low feed volume and three orders of magnitude lower HTO concentration compared to HDO concentration in deuterated water. We have identified several new approaches, such as tuning the diffusion coefficient of HTO, that may help achieve preferential transport of tritium (HTO) resulting in a substantially more concentrated permeate.« less

Bifunctional catalysts for upgrading of biomass-derived oxygenates: A review

DOE PAGES

Robinson, Allison M.; Hensley, Jesse E.; Medlin, J. Will

2016-06-21

Deoxygenation is an important reaction in the conversion of biomass-derived oxygenates to fuels and chemicals. A key route for biomass refining involves the production of pyrolysis oil through rapid heating of the raw biomass feedstock. Pyrolysis oil as produced is highly oxygenated, so the feasibility of this approach depends in large part on the ability to selectively deoxygenate pyrolysis oil components to create a stream of high-value finished products. Identification of catalytic materials that are active and selective for deoxygenation of pyrolysis oil components has therefore represented a major research area. One catalyst is rarely capable of performing the differentmore » types of elementary reaction steps required to deoxygenate biomass-derived compounds. For this reason, considerable attention has been placed on bifunctional catalysts, where two different active materials are used to provide catalytic sites for diverse reaction steps. Here, we review recent trends in the development of catalysts, with a focus on catalysts for which a bifunctional effect has been proposed. We summarize recent studies of hydrodeoxygenation (HDO) of pyrolysis oil and model compounds for a range of materials, including supported metal and bimetallic catalysts as well as transition-metal oxides, sulfides, carbides, nitrides, and phosphides. Particular emphasis is placed on how catalyst structure can be related to performance via molecular-level mechanisms. Finally, these studies demonstrate the importance of catalyst bifunctionality, with each class of materials requiring hydrogenation and C-O scission sites to perform HDO at reasonable rates.« less

Importance of tunneling in H-abstraction reactions by OH radicals. The case of CH4 + OH studied through isotope-substituted analogs

NASA Astrophysics Data System (ADS)

Lamberts, T.; Fedoseev, G.; Kästner, J.; Ioppolo, S.; Linnartz, H.

2017-03-01

We present a combined experimental and theoretical study focussing on the quantum tunneling of atoms in the reaction between CH4 and OH. The importance of this reaction pathway is derived by investigating isotope substituted analogs. Quantitative reaction rates needed for astrochemical models at low temperature are currently unavailable both in the solid state and in the gas phase. Here, we study tunneling effects upon hydrogen abstraction in CH4 + OH by focusing on two reactions: CH4 + OD → CH3 + HDO and CD4 + OH → CD3 + HDO. The experimental study shows that the solid-state reaction rate RCH4 + OD is higher than RCD4 + OH at 15 K. Experimental results are accompanied by calculations of the corresponding unimolecular and bimolecular reaction rate constants using instanton theory taking into account surface effects. For the work presented here, the unimolecular reactions are particularly interesting as these provide insight into reactions following a Langmuir-Hinshelwood process. The resulting ratio of the rate constants shows that the H abstraction (kCH4 + OD) is approximately ten times faster than D-abstraction (kCD4 + OH) at 65 K. We conclude that tunneling is involved at low temperatures in the abstraction reactions studied here. The unimolecular rate constants can be used by the modeling community as a first approach to describe OH-mediated abstraction reactions in the solid phase. For this reason we provide fits of our calculated rate constants that allow the inclusion of these reactions in models in a straightforward fashion.

THE ABUNDANCE, ORTHO/PARA RATIO, AND DEUTERATION OF WATER IN THE HIGH-MASS STAR-FORMING REGION NGC 6334 I

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

Emprechtinger, M.; Lis, D. C.; Monje, R. R.

2013-03-01

We present Herschel/HIFI observations of 30 transitions of water isotopologues toward the high-mass star-forming region NGC 6334 I. The line profiles of H{sup 16} {sub 2}O, H{sup 17} {sub 2}O, H{sup 18} {sub 2}O, and HDO show a complex pattern of emission and absorption components associated with the embedded hot cores, a lower-density envelope, two outflow components, and several foreground clouds, some associated with the NGC 6334 complex, others seen in projection against the strong continuum background of the source. Our analysis reveals an H{sub 2}O ortho/para ratio of 3 {+-} 0.5 in the foreground clouds, as well as themore » outflow. The water abundance varies from {approx}10{sup -8} in the foreground clouds and the outer envelope to {approx}10{sup -6} in the hot core. The hot core abundance is two orders of magnitude below the chemical model predictions for dense, warm gas, but within the range of values found in other Herschel/HIFI studies of hot cores and hot corinos. This may be related to the relatively low gas and dust temperature ({approx}100 K), or time-dependent effects, resulting in a significant fraction of water molecules still locked up in dust grain mantles. The HDO/H{sub 2}O ratio in NGC 6334 I, {approx}2 Multiplication-Sign 10{sup -4}, is also relatively low, but within the range found in other high-mass star-forming regions.« less

IR heterodyne spectrometer MILAHI for continuous monitoring observatory of Martian and Venusian atmospheres at Mt. Haleakalā, Hawaii

NASA Astrophysics Data System (ADS)

Nakagawa, Hiromu; Aoki, Shohei; Sagawa, Hideo; Kasaba, Yasumasa; Murata, Isao; Sonnabend, Guido; Sornig, Manuela; Okano, Shoichi; Kuhn, Jeffrey R.; Ritter, Joseph M.; Kagitani, Masato; Sakanoi, Takeshi; Taguchi, Makoto; Takami, Kosuke

2016-07-01

A new Mid-Infrared Laser Heterodyne Instrument (MILAHI) with >106 resolving power at 7-12 μm was developed for continuous monitoring of planetary atmospheres by using dedicated ground-based telescopes for planetary science at Mt. Haleakalā, Hawaii. Room-temperature-type quantum cascade lasers (QCLs) that cover wavelength ranges of 7.69-7.73, 9.54-9.59, and 10.28-10.33 μm have been newly installed as local oscillators to allow observation of CO2, CH4, H2O2, H2O, and HDO. Modeling and predictions by radiative transfer code gave the following scientific capabilities and measurement sensitivities of the MILAHI. (1) Temperature profiles are achieved at altitudes of 65-90 km on Venus, and the ground surface to 30 km on Mars. (2) New wind profiles are provided at altitudes of 75-90 km on Venus, and 5-25 km on Mars. (3) Direct measurements of the mesospheric wind and temperature are obtained from the Doppler-shifted emission line at altitudes of 110 km on Venus and 75 km on Mars. (4) Detections of trace gases and isotopic ratios are performed without any ambiguity of the reproducing the terrestrial atmospheric absorptions in the observed wavelength range. A HDO measurement of twice the Vienna Standard Mean Ocean Water (VSMOW) can be obtained by 15-min integration, while H2O of 75 ppm is provided by 3.62-h integration. The detectability of the 100 ppb-CH4 on Mars corresponds to an integration time of 32 h.

Synthesis and Performance Evaluations of SAPO-34 Membranes- Milestone Report for FCRD-MRWFD-2016-000263

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

Bhave, Ramesh R.; Jubin, Robert Thomas; Spencer, Barry B.

2016-07-01

This report describes the synthesis and evaluation of molecular sieve zeolite membranes to separate and concentrate tritiated water (HTO) from dilute HTO-bearing aqueous streams. Several silico alumino phosphate (SAPO-34) molecular sieve zeolite membranes were synthesized on tubular supports and characterized with gas and vapor permeation measurements. The pervaporation process performance was evaluated for the separation and concentration of tritiated water. Experiments were performed over a range of tritiated water concentration that correspond to the range anticipated in a nuclear fuel processing system that includes both acid and water streams recycling. The permeate was recovered under vacuum. The tritium concentration rangedmore » from 0.5 to 1 mCi/mL which is about 0.1 mg/L or 0.1 ppm. The separation factors calculated from the measured tritium concentrations ranged from 0.83-0.98. The HTO concentration was three orders of magnitude lower than prior experiments performed with simulated feed containing HDO (>100 ppm) using deuterated water where high separation factors (>10) were obtained using SAPO membranes on alumina disk supports. Although the membrane performance characterization results for HTO were lower than expected, they can be explained on the basis of low feed volume and three orders of magnitude lower HTO concentration compared to HDO concentration in deuterated water. Several new approaches are proposed, such as tuning the diffusion coefficient of HTO, and optimization of membrane thickness that may help achieve preferential transport of tritium (HTO) resulting in a substantially more concentrated permeate.« less

Widely tunable quantum cascade laser-based terahertz source.

PubMed

Danylov, Andriy A; Light, Alexander R; Waldman, Jerry; Erickson, Neal; Qian, Xifeng

2014-07-10

A compact, tunable, ultranarrowband terahertz source, Δν∼1  MHz, is demonstrated by upconversion of a 2.324 THz, free-running quantum cascade laser with a THz Schottky-diode-balanced mixer using a swept, synthesized microwave source to drive the nonlinearity. Continuously tunable radiation of 1 μW power is demonstrated in two frequency regions: ν(Laser) ± 0 to 50 GHz and ν(Laser) ± 70 to 115 GHz. The sideband spectra were characterized with a Fourier-transform spectrometer, and the radiation was tuned through CO, HDO, and D2O rotational transitions.

Vapor concentration monitor

DOEpatents

Bayly, John G.; Booth, Ronald J.

1977-01-01

An apparatus for monitoring the concentration of a vapor, such as heavy water, having at least one narrow bandwidth in its absorption spectrum, in a sample gas such as air. The air is drawn into a chamber in which the vapor content is measured by means of its radiation absorption spectrum. High sensitivity is obtained by modulating the wavelength at a relatively high frequency without changing its optical path, while high stability against zero drift is obtained by the low frequency interchange of the sample gas to be monitored and of a reference sample. The variable HDO background due to natural humidity is automatically corrected.

Water in dense molecular clouds

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

Wannier, P.G.; Kuiper, T.B.H.; Frerking, M.A.

1991-08-01

The G.P. Kuiper Airborne Observatory (KAO) was used to make initial observations of the half-millimeter ground-state transition of water in seven giant molecular clouds and in two late-type stars. No significant detections were made, and the resulting upper limits are significantly below those expected from other, indirect observations and from several theoretical models. The implied interstellar H2O/CO abundance is less than 0.003 in the cores of three giant molecular clouds. This value is less than expected from cloud chemistry models and also than estimates based on HDO and H3O(+) observations. 78 refs.

Effect of Blended Feedstock on Pyrolysis Oil Composition

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

Smith, Kristin M; Gaston, Katherine R

Current techno-economic analysis results indicate biomass feedstock cost represents 27% of the overall minimum fuel selling price for biofuels produced from fast pyrolysis followed by hydrotreating (hydro-deoxygenation, HDO). As a result, blended feedstocks have been proposed as a way to both reduce cost as well as tailor key chemistry for improved fuel quality. For this study, two feedstocks were provided by Idaho National Laboratory (INL). Both were pyrolyzed and collected under the same conditions in the National Renewable Energy Laboratory's (NREL) Thermochemical Process Development Unit (TCPDU). The resulting oil properties were then analyzed and characterized for statistical differences.

Kinetic isotopic fractionation and the origin of HDO and CH3D in the solar system

NASA Technical Reports Server (NTRS)

Yung, Yuk L.; Wen, Jun-Shan; Friedl, Randall R.; Pinto, Joseph P.; Bayes, Kyle D.

1988-01-01

It is suggested that photochemical enrichment processes driven by stellar UV emissions could result in a large deuterium fractionation of water and methane relative to H2 in the primitive solar nebula. These enrichment processes could have profoundly influenced the isotopic content of water in the terrestrial planets, if a large fraction of their volatiles had been added by impacts of meteorites and comets formed in the outer parts of the solar nebula. Efficient mixing could have exposed the material in the interior of the solar nebula to starlight.

A Deep Search for Biomarker Gases on Mars in 2009 - 2010: The Campaign and a Few Preliminary Results

NASA Astrophysics Data System (ADS)

Mumma, M. J.; Villanueva, G. L.; Novak, R.; Radeva, Y. L.; Kaufl, H.; Smette, A.; Hartogh, P.; Encrenaz, T.

2010-12-01

We searched for possible biomarker gases on Mars in the 2009-2010 observing season, emphasizing nine molecules (H2_O, CH_4_, C2_H_6_, C2_H_4_, CH3_OH, H_2_CO, H2_S, and N_2_O) of fundamental astrobiological importance along with HDO and CO2_. Our search utilized Earth’s most advanced ground-based infrared spectroscopic facilities in a campaign of several dozen observing runs spanning the period 19 August 2009 to 10 June 2010. Over this interval (L_s_ = 324 - 103 degrees), the season in Mars’ Northern hemisphere progressed from mid-winter, through vernal equinox and spring, and into early summer. We used long-slit high-resolution infrared spectrometers at the Keck and NASA-IRTF observatories in Hawaii, and the European Southern Observatory in Chile (VLT, Paranal). The spectral resolving powers ranged from ~ 35,000 (NIRSPEC/Keck and CSHELL/IRTF) to ~ 90,000 (CRIRES, VLT). At the sub-Earth point, the spatial resolution in non-AO mode ranged from ~600 km (FWHM) to ~ 400 km at Keck and IRTF. Using the adaptive optics (AO) mode at Keck and at VLT, we achieved an improved resolution of ~250 km (FWHM). We mapped the planet over the Earth-facing hemisphere by orienting the slit North-South in longitude and stepping it East-West across the planet, and we acquired deep searches over restricted longitude ranges by holding the slit fixed in position and taking sequential spectra as Mars rotated under it. Spectral lines of CO2_, H_2_O, HDO, and O2_ (a^1^Δg_) are obvious, even in the raw data. In the methane region near 3.3µm, removal of terrestrial and solar spectral lines revealed multiple lines of Mars H_2_O and CO2_, from which we extracted 2-D (lat-long) maps of Martian water vapor, atmospheric surface pressure and temperature. Subtraction of these features provided highly sensitive searches for trace gases. Preliminary results of searches for CH_4_, C2_H_4_, and C2_H_6_ will be presented in this paper. Radeva et al. (this meeting) will present preliminary results for ozone (derived from O2_ (^1^Δg_) near 1.27 µm). Villanueva et al. (this meeting) will present results for HDO (near 3.7 µm) and H_2_O (near 3.3 µm). Acknowledgements: This work was funded by NASA’s R&A Programs in Astrobiology (344-53-51), Planetary Astronomy (344-32-51-96), and Planetary Atmospheres (NNX09AB65G). We gratefully acknowledge the Director and staff of the European Southern Observatory, the Keck observatory and the NASA-IRTF observatory for supporting these observations.

Effect of dual-type oligosaccharides on constipation in loperamide-treated rats

PubMed Central

Han, Sung Hee; Hong, Ki Bae; Kim, Eun Young; Ahn, So Hyun

2016-01-01

BACKGROUND/OBJECTIVES Constipation is a condition that can result from intestinal deformation. Because humans have an upright posture, the effects of gravity can cause this shape deformation. Oligosaccharides are common prebiotics and their effects on bowel health are well known. However, studies of the physiological functionality of a product that contains both lactulose and galactooligosaccharides are insufficient. We investigated the constipation reduction effect of a dual-type oligosaccharide, Dual-Oligo, in loperamide-treated rats. MATERIALS/METHODS Dual-Oligo consists of galactooligosaccharides (15.80%) and lactulose (51.67%). Animals were randomly divided into four groups, the normal group (normal), control group (control), low concentration of Dual-Oligo (LDO) group, and high concentration of Dual-Oligo (HDO) group. After 7 days of oral administration, fecal pellet amount, fecal weight, water content of fecal were measured. Blood chemistry, short-chain fatty acid (SCFA), gastrointestinal transit ratio and length and intestinal mucosa were analyzed. RESULTS Dual-Oligo increased the fecal weight, and water content of feces in rats with loperamide-induced constipation. Gastrointestinal transit ratio and length and area of intestinal mucosa significantly increased after treatment with Dual-Oligo in loperamide-induced rats. A high concentration of Dual-Oligo tended to produce more acetic acid than that observed for the control group, and Dual-Oligo affected the production of total SCFA. Bifidobacteria concentration of cecal contents in the high-concentration oligosaccharide (HDO) and low-concentration oligosaccharide (LDO) groups was similar to the result of the normal group. CONCLUSIONS These results showed that Dual-Oligo is a functional material that is derived from a natural food product and is effective in ameliorating constipation. PMID:27909555

Quantification of real thermal, catalytic, and hydrodeoxygenated bio-oils via comprehensive two-dimensional gas chromatography with mass spectrometry.

PubMed

Silva, Raquel V S; Tessarolo, Nathalia S; Pereira, Vinícius B; Ximenes, Vitor L; Mendes, Fábio L; de Almeida, Marlon B B; Azevedo, Débora A

2017-03-01

The elucidation of bio-oil composition is important to evaluate the processes of biomass conversion and its upgrading, and to suggest the proper use for each sample. Comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC×GC-TOFMS) is a widely applied analytical approach for bio-oil investigation due to the higher separation and resolution capacity from this technique. This work addresses the issue of analytical performance to assess the comprehensive characterization of real bio-oil samples via GC×GC-TOFMS. The approach was applied to the individual quantification of compounds of real thermal (PWT), catalytic process (CPO), and hydrodeoxygenation process (HDO) bio-oils. Quantification was performed with reliability using the analytical curves of oxygenated and hydrocarbon standards as well as the deuterated internal standards. The limit of quantification was set at 1ngµL -1 for major standards, except for hexanoic acid, which was set at 5ngµL -1 . The GC×GC-TOFMS method provided good precision (<10%) and excellent accuracy (recovery range of 70-130%) for the quantification of individual hydrocarbons and oxygenated compounds in real bio-oil samples. Sugars, furans, and alcohols appear as the major constituents of the PWT, CPO, and HDO samples, respectively. In order to obtain bio-oils with better quality, the catalytic pyrolysis process may be a better option than hydrogenation due to the effective reduction of oxygenated compound concentrations and the lower cost of the process, when hydrogen is not required to promote deoxygenation in the catalytic pyrolysis process. Copyright © 2016 Elsevier B.V. All rights reserved.

Eosinophil-mediated signalling attenuates inflammatory responses in experimental colitis

PubMed Central

Masterson, Joanne C; McNamee, Eóin N; Fillon, Sophie A; Hosford, Lindsay; Harris, Rachel; Fernando, Shahan D; Jedlicka, Paul; Iwamoto, Ryo; Jacobsen, Elizabeth; Protheroe, Cheryl; Eltzschig, Holger K; Colgan, Sean P; Arita, Makoto; Lee, James J; Furuta, Glenn T

2015-01-01

Objective Eosinophils reside in the colonic mucosa and increase significantly during disease. Although a number of studies have suggested that eosinophils contribute to the pathogenesis of GI inflammation, the expanding scope of eosinophil-mediated activities indicate that they also regulate local immune responses and modulate tissue inflammation. We sought to define the impact of eosinophils that respond to acute phases of colitis in mice. Design Acute colitis was induced in mice by administration of dextran sulfate sodium, 2,4,6-trinitrobenzenesulfonic acid or oxazolone to C57BL/6J (control) or eosinophil deficient (PHIL) mice. Eosinophils were also depleted from mice using antibodies against interleukin (IL)-5 or by grafting bone marrow from PHIL mice into control mice. Colon tissues were collected and analysed by immunohistochemistry, flow cytometry and reverse transcription PCR; lipids were analysed by mass spectroscopy. Results Eosinophil-deficient mice developed significantly more severe colitis, and their colon tissues contained a greater number of neutrophils, than controls. This compensatory increase in neutrophils was accompanied by increased levels of the chemokines CXCL1 and CXCL2, which attract neutrophils. Lipidomic analyses of colonic tissue from eosinophil-deficient mice identified a deficiency in the docosahexaenoic acid-derived anti-inflammatory mediator 10, 17- dihydroxydocosahexaenoic acid (diHDoHE), namely protectin D1 (PD1). Administration of an exogenous PD1-isomer (10S, 17S-DiHDoHE) reduced the severity of colitis in eosinophil-deficient mice. The PD1-isomer also attenuated neutrophil infiltration and reduced levels of tumour necrosis factor-α, IL-1β, IL-6 and inducible NO-synthase in colons of mice. Finally, in vitro assays identified a direct inhibitory effect of PD1-isomer on neutrophil transepithelial migration. Conclusions Eosinophils exert a protective effect in acute mouse colitis, via production of anti-inflammatory lipid mediators. PMID:25209655

Ab Initio Calculations of Water Line Strengths

NASA Technical Reports Server (NTRS)

Schwenke, David W.; Partridge, Harry

1998-01-01

We report on the determination of a high quality ab initiu potential energy surface (PES) and dipole moment function for water. This PES is empirically adjusted to improve the agreement between the computed line positions and those from the HITRAN 92 data base with J less than 6 for H2O. The changes in the PES are small, nonetheless including an estimate of core (oxygen 1s) electron correlation greatly improves the agreement with experiment. Using this adjusted PES, we can match 30,092 of the 30,117 transitions in the HITRAN 96 data base for H2O with theoretical lines. The 10,25,50,75, and 90 percentiles of the difference between the calculated and tabulated line positions are -0.11, -0.04, -0.01, 0.02, and 0.07 l/cm. Non-adiabatic effects are not explicitly included. About 3% of the tabulated line positions appear to be incorrect. Similar agreement using this adjusted PES is obtained for the oxygen 17 and oxygen 18 isotopes. For HDO, the agreement is not as good, with root-mean-square error of 0.25 l/cm for lines with J less than 6. This error is reduced to 0.02 l/cm by including a small asymmetric correction to the PES, which is parameterized by simultaneously fitting to HDO md D2O data. Scaling this correction by mass factors yields good results for T2O and HTO. The intensities summed over vibrational bands are usually in good agreement between the calculations and the tabulated results, but individual lines strengths can differ greatly. A high temperature list consisting of 307,721,352 lines is generated for H2O using our PES and dipole moment function.

Laboratory measurements of HDO/H2O isotopic fractionation during ice deposition in simulated cirrus clouds.

PubMed

Lamb, Kara D; Clouser, Benjamin W; Bolot, Maximilien; Sarkozy, Laszlo; Ebert, Volker; Saathoff, Harald; Möhler, Ottmar; Moyer, Elisabeth J

2017-05-30

The stable isotopologues of water have been used in atmospheric and climate studies for over 50 years, because their strong temperature-dependent preferential condensation makes them useful diagnostics of the hydrological cycle. However, the degree of preferential condensation between vapor and ice has never been directly measured at temperatures below 233 K (-40 °C), conditions necessary to form cirrus clouds in the Earth's atmosphere, routinely observed in polar regions, and typical for the near-surface atmospheric layers of Mars. Models generally assume an extrapolation from the warmer experiments of Merlivat and Nief [Merlivat L, Nief G (1967) Tellus 19:122-127]. Nonequilibrium kinetic effects that should alter preferential partitioning have also not been well characterized experimentally. We present here direct measurements of HDO/H 2 O equilibrium fractionation between vapor and ice ([Formula: see text]) at cirrus-relevant temperatures, using in situ spectroscopic measurements of the evolving isotopic composition of water vapor during cirrus formation experiments in a cloud chamber. We rule out the recent proposed upward modification of [Formula: see text], and find values slightly lower than Merlivat and Nief. These experiments also allow us to make a quantitative validation of the kinetic modification expected to occur in supersaturated conditions in the ice-vapor system. In a subset of diffusion-limited experiments, we show that kinetic isotope effects are indeed consistent with published models, including allowing for small surface effects. These results are fundamental for inferring processes on Earth and other planets from water isotopic measurements. They also demonstrate the utility of dynamic in situ experiments for studying fractionation in geochemical systems.

Performance of the Chicago Water Isotope Spectrometer in the UTLS during the Asian Monsoon

NASA Astrophysics Data System (ADS)

Gaeta, D. C.; Clouser, B.; Sarkozy, L.; Singer, C. E.; Moyer, E. J.

2017-12-01

The preferential condensation of water vapor isotopologues makes the isotopic composition of water vapor a useful tracer of the processes responsible for the distribution of water in the UTLS, but the UTLS also offers particular challenges for its measurement. We report here on the field performance of a new instrument designed for measurement of HDO and H2O in the UTLS region: the Chicago Water Isotope Spectrometer (Chi-WIS). Chi-WIS is a laser-based infrared absorption spectrometer at 2.65 μm that uses a high-reflectivity optical cavity to obtain 6 km of effective path length, allowing sensitive measurements of scarce molecules. During the 2017 StratoClim aircraft campaign in Kathmandu, Nepal, Chi-WIS flew aboard the M-55 Geophysica high-altitude research aircraft in a series of flights to probe the Asian Monsoon. Preliminary results show in-flight performance consistent with laboratory performance and the achievement of design targets necessary to reach UTLS science goals. Residual noise on spectra is stable across flights at 4-5x10-4 with 1 second averaging (i.e. absorption depth of .04-.05%); the instrument is robust in terms of alignment and shows no evidence of optical resonances. The resulting measurement precision is as expected from these characteristics. Because we use a relatively strong water line, the water vapor measurement is extremely precise: constant-altitude flight legs in the stratosphere at 4 ppm H2O show 1 s standard deviation 0.03 ppmv for 1 s averaging, and 0.08 ppbv for HDO with 10 s averaging. We show comparisons with other StratoClim instruments and examples of how these measurements resolve scientifically relevant atmospheric features.

Laboratory measurements of HDO/H2O isotopic fractionation during ice deposition in simulated cirrus clouds

PubMed Central

Lamb, Kara D.; Clouser, Benjamin W.; Bolot, Maximilien; Sarkozy, Laszlo; Ebert, Volker; Saathoff, Harald; Möhler, Ottmar; Moyer, Elisabeth J.

2017-01-01

The stable isotopologues of water have been used in atmospheric and climate studies for over 50 years, because their strong temperature-dependent preferential condensation makes them useful diagnostics of the hydrological cycle. However, the degree of preferential condensation between vapor and ice has never been directly measured at temperatures below 233 K (−40 °C), conditions necessary to form cirrus clouds in the Earth’s atmosphere, routinely observed in polar regions, and typical for the near-surface atmospheric layers of Mars. Models generally assume an extrapolation from the warmer experiments of Merlivat and Nief [Merlivat L, Nief G (1967) Tellus 19:122–127]. Nonequilibrium kinetic effects that should alter preferential partitioning have also not been well characterized experimentally. We present here direct measurements of HDO/H2O equilibrium fractionation between vapor and ice (αeq) at cirrus-relevant temperatures, using in situ spectroscopic measurements of the evolving isotopic composition of water vapor during cirrus formation experiments in a cloud chamber. We rule out the recent proposed upward modification of αeq, and find values slightly lower than Merlivat and Nief. These experiments also allow us to make a quantitative validation of the kinetic modification expected to occur in supersaturated conditions in the ice–vapor system. In a subset of diffusion-limited experiments, we show that kinetic isotope effects are indeed consistent with published models, including allowing for small surface effects. These results are fundamental for inferring processes on Earth and other planets from water isotopic measurements. They also demonstrate the utility of dynamic in situ experiments for studying fractionation in geochemical systems. PMID:28495968

NASA Study Hints at Possible Change in Water ‘Fingerprint’ of Comet

NASA Image and Video Library

2017-12-08

A trip past the sun may have selectively altered the production of one form of water in a comet – an effect not seen by astronomers before, a new NASA study suggests. Astronomers from NASA’s Goddard Space Flight Center in Greenbelt, Maryland, observed the Oort cloud comet C/2014 Q2, also called Lovejoy, when it passed near Earth in early 2015. Through NASA’s partnership in the W. M. Keck Observatory on Mauna Kea, Hawaii, the team observed the comet at infrared wavelengths a few days after Lovejoy passed its perihelion – or closest point to the sun. The team focused on Lovejoy’s water, simultaneously measuring the release of H2O along with production of a heavier form of water, HDO. Water molecules consist of two hydrogen atoms and one oxygen atom. A hydrogen atom has one proton, but when it also includes a neutron, that heavier hydrogen isotope is called deuterium, or the “D” in HDO. From these measurements, the researchers calculated the D-to-H ratio – a chemical fingerprint that provides clues about exactly where comets (or asteroids) formed within the cloud of material that surrounded the young sun in the early days of the solar system. Researchers also use the D-to-H value to try to understand how much of Earth’s water may have come from comets versus asteroids. Read more: go.nasa.gov/2lvd6Vt NASA image use policy. NASA Goddard Space Flight Center enables NASA’s mission through four scientific endeavors: Earth Science, Heliophysics, Solar System Exploration, and Astrophysics. Goddard plays a leading role in NASA’s accomplishments by contributing compelling scientific knowledge to advance the Agency’s mission. Follow us on Twitter Like us on Facebook Find us on Instagram

Mild Biomass Liquefaction Process for Economic Production of Stabilized Refinery-Ready Bio-oil

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

Gangwal, Santosh; Meng, Jiajia; McCabe, Kevin

Southern Research (SR) in cooperation with U.S. Department of Energy (DOE), Bioenergy Technology Office (BETO), investigated a biomass liquefaction process for economic production of stabilized refinery-ready bio-oil. The project was awarded by DOE under a Funding Opportunity Announcement (DE-FOA-0000686) for Bio-oil Stabilization and Commoditization that intended to evaluate the feasibility of using bio-oil as a potential feedstock in an existing petroleum refinery. SR investigated Topic Area 1 of the FOA at Technology Readiness Level 2-3 to develop thermochemical liquefaction technologies for producing a bio-oil feedstock from high-impact biomass that can be utilized within a petroleum refinery. Bio-oil obtained from fastmore » pyrolysis of biomass is a green intermediate that can be further upgraded into a biofuel for blending in a petroleum refinery using a hydro-deoxygenation (HDO) route. Co-processing pyrolysis bio-oil in a petroleum refinery is an attractive approach to leverage the refinery’s existing capital. However, the petroleum industry is reluctant to accept pyrolysis bio-oil because of a lack of a standard definition for an acceptable bio-oil feedstock in existing refinery processes. Also per BETO’s multiyear program plan, fast pyrolysis-based bio-fuel is presently not cost competitive with petroleum-based transportation fuels. SR aims to develop and demonstrate a cost-effective low-severity thermal liquefaction and hydrodeoxygenation (HDO) process to convert woody biomass to stabilized bio-oils that can be directly blended with hydrotreater input streams in a petroleum refinery for production of gasoline and/or diesel range hydrocarbons. The specific project objectives are to demonstrate the processes at laboratory scale, characterize the bio-oil product and develop a plan in partnership with a refinery company to move the technology towards commercialization.« less

Using the full IASI spectrum for the physical retrieval of temperature, H2O, HDO, O3, minor and trace gases

NASA Astrophysics Data System (ADS)

Serio, C.; Blasi, M. G.; Liuzzi, G.; Masiello, G.; Venafra, S.

2017-02-01

IASI (Infrared Atmospheric Sounder Interferometer) is flying on the European MetOp series of weather satellites. Besides acquiring temperature and humidity data, IASI also observes the infrared emission of the main minor and trace atmospheric components with high precision. The retrieval of these gases would be highly beneficial to the efforts of scientists monitoring Earths climate. IASI retrieval capability and algorithms have been mostly driven by Numerical Weather Prediction centers, whose limited resources for data transmission and computing is hampering the full exploitation of IASI information content. The quest for real or nearly real time processing has affected the precision of the estimation of minor and trace gases, which are normally retrieved on a very coarse spatial grid. The paper presents the very first retrieval of the complete suite of IASI target parameters by exploiting all its 8461 channels. The analysis has been exemplified for sea surface and the target parameters will include sea surface temperature, temperature profile, water vapour and HDO profiles, ozone profile, total column amount of CO, CO2, CH4, N2O, SO2, HNO3, NH3, OCS and CF4. Concerning CO2, CH4 and N2O, it will be shown that their colum amount can be obtained for each single IASI IFOV (Instantaneous Field of View) with a precision better than 1-2%, which opens the possibility to analyze, e.g., the formation of regional patterns of greenhouse gases. To assess the quality of the retrieval, a case study has been set up which considers two years of IASI soundings over the Hawaii, Manua Loa validation station.

Synthesis and Hydrodeoxygenation Properties of Ruthenium Phosphide Catalysts

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

Bowker, Richard H.; Smith, Mica C.; Pease, Melissa

2011-07-01

Ru2P/SiO2 and RuP/SiO2 catalysts were prepared by the temperature-programmed reduction (TPR) of uncalcined precursors containing hypophosphite ion (H2PO2-) as the phosphorus source. The Ru2P/SiO2 and RuP/SiO2 catalysts had small average particle sizes (~4 nm) and high CO chemisorption capacities (90-110 umol/g). The Ru phosphide catalysts exhibited similar or higher furan (C4H4O) hydrodeoxygenation (HDO) activities than did a Ru/SiO2 catalyst, and the phosphide catalysts favored C4 hydrocarbon products while the Ru metal catalyst produced primarily C3 hydrocarbons.

What's New With Hale Bopp?

NASA Astrophysics Data System (ADS)

Shylaja, B. S.

1997-06-01

The comet Hale-Bopp has provided a great opportunity to astrophysicists. It is bright and it has been available for observations for a long period of time. A good number of large telescopes all over the northern hemisphere have been deployed for observations of this comet. Within a month of its discovery came the first result that the comet was quite active even when it was beyond Jupiter. Jets of gas and dust continued to stream out one after the other. This created the suspicion that the magnitude estimates may turn out to be only the limits rather than the actual values. The anxiety, so created disappeared only when the comet reached the visibility limits in late 1996. By the time it reached the perihelion on April 1, it was not fooling around anymore and kept up the promise of a 'civilized comet', the one that could be located without a finding chart. As is well known, the magnitude after the perihelion passage, would be slightly higher than the estimated value. The two-tail structure was first noticed a few months prior to the perihelion. The gradation in colour from blue of the ion tail to yellow of the dust tail was quite conspicuous. A simple binocular could easily resolve the two. Interestingly, just after the perihelion, there was a flare and the associated storm on the sun due to which a temporary increase in the solar wind particle density can occur. It would be extremely interesting to find the related effects on the tail, especially on the ion component. The solar and cometary physicists are (as on April 26th) eagerly looking forward to monitoring the changes. The ion tail has grown to about 15 degrees in the sky and is expected to get disrupted after the solar storm. On the other hand, the dust tail which grew to a full length of 45 degrees offered a glorious sight in the evening sky. The new moon at the time of perihelion enhanced the spectacle. In the middle of April quite suddenly, a third tail, a sharp yellow one, showed up. This was attributed to the presence of the neutral sodium component. Comets Halley and Hyakutake both had shown this type of tail structure. Last year comet Hyakutake made news for it was emitting soft X-rays, not a known cometary trait until then. Hale Bopp has followed suit. The LECS instrument onboard BeppoSAX spacecraft provided the news for the Netherlands Team. A thermal bremstrahlung model for 0.36 keV X-rays compares well with that of Hyakutake. This implies that the luminosity of the lines of carbon or oxygen in X-rays is less than 10 per cent of the continuum. Results on the coma structure and rotation of the nucleus of the Hale Bopp have started appearing already. A change in the direction of rotation during February 1997 has been observed. The list of molecules detected from spectroscopic investigations is ever increasing - H2O, HDO, OH H2O(+), CO, CO2, CO(+), HCO(+), H2S, SO, SO2, H2CS, OCS, CS, CH3OH (Plenty of alcohol!) H2CO, HCOOH, CH3CN, HNC, HC3N, HNCO, CN, NH3, NH2, NH2CHO, NHCH4, C2H2, C2H6, C3, C2, Na and many isotopes! The detection of deuterated water (HDO, heavy water) has provided a first measure of D/H ratio. Meir (University of Hawaii) and his team calculated HDO production rate of 4 x 1026 molecules/sec. The production rate of water is 2 x 1030 making the HDO/H2O ratio as 2 x 104. This makes Hale Bopp a "normal comet", akin to Halley and Hyakutake. With more than 3000 images on the web sites, the comet Hale Bopp is providing a wealth of information on the various aspects of the cometary science. With almost 300 tons of cometary material falling onto the earth every year and with the detection of frozen water on moon and mercury (obviously the sources have to be comets) the comets are believed to be promoters of life on earth.

Quantitatively probing water and its isotopomers: from theory to experiments; the contribution of a chemical and astrophysical European network 'Our Astrochemical History'

NASA Astrophysics Data System (ADS)

Wiesenfeld, Laurent

2015-08-01

In order to retrieve actual molecular abundances from astrophysical observations of molecular spectral lines, knowledge of the rotational levels excitation schemes is essential to go beyond Local Thermodynamical Equilibrium. These rates are almost always obtained from theoretical investigations, by computing classical or quantum dynamics of the interaction of molecules with these colliders (roueff2013).Our laboratories have recently calculated a set of collision coefficients characterizing the efficiency of energy transfer between molecular hydrogen of helium and a large variety of interstellar molecules. One of the main goal has been water and its isotopomers, computingrates for H2O, HDO and D2O in collision with H2 (valiron2008,faure2012,daniel2011).We felt it necessary to have a multidisciplinary approach: theoretical on the one hand, experimental on the second. Indeed, excitation coefficient computation is a process involving many codes and approximations. Hence we compared our theoretical results to several experiments: spectroscopy of the H2O-H2 van der Waals complex (vanderavoird 2012), differential cross sections (yang 2010, 2011), pressure broadening (drouin 2012).Thanks to these precise determinations, many water abundances could be quantitatively measured, like the HDO/H2O ratio (coutens 2012).While the excitation of water is by now well understood, much remains to be done for heavier molecules, paving the way to quantitative measures of complex organic molecules . A multi disciplinary approach is necessary, that keeps in mind the necessities of actual astrophysical observations. To do so, we describe the European COST network ‘Our Astrochemical History’ (http://prague2015astrohistory.vscht.cz/) , which brings together specialists of many areas of chemistry together with astronomy, in order to address this kind of problem. It focussses on the molecular evolution towards higher complexity and aim sat delivering new schemes for physical chemistry at large, like chemistry of transient species and photochemistry, in gas or on surfaces.

Measurements of CO2, CH4, H2O, and HDO over a 2-km Outdoor Path with Dual-Comb Spectroscopy

NASA Astrophysics Data System (ADS)

Rieker, G. B.; Giorgetta, F. R.; Coddington, I.; Swann, W. C.; Sinclair, L. C.; Cromer, C.; Baumann, E.; Newbury, N. R.; Kofler, J.; Petron, G.; Sweeney, C.; Tans, P. P.

2013-12-01

We demonstrate simultaneous sensing of CO2, CH4, H2O, and HDO over a 2-km outdoor open air path using dual-frequency-comb absorption spectroscopy (DCS). Our implementation of the DCS technique simultaneously offers broad spectral coverage (>8 THz, 267 cm-1) and fine spectral point spacing (100 MHz, 0.0033 cm-1) with a coherent eye-safe beam. The spectrometer, which is adapted from [Zolot et al., 2012], consists of two mutually coherent Erbium-doped fiber frequency-comb lasers which create a broad spectrum of perfectly spaced narrow linewidth frequency elements (';comb teeth') near 1.6 μm. The comb light is transmitted by a telescope and active steering mirrors from the roof of the NIST Boulder laboratory to a 50-cm flat mirror located 1 km away. The return light is received by a second telescope and carried via multimode fiber to a detector. The greenhouse gas absorption attenuates the teeth from the two combs that are coincident with the relevant molecular resonant frequencies. We purposefully offset the frequencies between the two frequency combs in a Vernier-like fashion so that each pair of comb teeth from the two combs results in a unique rf heterodyne beat frequency on the photodiode. The spectral spacing between subsequent comb teeth pairs is 100 MHz, far lower than the ~4 GHz linewidths of small molecule absorption features in the atmosphere. Because of the narrow comb linewidth, there is an essentially negligible instrument lineshape. The measured absorption spectrum can thus resolve neighboring absorption features of different species, and can be compared directly with HITRAN and recent greenhouse gas absorption models developed for satellite- and ground-based carbon observatories to determine the path-integrated concentrations of the absorbing species. Measurements covering the complete 30013←00001 absorption band of CO2 and absorption features of CH4, H2O and HDO between 1.6-1.67 μm were performed under a variety of atmospheric conditions. During windy conditions when the atmosphere is well-mixed and species concentrations are stable, long-time-average data (240 min) are used to achieve high signal-to-noise ratio for careful comparisons of different spectral absorption models to the measured spectrum. Shorter five minute time resolution spectra are used to track fluctuations in atmospheric greenhouse gas concentrations over diurnal cycles and different weather conditions, and compared with simultaneous point-sampled measurements using a commercial cavity ringdown-based gas sensor. A. M. Zolot, F. R. Giorgetta, E. Baumann, J. W. Nicholson, W. C. Swann, I. Coddington, and N. R. Newbury (2012), Direct-Comb Molecular Spectroscopy with Accurate, Resolved Comb Teeth over 43 THz, Opt. Lett., 37(4), 638-640. a) Transmitted intensity spectrum over the 2-km outdoor path showing the spectral intensity variations of the combs and fine structure from gas absorption. b) Background-corrected absorbance of CO2 (blue) fitted with a Hitran model (red). The CO2 concentration measured from the fit is 408 ppm.

Bio-aviation fuel production from hydroprocessing castor oil promoted by the nickel-based bifunctional catalysts.

PubMed

Liu, Siyang; Zhu, Qingqing; Guan, Qingxin; He, Liangnian; Li, Wei

2015-05-01

Bio-aviation fuel was firstly synthesized by hydroprocessing castor oil in a continuous-flow fixed-bed microreactor with the main objective to obtain the high yield of aviation fuel and determine the elemental compositions of the product phases as well as the reaction mechanism. Highest aviation range alkane yields (91.6 wt%) were achieved with high isomer/n-alkane ratio (i/n) 4.4-7.2 over Ni supported on acidic zeolites. In addition, different fuel range alkanes can be obtained by adjusting the degree of hydrodeoxygenation (HDO) and hydrocracking. And the observations are rationalized by a set of reaction pathways for the various product phases. Copyright © 2015 Elsevier Ltd. All rights reserved.

Communication: Disorder-suppressed vibrational relaxation in vapor-deposited high-density amorphous ice

NASA Astrophysics Data System (ADS)

Shalit, Andrey; Perakis, Fivos; Hamm, Peter

2014-04-01

We apply two-dimensional infrared spectroscopy to differentiate between the two polyamorphous forms of glassy water, low-density (LDA) and high-density (HDA) amorphous ices, that were obtained by slow vapor deposition at 80 and 11 K, respectively. Both the vibrational lifetime and the bandwidth of the 1-2 transition of the isolated OD stretch vibration of HDO in H2O exhibit characteristic differences when comparing hexagonal (Ih), LDA, and HDA ices, which we attribute to the different local structures - in particular the presence of interstitial waters in HDA ice - that cause different delocalization lengths of intermolecular phonon degrees of freedom. Moreover, temperature dependent measurements show that the vibrational lifetime closely follows the structural transition between HDA and LDA phases.

Selective One-Pot Production of High-Grade Diesel-Range Alkanes from Furfural and 2-Methylfuran over Pd/NbOPO4.

PubMed

Xia, Qineng; Xia, Yinjiang; Xi, Jinxu; Liu, Xiaohui; Zhang, Yongguang; Guo, Yong; Wang, Yanqin

2017-02-22

A one-pot method for the selective production of high-grade diesel-range alkanes from biomass-derived furfural and 2-methylfuran (2-MF) was developed by combining the hydroxyalkylation/alkylation (HAA) condensation of furfural with 2-MF and the subsequent hydrodeoxygenation (HDO) over a multifunctional Pd/NbOPO 4 catalyst. The effects of various reaction conditions as well as a variety of solid-acid catalysts and metal-loaded NbOPO 4 catalysts were systematically investigated to optimize the reaction conditions for both reactions. Under the optimal reaction conditions up to 89.1 % total yield of diesel-range alkanes was obtained from furfural and 2-MF by this one-pot method. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pt-based Bi-metallic Monolith Catalysts for Partial Upgrading of Microalgae Oil

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

Lawal, Adeniyi; Manganaro, James; Goodall, Brian

Valicor’s proprietary wet extraction process in conjunction with thermochemical pre-treatment was performed on algal biomass from two different algae strains, Nannochloropsis Salina (N.S.) and Chlorella to produce algae oils. Polar lipids such as phospholipids were hydrolyzed, and metals and metalloids, known catalyst poisons, were separated into the aqueous phase, creating an attractive “pre-refined” oil for hydrodeoxygenation (HDO) upgrading by Stevens. Oil content and oil extraction efficiency of approximately 30 and 90% respectively were achieved. At Stevens, we formulated a Pt-based bi-metallic catalyst which was demonstrated to be effective in the hydro-treating of the algae oils to produce ‘green’ diesel. Themore » bi-metallic catalyst was wash-coated on a monolith, and in conjunction with a high throughput high pressure (pilot plant) reactor system, was used in hydrotreating algae oils from N.S. and Chlorella. Mixtures of these algae oils and refinery light atmospheric gas oil (LAGO) supplied by our petroleum refiner partner, Marathon Petroleum Corporation, were co-processed in the pilot plant reactor system using the Pt-based bi-metallic monolith catalyst. A 26 wt% N.S. algae oil/74 wt % LAGO mixture hydrotreated in the reactor system was subjected to the ASTM D975 Diesel Fuel Specification Test and it met all the important requirements, including a cetane index of 50.5. An elemental oxygen analysis performed by an independent and reputable lab reported an oxygen content of trace to none found. The successful co-processing of a mixture of algae oil and LAGO will enable integration of algae oil as a refinery feedstock which is one of the goals of DOE-BETO. We have presented experimental data that show that our precious metal-based catalysts consume less hydrogen than the conventional hydrotreating catalyst NiMo Precious metal catalysts favor the hydrodecarbonylation/hydrodecarboxylation route of HDO over the dehydration route preferred by base metal catalysts, and consumes less hydrogen, if methanation can be mitigated. Our methanation data on Pt and Rh indicate effective suppression of methanation. Our data also show that our catalysts are less susceptible to coking; and unlike NiMo and CoMo, precious metal catalysts are not deactivated by water, a by-product of HDO of algae oil. Finally, our catalysts do not need to be sulfided to be active. A rigorous techno-economic analysis of our process for commercial scale production of 10,000 barrels per day of hydrotreated algae oil, with nutraceuticals co-product claiming only 0.05% of the raw algae oil, indicates an estimated plant gate price of ~$10/gal. Sensitivity analysis shows that critical parameters affecting sale price include (1) algae doubling time (2) biomass oil content (3) CAPEX, and (4) moisture content of post extracted algae residue. Modest improvements in these areas will result in enhanced and competitive economics. Based on a life cycle assessment for greenhouse gas emission, we found that if algae oil replaced 10% of the US consumption, this would result in a CO2e reduction of 210,000 tons per day. Improving the drying process for animal feed by 50% would result in further significant reduction in CO2e.« less

Seasonal/Diurnal Mapping of Ozone and Water in the Martian Atmosphere

NASA Technical Reports Server (NTRS)

Novak, R. E.; Mumma, M. J.; DiSanti, M. A.; DelloRusso, N.; Magee-Sauer, K.; Bonev, B.

2003-01-01

Ozone and water are key species for understanding the stability and evolution of Mars atmosphere; they are closely linked (along with CO, H, OH, and O) through photochemistry. Photolysis of water produces the OH radical (thought to catalyze reformation of CO2 from CO and O2) and atomic hydrogen (which reacts with O3 forming OH and O2). Atomic hydrogen also reacts with O2 (forming HO2), thereby reducing the amount of O2 available to reform O3 from collisions between O and O2. Hence ozone and water should be anti-correlated on Mars. Photolysis of O3 produces O2(a(sup 1) delta g) with 90% efficiency, and the resulting emission band system near 1.27 mm traces the presence and abundance of ozone. This approach was initially used to study ozone on Earth and then applied to Mars. In 1997, we measured several lines of the O2(a(sup 1) delta g) emission using CSHELL at the NASA IRTF; the O2(a(sup 1) delta g) state is also quenched by collisions with CO2. This quenching dominates at lower altitudes so that the detected emissions are used to detect ozone column densities above 20 km. The slit was positioned N-S along Mars' central meridian resulting in a one-dimensional map of ozone. Nearly simultaneous maps may be made of water using CSHELL by detecting the v1 fundamental band of HDO near 3.67 microns and using the D/H ratio for Mars. This technique was used by DiSanti and Mumma. With CSHELL, measurements for both O2(a(sup 1) delta g) emissions and HDO absorptions can be made during the day or night. Since January, 1997, we have repeated these measurements at different times during the Martian year. For all of these dates, we have positioned the slit N-S along the central meridian; for some of these dates, we have also stepped the slit across the planet at 1 arc-sec intervals generating a 2-dimensional map. We have also positioned the slit E-W on Mars thus providing diurnal variations of ozone and water along the slit.

Crystal structure and infrared spectra of dicesium trans-tetraaquadichlorochromium(III) chloride

NASA Astrophysics Data System (ADS)

Neumann, E.; Stefov, V.; Šoptrajanov, B.; Engelen, B.; Lutz, H. D.

2004-12-01

The crystal structure of dicesium trans-tetraaquadichlorochromium(III) chloride Cs 2Cr IIICl 5·4H 2O with trans-[M IIIX 2(H 2O) 4] + complex ions (space group C2/c, Z=4, a=1915.3(4) pm, b=614.1(1) pm, c=1392.0(3) pm, and β=118.24(3)°, final R1=0.0246 for 2100 unique reflections) was redetermined by single-crystal X-ray diffraction studies. It was found to crystallize in a 2c super structure of the structure reported previously (Inorg. Chem. 20 (1981) 1566; Inorg. Chem. 36 (1997) 2248). The obtained structure data now agree with the results of infrared spectroscopic studies, which has been confirmed in this work, namely that there are two different hydrate H 2O molecules in the structure. Phase transitions, static or dynamic disorder of the hydrate H 2O molecules, and space group C2/m proposed in the literature were ruled out. The coordinates of the four hydrogen positions derived from the X-ray data have been improved via the O-H distances derived from the wave numbers of the OD stretching modes of matrix isolated HDO molecules (2426, 2323, and 2306 cm -1, 263 K) by using the νOD versus rO-H correlation curve reported in the literature (J. Mol. Struct. 404 (1997) 63). The νOD versus rH⋯Cl correlation curve reported by Mikenda (J. Mol. Struct. 147 (1986) 1) should be improved, especially for strong hydrogen bonds. The two hydrate H 2O molecules of the title compound are strongly distorted with a weak and a relatively strong O-H⋯Cl hydrogen bond each thus intramolecular coupling of the two OH stretching vibrations to coupled ones is largely reduced and, hence, the wavenumbers of the OH and OD stretching modes of the HDO molecules mainly resemble those of the H 2O and D 2O molecules. The strength of the hydrogen bonds is in accordance with the predictions of the competitive and synergetic effects. Chloro ligands are weaker hydrogen bond acceptor groups than chloride ions.

Tracing early evolutionary stages of high-mass star formation with molecular lines

NASA Astrophysics Data System (ADS)

Marseille, M. G.; van der Tak, F. F. S.; Herpin, F.; Jacq, T.

2010-11-01

Context. Despite its major role in the evolution of the interstellar medium, the formation of high-mass stars (M ≥ 10 M_⊙) remains poorly understood. Two types of massive star cluster precursors, the so-called massive dense cores (MDCs), have been observed, which differ in terms of their mid-infrared brightness. The origin of this difference has not yet been established and may be the result of evolution, density, geometry differences, or a combination of these. Aims: We compare several molecular tracers of physical conditions (hot cores, shocks) observed in a sample of mid-IR weakly emitting MDCs with previous results obtained in a sample of exclusively mid-IR bright MDCs. We attempt to understand the differences between these two types of object. Methods: We present single-dish observations of HDO, H_218O, SO2, and CH3OH lines at λ = 1.3-3.5 mm. We study line profiles and estimate abundances of these molecules, and use a partial correlation method to search for trends in the results. Results: The detection rates of thermal emission lines are found to be very similar for both mid-IR quiet and bright objects. The abundances of H2O, HDO (10-13 to 10-9 in the cold outer envelopes), SO2 and CH3OH differ from source to source but independently of their mid-IR flux. In contrast, the methanol class I maser emission, a tracer of outflow shocks, is found to be strongly anti-correlated with the 12 μm source brightnesses. Conclusions: The enhancement of the methanol maser emission in mid-IR quiet MDCs may be indicative of a more embedded nature. Since total masses are similar between the two samples, we suggest that the matter distribution is spherical around mid-IR quiet sources but flattened around mid-IR bright ones. In contrast, water emission is associated with objects containing a hot molecular core, irrespective of their mid-IR brightness. These results indicate that the mid-IR brightness of MDCs is an indicator of their evolutionary stage.

Isotopic Ratios of H, C, N, O, and S in Comets C2012 F6 (lemmon) and C2014 Q2 (lovejoy) * ** ***

NASA Technical Reports Server (NTRS)

Biver, N.; Moreno, R.; Sandqvist, Aa.; Bockelee-Morvan, D.; Colom, P.; Crovisier, J.; Lis, D. C.; Bossier, J.; Debout, V.; Paubert, G.;

Evaluating climate model performance in the tropics with retrievals of water isotopic composition from Aura TES

NASA Astrophysics Data System (ADS)

Field, Robert; Kim, Daehyun; Kelley, Max; LeGrande, Allegra; Worden, John; Schmidt, Gavin

2014-05-01

Observational and theoretical arguments suggest that satellite retrievals of the stable isotope composition of water vapor could be useful for climate model evaluation. The isotopic composition of water vapor is controlled by the same processes that control water vapor amount, but the observed distribution of isotopic composition is distinct from amount itself . This is due to the fractionation that occurs between the abundant H216O isotopes (isotopologues) and the rare and heavy H218O and HDO isotopes during evaporation and condensation. The fractionation physics are much simpler than the underlying moist physics; discrepancies between observed and modeled isotopic fields are more likely due to problems in the latter. Isotopic measurements therefore have the potential for identifying problems that might not be apparent from more conventional measurements. Isotopic tracers have existed in climate models since the 1980s but it is only since the mid 2000s that there have been enough data for meaningful model evaluation in this sense, in the troposphere at least. We have evaluated the NASA GISS ModelE2 general circulation model over the tropics against water isotope (HDO/H2O) retrievals from the Aura Tropospheric Emission Spectrometer (TES), alongside more conventional measurements. A small ensemble of experiments was performed with physics perturbations to the cumulus and planetary boundary layer schemes, done in the context of the normal model development process. We examined the degree to which model-data agreement could be used to constrain a select group of internal processes in the model, namely condensate evaporation, entrainment strength, and moist convective air mass flux. All are difficult to parameterize, but exert strong influence over model performance. We found that the water isotope composition was significantly more sensitive to physics changes than precipitation, temperature or relative humidity through the depth of the tropical troposphere. Among the processes considered, this was most closely, and fairly exclusively, related to mid-tropospheric entrainment strength. This demonstrates that water isotope retrievals have considerable potential alongside more conventional measurements for climate model evaluation and development.

Thermal structure and minor species distribution of Venus mesosphere by ALMA submm observations

NASA Astrophysics Data System (ADS)

Piccialli, Arianna; Moreno, Raphael; Encrenaz, Therese; Fouchet, Thierry; Lellouch, Emmanuel; Moullet, Arielle; Widemann, Thomas

2015-11-01

Venus upper atmosphere (70-150 km altitude) is a transition region characterized by a complex dynamics: strong retrograde zonal winds dominate the lower mesosphere while a solar-to-antisolar circulation is observed in the upper mesosphere/lower thermosphere. In addition, photochemical processes play an important role at these altitudes and affect the thermal structure and chemical stability of the entire atmosphere. Sulfur dioxide and water vapor are key species in the photochemical cycles taking place in the troposphere and mesosphere of Venus. They are carried by convective transport, together with the Hadley circulation, up to about 60 km where SO2 is photodissociated and oxydated, leading to the formation of H2SO4 which condenses in the clouds enshrouding the planet. Previous observations obtained by several instruments on board Venus Express and during ground-based campaigns have shown evidence of strong temporal variations, both on day-to-day as well as longer timescales, of density, temperature and SO2 abundance. Such strong variability is still not well understood.Submillimeter observations obtained with the Atacama Large Millimeter Array (ALMA) offer the possibility of probing Venus upper mesosphere and of monitoring minor species, winds and the thermal structure. A first set of observations was obtained on November 14, 15, 26 and 27, 2011 during the first ALMA Early Science observation cycle. These observations targeted SO2, SO, HDO and CO transitions around 345 GHz during four sequences of 30 minutes each. The Venus’ disk was about 11” with an illumination factor of 90%, so that mostly the dayside of the planet was mapped.Assuming nominal night-time and dayside CO abundance profiles from Clancy et al. 2013, we retrieved vertical temperature profiles over the entire disk as a function of latitude and local time for the four days of observation. Temperature profiles were later used to derive the abundances of minor species (HDO, SO, SO2) in each pixel of the disk in order to study their spatial and temporal variability.

Vibrational spectroscopy of water in hydrated lipid multi-bilayers. I. Infrared spectra and ultrafast pump-probe observables.

PubMed

Gruenbaum, S M; Skinner, J L

2011-08-21

The vibrational spectroscopy of hydration water in dilauroylphosphatidylcholine lipid multi-bilayers is investigated using molecular dynamics simulations and a mixed quantum/classical model for the OD stretch spectroscopy of dilute HDO in H(2)O. FTIR absorption spectra, and isotropic and anisotropic pump-probe decay curves have been measured experimentally as a function of the hydration level of the lipid multi-bilayer, and our goal is to make connection with these experiments. To this end, we use third-order response functions, which allow us to include non-Gaussian frequency fluctuations, non-Condon effects, molecular rotations, and a fluctuating vibrational lifetime, all of which we believe are important for this system. We calculate the response functions using existing transition frequency and dipole maps. From the experiments it appears that there are two distinct vibrational lifetimes corresponding to HDO molecules in different molecular environments. In order to obtain these lifetimes, we consider a simple two-population model for hydration water hydrogen bonds. Assuming a different lifetime for each population, we then calculate the isotropic pump-probe decay, fitting to experiment to obtain the two lifetimes for each hydration level. With these lifetimes in hand, we then calculate FTIR spectra and pump-probe anisotropy decay as a function of hydration. This approach, therefore, permits a consistent calculation of all observables within a unified computational scheme. Our theoretical results are all in qualitative agreement with experiment. The vibrational lifetime of lipid-associated OD groups is found to be systematically shorter than that of the water-associated population, and the lifetimes of each population increase with decreasing hydration, in agreement with previous analysis. Our theoretical FTIR absorption spectra successfully reproduce the experimentally observed red-shift with decreasing lipid hydration, and we confirm a previous interpretation that this shift results from the hydrogen bonding of water to the lipid phosphate group. From the pump-probe anisotropy decay, we confirm that the reorientational motions of water molecules slow significantly as hydration decreases, with water bound in the lipid carbonyl region undergoing the slowest rotations. © 2011 American Institute of Physics

Vibrational spectroscopy of water in hydrated lipid multi-bilayers. I. Infrared spectra and ultrafast pump-probe observables

PubMed Central

Gruenbaum, S. M.; Skinner, J. L.

2011-01-01

The vibrational spectroscopy of hydration water in dilauroylphosphatidylcholine lipid multi-bilayers is investigated using molecular dynamics simulations and a mixed quantum∕classical model for the OD stretch spectroscopy of dilute HDO in H2O. FTIR absorption spectra, and isotropic and anisotropic pump-probe decay curves have been measured experimentally as a function of the hydration level of the lipid multi-bilayer, and our goal is to make connection with these experiments. To this end, we use third-order response functions, which allow us to include non-Gaussian frequency fluctuations, non-Condon effects, molecular rotations, and a fluctuating vibrational lifetime, all of which we believe are important for this system. We calculate the response functions using existing transition frequency and dipole maps. From the experiments it appears that there are two distinct vibrational lifetimes corresponding to HDO molecules in different molecular environments. In order to obtain these lifetimes, we consider a simple two-population model for hydration water hydrogen bonds. Assuming a different lifetime for each population, we then calculate the isotropic pump-probe decay, fitting to experiment to obtain the two lifetimes for each hydration level. With these lifetimes in hand, we then calculate FTIR spectra and pump-probe anisotropy decay as a function of hydration. This approach, therefore, permits a consistent calculation of all observables within a unified computational scheme. Our theoretical results are all in qualitative agreement with experiment. The vibrational lifetime of lipid-associated OD groups is found to be systematically shorter than that of the water-associated population, and the lifetimes of each population increase with decreasing hydration, in agreement with previous analysis. Our theoretical FTIR absorption spectra successfully reproduce the experimentally observed red-shift with decreasing lipid hydration, and we confirm a previous interpretation that this shift results from the hydrogen bonding of water to the lipid phosphate group. From the pump-probe anisotropy decay, we confirm that the reorientational motions of water molecules slow significantly as hydration decreases, with water bound in the lipid carbonyl region undergoing the slowest rotations. PMID:21861584

Analysing the origin of rain- and subsurface water in seasonal wetlands of north-central Namibia

NASA Astrophysics Data System (ADS)

Hiyama, Tetsuya; Kanamori, Hironari; Kambatuku, Jack R.; Kotani, Ayumi; Asai, Kazuyoshi; Mizuochi, Hiroki; Fujioka, Yuichiro; Iijima, Morio

2017-03-01

We investigated the origins of rain- and subsurface waters of north-central Namibia’s seasonal wetlands, which are critical to the region’s water and food security. The region includes the southern part of the Cuvelai system seasonal wetlands (CSSWs) of the Cuvelai Basin, a transboundary river basin covering southern Angola and northern Namibia. We analysed stable water isotopes (SWIs) of hydrogen (HDO) and oxygen (H2 18O) in rainwater, surface water and shallow groundwater. Rainwater samples were collected during every rainfall event of the rainy season from October 2013 to April 2014. The isotopic ratios of HDO (δD) and oxygen H2 18O (δ 18O) were analysed in each rainwater sample and then used to derive the annual mean value of (δD, δ 18O) in precipitation weighted by each rainfall volume. Using delta diagrams (plotting δD vs. δ 18O), we showed that the annual mean value was a good indicator for determining the origins of subsurface waters in the CSSWs. To confirm the origins of rainwater and to explain the variations in isotopic ratios, we conducted atmospheric water budget analysis using Tropical Rainfall Measuring Mission (TRMM) multi-satellite precipitation analysis (TMPA) data and ERA-Interim atmospheric reanalysis data. The results showed that around three-fourths of rainwater was derived from recycled water at local-regional scales. Satellite-observed outgoing longwave radiation (OLR) and complementary satellite data from MODerate-resolution Imaging Spectroradiometer (MODIS) and Advanced Microwave Scanning Radiometer (AMSR) series implied that the isotopic ratios in rainwater were affected by evaporation of raindrops falling from convective clouds. Consequently, integrated SWI analysis of rain-, surface and subsurface waters, together with the atmospheric water budget analysis, revealed that shallow groundwater of small wetlands in this region was very likely to be recharged from surface waters originating from local rainfall, which was temporarily pooled in small wetlands. This was also supported by tritium (3H) counting of the current rain- and subsurface waters in the region. We highly recommend that shallow groundwater not be pumped intensively to conserve surface and subsurface waters, both of which are important water resources in the region.

Immersion Gratings for Infrared High-resolution Spectroscopy

NASA Astrophysics Data System (ADS)

Sarugaku, Yuki; Ikeda, Yuji; Kobayashi, Naoto; Kaji, Sayumi; Sukegawa, Takashi; Sugiyama, Shigeru; Nakagawa, Takao; Arasaki, Takayuki; Kondo, Sohei; Nakanishi, Kenshi; Yasui, Chikako; Kawakita, Hideyo

2016-10-01

High-resolution spectroscopy in the infrared wavelength range is essential for observations of minor isotopologues, such as HDO for water, and prebiotic organic molecules like hydrocarbons/P-bearing molecules because numerous vibrational molecular bands (including non-polar molecules) are located in this wavelength range. High spectral resolution enables us to detect weak lines without spectral line confusion. This technique has been widely used in planetary sciences, e.g., cometary coma (H2O, CO, and organic molecules), the martian atmosphere (CH4, CO2, H2O and HDO), and the upper atmosphere of gas giants (H3+ and organic molecules such as C2H6). Spectrographs with higher resolution (and higher sensitivity) still have a potential to provide a plenty of findings. However, because the size of spectrographs scales with the spectral resolution, it is difficult to realize it.Immersion grating (IG), which is a diffraction grating wherein the diffraction surface is immersed in a material with a high refractive index (n > 2), provides n times higher spectral resolution compared to a reflective grating of the same size. Because IG reduces the size of spectrograph to 1/n compared to the spectrograph with the same spectral resolution using a conventional reflective grating, it is widely acknowledged as a key optical device to realize compact spectrographs with high spectral resolution.Recently, we succeeded in fabricating a CdZnTe immersion grating with the theoretically predicted diffraction efficiency by machining process using an ultrahigh-precision five-axis processing machine developed by Canon Inc. Using the same technique, we completed a practical germanium (Ge) immersion grating with both a reflection coating on the grating surface and the an AR coating on the entrance surface. It is noteworthy that the wide wavelength range from 2 to 20 um can be covered by the two immersion gratings.In this paper, we present the performances and the applications of the immersion gratings, including the development of a long-NIR (2-5um) high-resolution (R=80,000) spectrograph with Ge-immersion grating, VINROUGE, which is a prototype for the TMT MIR instrument.

Comparison of the hanging-drop technique and running-drip method for identifying the epidural space in dogs.

PubMed

Martinez-Taboada, Fernando; Redondo, José I

2017-03-01

To compare the running-drip and hanging-drop techniques for locating the epidural space in dogs. Prospective, randomized, clinical trial. Forty-five healthy dogs requiring epidural anaesthesia. Dogs were randomized into four groups and administered epidural anaesthesia in sternal (S) or lateral (L) recumbency. All blocks were performed by the same person using Tuohy needles with either a fluid-prefilled hub (HDo) or connected to a drip set attached to a fluid bag elevated 60 cm (RDi). The number of attempts, 'pop' sensation, clear drop aspiration or fluid dripping, time to locate the epidural space (TTLES) and presence of cerebrospinal fluid (CSF) were recorded. A morphine-bupivacaine combination was injected after positive identification. The success of the block was assessed by experienced observers based on perioperative usage of rescue analgesia. Data were checked for normality. Binomial variables were analysed with the chi-squared or Fisher's exact test as appropriate. Non-parametric data were analysed using Kruskal-Wallis and Mann-Whitney tests. Normal data were studied with an anova followed by a Tukey's means comparison for groups of the same size. A p-value of < 0.05 was considered to indicate statistical significance. Lateral recumbency HDo required more attempts (six of 11 dogs required more than one attempt) than SRDi (none of 11 dogs) (p = 0.0062). Drop aspiration was observed more often in SHDo (nine of 11 dogs) than in LHDo (two of 11 dogs) (p = 0.045). Mean (range) TTLES was longer in LHDo [47 (18-82) seconds] than in SHDo [20 (14-79) seconds] (p = 0.006) and SRDi [(34 (17-53) seconds] (p = 0.038). There were no differences in 'pop' sensation, presence of CSF, rescue analgesia or pain scores between the groups. The running-drip method is a useful and fast alternative technique for identifying the epidural space in dogs. The hanging-drop technique in lateral recumbency was more difficult to perform than the other methods, requiring more time and attempts. Copyright © 2017 Association of Veterinary Anaesthetists and American College of Veterinary Anesthesia and Analgesia. Published by Elsevier Ltd. All rights reserved.

THE HYPERFINE STRUCTURE OF THE ROTATIONAL SPECTRUM OF HDO AND ITS EXTENSION TO THE THz REGION: ACCURATE REST FREQUENCIES AND SPECTROSCOPIC PARAMETERS FOR ASTROPHYSICAL OBSERVATIONS

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

Cazzoli, Gabriele; Lattanzi, Valerio; Puzzarini, Cristina

2015-06-10

The rotational spectrum of the mono-deuterated isotopologue of water, HD{sup 16}O, has been investigated in the millimeter- and submillimeter-wave frequency regions, up to 1.6 THz. The Lamb-dip technique has been exploited to obtain sub-Doppler resolution and to resolve the hyperfine (hf) structure due to the deuterium and hydrogen nuclei, thus enabling the accurate determination of the corresponding hf parameters. Their experimental determination has been supported by high-level quantum-chemical calculations. The Lamb-dip measurements have been supplemented by Doppler-limited measurements (weak high-J and high-frequency transitions) in order to extend the predictive capability of the available spectroscopic constants. The possibility of resolving hfmore » splittings in astronomical spectra has been discussed.« less

Measurement of stratospheric trace constituent distributions from balloon-borne far infrared observations

NASA Technical Reports Server (NTRS)

Abbas, M. M.; Guo, J.; Carli, B.; Mencaraglia, F.; Bonetti, A.

1987-01-01

FIR limb thermal emission spectra obtained from balloon-borne measurements made as a part of the Balloon Intercomparison Campaign (BIC) have been analyzed for retrieval of stratospheric trace-constituent distributions. The measurements were made with a high-resolution Michelson interferometer and covered the 15-180/cm spectral range with an unapodized spectral resolution of 0.0033/cm. The retrieved vertical profiles of O3, H2O, HDO, HCN, CO, and isotopes of O3 are presented. The results are compared with the BIC measurements for O3 and H2O made from the same balloon gondola and with other published data. A comparison of the simultaneously retrieved profiles for several gases with the published data shows good agreement and indicates the validity of the FIR data and retrieval techniques and the accuracy of the inferred profiles.

Application, Deactivation, and Regeneration of Heterogeneous Catalysts in Bio-Oil Upgrading

DOE PAGES

Cheng, Shouyun; Wei, Lin; Zhao, Xianhui; ...

2016-12-07

The massive consumption of fossil fuels and associated environmental issues are leading to an increased interest in alternative resources such as biofuels. The renewable biofuels can be upgraded from bio-oils that are derived from biomass pyrolysis. Catalytic cracking and hydrodeoxygenation (HDO) are two of the most promising bio-oil upgrading processes for biofuel production. Heterogeneous catalysts are essential for upgrading bio-oil into hydrocarbon biofuel. Although advances have been achieved, the deactivation and regeneration of catalysts still remains a challenge. This review focuses on the current progress and challenges of heterogeneous catalyst application, deactivation, and regeneration. The technologies of catalysts deactivation, reduction,more » and regeneration for improving catalyst activity and stability are discussed. Some suggestions for future research including catalyst mechanism, catalyst development, process integration, and biomass modification for the production of hydrocarbon biofuels are provided.« less

Application, Deactivation, and Regeneration of Heterogeneous Catalysts in Bio-Oil Upgrading

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

Cheng, Shouyun; Wei, Lin; Zhao, Xianhui

The massive consumption of fossil fuels and associated environmental issues are leading to an increased interest in alternative resources such as biofuels. The renewable biofuels can be upgraded from bio-oils that are derived from biomass pyrolysis. Catalytic cracking and hydrodeoxygenation (HDO) are two of the most promising bio-oil upgrading processes for biofuel production. Heterogeneous catalysts are essential for upgrading bio-oil into hydrocarbon biofuel. Although advances have been achieved, the deactivation and regeneration of catalysts still remains a challenge. This review focuses on the current progress and challenges of heterogeneous catalyst application, deactivation, and regeneration. The technologies of catalysts deactivation, reduction,more » and regeneration for improving catalyst activity and stability are discussed. Some suggestions for future research including catalyst mechanism, catalyst development, process integration, and biomass modification for the production of hydrocarbon biofuels are provided.« less

A Herschel Study of D/H in Water in the Jupiter-family Comet 45P/Honda-Mrkos-Pajdušáková and Prospects for D/H Measurements with CCAT

NASA Astrophysics Data System (ADS)

Lis, D. C.; Biver, N.; Bockelée-Morvan, D.; Hartogh, P.; Bergin, E. A.; Blake, G. A.; Crovisier, J.; de Val-Borro, M.; Jehin, E.; Küppers, M.; Manfroid, J.; Moreno, R.; Rengel, M.; Szutowicz, S.

2013-09-01

We present Herschel observations of water isotopologues in the atmosphere of the Jupiter-family comet 45P/Honda-Mrkos-Pajdušáková. No HDO emission is detected, with a 3σ upper limit of 2.0 × 10-4 for the D/H ratio. This value is consistent with the earlier Herschel measurement in the Jupiter-family comet 103P/Hartley 2. The canonical value of 3 × 10-4 measured pre-Herschel in a sample of Oort-cloud comets can be excluded at a 4.5σ level. The observations presented here further confirm that a diversity of D/H ratios exists in the comet population and emphasize the need for additional measurements with future ground-based facilities, such as CCAT, in the post-Herschel era.

First results of the observations of trace gases in the Martian atmosphere by the Planetary Fourier Spectrometer onboard the Mars Express

NASA Astrophysics Data System (ADS)

Titov, D. V.; Ignatiev, N.; Formisano, V.; Grassi, D.; Giuranna, M.; Maturilli, A.; Piccioni, G.; Moroz, V. I.; Lellouch, E.; Encrenaz, T.; Pfs Team

High spectral resolution observations of Mars by the PFS/Mars Express provide new insight into the atmospheric composition. Spectral features of atmospheric CO2 and its isotopes at 15, 4.3, 2.7, 1.4 μ m, CO at 4.7 and 2.35 μ m, and H2O at 40, 2.56, and 1.38 μ m as well as solar spectral features are clearly identified in the PFS spectra. HDO spectral details at 3.7 μ m were also tentatively detected. The paper will present qualitative and quantitative analysis of the PFS spectra in the regions of spectral bands of trace gases. Abundance of minor constituents will be determined using complete radiative transfer modeling including possible non-LTE effects. We will also present results of search for other minor species with emphasis on the limb observations that provide higher air mass factor.

Strong Water Isotopic Anomalies in the Martian Atmosphere: Probing Current and Ancient Reservoirs

NASA Technical Reports Server (NTRS)

Villanueva, G. L.; Mumma, M. J.; Novak, R. E.; Käufl, H. U.; Hartogh, P.; Encrenaz, T.; Tokunaga, A.; Khayat, A.; Smith, M. D.

2015-01-01

We measured maps of atmospheric water (H2O) and its deuterated form (HDO) across the martian globe, showing strong isotopic anomalies and a significant high deuterium/hydrogen (D/H) enrichment indicative of great water loss. The maps sample the evolution of sublimation from the north polar cap, revealing that the released water has a representative D/H value enriched by a factor of about 7 relative to Earth's ocean [Vienna standard mean ocean water (VSMOW)]. Certain basins and orographic depressions show even higher enrichment, whereas high-altitude regions show much lower values (1 to 3 VSMOW). Our atmospheric maps indicate that water ice in the polar reservoirs is enriched in deuterium to at least 8 VSMOW, which would mean that early Mars (4.5 billion years ago) had a global equivalent water layer at least 137 meters deep.

A HERSCHEL STUDY OF D/H IN WATER IN THE JUPITER-FAMILY COMET 45P/HONDA-MRKOS-PAJDUSAKOVA AND PROSPECTS FOR D/H MEASUREMENTS WITH CCAT

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

Lis, D. C.; Blake, G. A.; Biver, N.

We present Herschel observations of water isotopologues in the atmosphere of the Jupiter-family comet 45P/Honda-Mrkos-Pajdusakova. No HDO emission is detected, with a 3{sigma} upper limit of 2.0 Multiplication-Sign 10{sup -4} for the D/H ratio. This value is consistent with the earlier Herschel measurement in the Jupiter-family comet 103P/Hartley 2. The canonical value of 3 Multiplication-Sign 10{sup -4} measured pre-Herschel in a sample of Oort-cloud comets can be excluded at a 4.5{sigma} level. The observations presented here further confirm that a diversity of D/H ratios exists in the comet population and emphasize the need for additional measurements with future ground-based facilities,more » such as CCAT, in the post-Herschel era.« less

Strong water isotopic anomalies in the martian atmosphere: probing current and ancient reservoirs.

PubMed

Villanueva, G L; Mumma, M J; Novak, R E; Käufl, H U; Hartogh, P; Encrenaz, T; Tokunaga, A; Khayat, A; Smith, M D

2015-04-10

We measured maps of atmospheric water (H2O) and its deuterated form (HDO) across the martian globe, showing strong isotopic anomalies and a significant high deuterium/hydrogen (D/H) enrichment indicative of great water loss. The maps sample the evolution of sublimation from the north polar cap, revealing that the released water has a representative D/H value enriched by a factor of about 7 relative to Earth's ocean [Vienna standard mean ocean water (VSMOW)]. Certain basins and orographic depressions show even higher enrichment, whereas high-altitude regions show much lower values (1 to 3 VSMOW). Our atmospheric maps indicate that water ice in the polar reservoirs is enriched in deuterium to at least 8 VSMOW, which would mean that early Mars (4.5 billion years ago) had a global equivalent water layer at least 137 meters deep. Copyright © 2015, American Association for the Advancement of Science.

Heavy water stratification in a low-mass protostar

NASA Astrophysics Data System (ADS)

Coutens, A.; Vastel, C.; Cazaux, S.; Bottinelli, S.; Caux, E.; Ceccarelli, C.; Demyk, K.; Taquet, V.; Wakelam, V.

2013-05-01

Context. Despite the low elemental deuterium abundance in the Galaxy, enhanced molecular deuterium fractionation has been found in the environments of low-mass star-forming regions and, in particular, the Class 0 protostar IRAS 16293-2422. Aims: The key program Chemical HErschel Surveys of Star forming regions (CHESS) aims at studying the molecular complexity of the interstellar medium. The high sensitivity and spectral resolution of the Herschel/HIFI (Heterodyne Instrument for Far-Infrared) instrument provide a unique opportunity to observe the fundamental 11,1-00,0 transition of ortho-D2O at 607 GHz and the higher energy 21,2-10,1 transition of para-D2O at 898 GHz, both of which are inaccessible from the ground. Methods: The ortho-D2O transition at 607 GHz was previously detected. We present in this paper the first tentative detection for the para-D2O transition at 898 GHz. The spherical Monte Carlo radiative transfer code RATRAN was used to reproduce the observed line profiles of D2O with the same method that was used to reproduce the HDO and H218O line profiles in IRAS 16293-2422. Results: As for HDO, the absorption component seen on the D2O lines can only be reproduced by adding an external absorbing layer, possibly created by the photodesorption of the ices at the edges of the molecular cloud. The D2O column density is found to be about 2.5 × 1012 cm-2 in this added layer, leading to a D2O/H2O ratio of about 0.5%. At a 3σ uncertainty, upper limits of 0.03% and 0.2% are obtained for this ratio in the hot corino and the colder envelope of IRAS 16293-2422, respectively. Conclusions: The deuterium fractionation derived in our study suggests that the ices present in IRAS 16293-2422 formed on warm dust grains (~15-20 K) in dense (~104-5 × 104 cm-3) translucent clouds. These results allow us to address the earliest phases of star formation and the conditions in which ices form. Based on Herschel/HIFI observations. Herschel is an ESA space observatory with scientific instruments provided by European-led principal Investigator consortia and with important participation from NASA.

The OD/OH Isotope Ratio in Comets 8P/Tuttle and C/2012 F6 (Lemmon)

NASA Astrophysics Data System (ADS)

Rousselot, Philippe; Jehin, Emmanuel; Hutsemekers, Damien; Manfroid, Jean; Decock, Alice; Bockelee-Morvan, Dominique

2016-10-01

The determination of isotopic ratios in solar system objects is an important source of information about their origin, especially for comets. Among these ratios the D/H is of particular importance because of its sensitivity to fractionation processes and physical environment, and the abundance of hydrogen in the solar system. The main molecule used to derive this ratio in comets is water. So far, apart water, only HCN has permitted to derive D/H ratio and not only upper limits.Most of the existing determinations of D/H in water molecules have been obtained by spectroscopic observations of water lines in the sub-mm or near infrared range [1,2]. So far only one measurement has been based on OD/OH emission lines radicals in the near-UV [3] and another one on the Lyman-alpha D emission [4]. In situ measurements have also been obtained in comets 1P/Halley and 67P/Churyumov-Gerasimenko using mass spectrometer [5,6,7,8].In this work we have used the OH and OD ultraviolet bands at 310 nm observed with the ESO 8-m Very Large Telescope feeding the Ultraviolet-Visual Echelle Spectrograph (UVES) for measuring the D/H ratio in comets 8P/Tuttle and C/2012 F6 (Lemmon). The OH and OD being the photodissociation products of H2O and HDO such observations allow to derive D/H ratio for water molecules. This work constitutes an independant determination of the D/H ratios already published for these comets and based on observations performed in the sub-mm and near infrared range of H2O and HDO lines. We present our modeling, data analysis and numerical values obtained for this ratio.[1] D. Bockelée-Morvan et al., 2015, SSR 197, 47-83 [2] N. Biver et al., 2016, A&A 589, id A78, 11p [3] D. Hutsemékers et al., 2008, A&A 490, L31 [4] H.A. Weaver et al., 2008, LPI Contributions 1405, 8216 [5] H. Balsiger, K. Altwegg, J. Geiss, 1995, JGR 100, 5827 [6] P. Eberhardt et al., 1995, A&A 302, 301 [7] R.H. Brown et al., 2012, PSS 60, 166 [8] K. Alwegg et al., 2015, Science 347, article id. 1261952

Gene expression analysis of the biocontrol fungus Trichoderma harzianum in the presence of tomato plants, chitin, or glucose using a high-density oligonucleotide microarray.

PubMed

Samolski, Ilanit; de Luis, Alberto; Vizcaíno, Juan Antonio; Monte, Enrique; Suárez, M Belén

2009-10-13

It has recently been shown that the Trichoderma fungal species used for biocontrol of plant diseases are capable of interacting with plant roots directly, behaving as symbiotic microorganisms. With a view to providing further information at transcriptomic level about the early response of Trichoderma to a host plant, we developed a high-density oligonucleotide (HDO) microarray encompassing 14,081 Expressed Sequence Tag (EST)-based transcripts from eight Trichoderma spp. and 9,121 genome-derived transcripts of T. reesei, and we have used this microarray to examine the gene expression of T. harzianum either alone or in the presence of tomato plants, chitin, or glucose. Global microarray analysis revealed 1,617 probe sets showing differential expression in T. harzianum mycelia under at least one of the culture conditions tested as compared with one another. Hierarchical clustering and heat map representation showed that the expression patterns obtained in glucose medium clustered separately from the expression patterns observed in the presence of tomato plants and chitin. Annotations using the Blast2GO suite identified 85 of the 257 transcripts whose probe sets afforded up-regulated expression in response to tomato plants. Some of these transcripts were predicted to encode proteins related to Trichoderma-host (fungus or plant) associations, such as Sm1/Elp1 protein, proteases P6281 and PRA1, enchochitinase CHIT42, or QID74 protein, although previously uncharacterized genes were also identified, including those responsible for the possible biosynthesis of nitric oxide, xenobiotic detoxification, mycelium development, or those related to the formation of infection structures in plant tissues. The effectiveness of the Trichoderma HDO microarray to detect different gene responses under different growth conditions in the fungus T. harzianum strongly indicates that this tool should be useful for further assays that include different stages of plant colonization, as well as for expression studies in other Trichoderma spp. represented on it. Using this microarray, we have been able to define a number of genes probably involved in the transcriptional response of T. harzianum within the first hours of contact with tomato plant roots, which may provide new insights into the mechanisms and roles of this fungus in the Trichoderma-plant interaction.

Gene expression analysis of the biocontrol fungus Trichoderma harzianum in the presence of tomato plants, chitin, or glucose using a high-density oligonucleotide microarray

PubMed Central

2009-01-01

Background It has recently been shown that the Trichoderma fungal species used for biocontrol of plant diseases are capable of interacting with plant roots directly, behaving as symbiotic microorganisms. With a view to providing further information at transcriptomic level about the early response of Trichoderma to a host plant, we developed a high-density oligonucleotide (HDO) microarray encompassing 14,081 Expressed Sequence Tag (EST)-based transcripts from eight Trichoderma spp. and 9,121 genome-derived transcripts of T. reesei, and we have used this microarray to examine the gene expression of T. harzianum either alone or in the presence of tomato plants, chitin, or glucose. Results Global microarray analysis revealed 1,617 probe sets showing differential expression in T. harzianum mycelia under at least one of the culture conditions tested as compared with one another. Hierarchical clustering and heat map representation showed that the expression patterns obtained in glucose medium clustered separately from the expression patterns observed in the presence of tomato plants and chitin. Annotations using the Blast2GO suite identified 85 of the 257 transcripts whose probe sets afforded up-regulated expression in response to tomato plants. Some of these transcripts were predicted to encode proteins related to Trichoderma-host (fungus or plant) associations, such as Sm1/Elp1 protein, proteases P6281 and PRA1, enchochitinase CHIT42, or QID74 protein, although previously uncharacterized genes were also identified, including those responsible for the possible biosynthesis of nitric oxide, xenobiotic detoxification, mycelium development, or those related to the formation of infection structures in plant tissues. Conclusion The effectiveness of the Trichoderma HDO microarray to detect different gene responses under different growth conditions in the fungus T. harzianum strongly indicates that this tool should be useful for further assays that include different stages of plant colonization, as well as for expression studies in other Trichoderma spp. represented on it. Using this microarray, we have been able to define a number of genes probably involved in the transcriptional response of T. harzianum within the first hours of contact with tomato plant roots, which may provide new insights into the mechanisms and roles of this fungus in the Trichoderma-plant interaction. PMID:19825185

First Satellite Observations of Lower Tropospheric Ammonia and Methanol

NASA Technical Reports Server (NTRS)

Beer, Reinhard; Shephard, Mark W.; Kulawik, Susan S.; Clough, Shepard A.; Eldering, Annmarie; Bowman, Kevin W.; Sander, Stanley P.; Fisher, Brendan M.; Payne, Vivienne H.; Luo, Mingzhao;

Deuterium trapping in the carbon-silicon co-deposition layers prepared by RF sputtering in D2 atmosphere

NASA Astrophysics Data System (ADS)

Zhang, Hongliang; Zhang, Weiyuan; Su, Ranran; Tu, Hanjun; Shi, Liqun; Hu, Jiansheng

2018-04-01

Deuterated carbon-silicon layers co-deposited on graphite and silicon substrates by radio frequency magnetron sputtering in pure D2 plasma were produced to study deuterium trapping and characteristics of the C-Si layers. The C-Si co-deposited layers were examined by ion beam analysis (IBA), Raman spectroscopy (RS), infrared absorption (IR) spectroscopy, thermal desorption spectroscopy (TDS) and scanning electron microscopy (SEM). It was found that the growth rate of the C-Si co-deposition layer decreased with increasing temperature from 350 K to 800 K, the D concentration and C/Si ratios increased differently on graphite and silicon substrates. TDS shows that D desorption is mainly as D2, HD, HDO, CD4, and C2D4 and release peaks occurred at temperatures of less than 900 K. RS and IR analysis reveal that the structure of the C-Si layers became more disordered with increasing temperatures. Rounded areas of peeling with 1-2 μm diameters were observed on the surface.

Biofuel Production from Jatropha Bio-Oil Derived Fast Pyrolysis: Effect and Mechanism of CoMoS Supported on Al2O3

NASA Astrophysics Data System (ADS)

Rodseanglung, T.; Ratana, T.; Phongaksorn, M.; Tungkamani, S.

2018-03-01

The aims of this research was to understand the CoMo/Al2O3 sulfide catalyst effect to remove oxygen-containing and nitrogen-containing molecules from Jatropha bio-oil derived fast pyrolysis converted to biofuels via hydrotreating process. The activity and selectivity of CoMo/γ-Al2O3 sulfided catalysts in hydrodeoxygenation (HDO) of Jatropha bio-oil derived fast pyrolysis was evaluated in a Parr batch reactor under 50 bar of H2 atmosphere for 2 h at 300 320 and 340 °C. It appeared that the CoMo/Al2O3 sulfide catalyst have high performance in activity for promoting the fatty acid, fatty ester, fatty amide and fatty nitrile compounds were converted to paraffin/olefin (Diesel range), this could be the CUS site on supported Al2O3 catalyst. The difference in selectivity products allowed us to propose a reaction scheme.

Synthesis of α-MoC1-x Nanoparticles with a Surface-Modified SBA-15 Hard Template: Determination of Structure-Function Relationships in Acetic Acid Deoxygenation.

PubMed

Baddour, Frederick G; Nash, Connor P; Schaidle, Joshua A; Ruddy, Daniel A

2016-07-25

Surface modification of mesoporous SBA-15 silica generated a hydrophobic environment for a molybdenum diamine (Mo-diamine) precursor solution, enabling direct growth of isolated 1.9±0.4 nm α-MoC1-x nanoparticles (NPs) inside the pores of the support. The resulting NP catalysts are bifunctional, and compared to bulk α-MoC1-x and β-Mo2 C, the NPs exhibit a greater acid-site:H-site ratio and a fraction of stronger acid sites. The greater acid-site:H-site ratio results in higher decarbonylation (DCO) selectivity during acetic acid hydrodeoxygenation (HDO) reactions, and the stronger acid sites lead to higher activity and ketonization (KET) selectivity at high temperatures. The hard-templating synthetic method could be a versatile route toward carbide NPs of varying size, composition, and phase, on a range of mesoporous oxide supports. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic hydroprocessing of coal-derived gasification residues to fuel blending stocks: effect of reaction variables and catalyst on hydrodeoxygenation (HDO), hydrodenitrogenation (HDN), and hydrodesulfurization (HDS)

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

Dieter Leckel

2006-10-15

Gas liquors, tar oils, and tar products resulting from the coal gasification of a high-temperature Fischer-Tropsch plant can be successfully refined to fuel blending components by the use of severe hydroprocessing conditions. High operating temperatures and pressures combined with low space velocities ensure the deep hydrogenation of refractory oxygen, sulfur, and nitrogen compounds. Hydrodeoxygenation, particularly the removal of phenolic components, hydrodesulfurization, and hydrodenitrogenation were obtained at greater than 99% levels using the NiMo and NiW on {gamma}-Al{sub 2}O{sub 3} catalysts. Maximum deoxygenation activity was achieved using the NiMo/{gamma}-Al{sub 2}O{sub 3} catalyst having a maximum pore size distribution in the rangemore » of 110-220{angstrom}. The NiMo/{gamma}-Al{sub 2}O{sub 3} catalyst, which also has a relatively high proportion of smaller pore sizes (35-60 {angstrom}), displays lower hydrogenation activity. 30 refs., 1 fig. 8 tabs.« less

Deuterated formaldehyde in the low-mass protostar HH212

NASA Astrophysics Data System (ADS)

Sahu, Dipen; Minh, Y. C.; Lee, Chin-Fei; Liu, Sheng-Yuan; Das, Ankan; Chakrabarti, S. K.; Sivaraman, Bhala

2018-04-01

HH212, a nearby (400 pc) object in Orion, is a class 0 protostellar system with a Keplerian disc and collimated bipolar SiO jets. Deuterated water, HDO, and a deuterated complex molecule, methanol (CH2DOH), have been reported in the source. Here, we report the HDCO (deuterated formaldehyde) line observation from Atacama Large Millimeter Array data to probe the inner region of HH212. We compare HDCO line with other molecular lines to understand the possible chemistry and physics of the source. The distribution of HDCO emission suggests that it may be associated with the base of the outflow. The emission also shows a rotation but it is not associated with the Keplerian rotation of disc or the rotating infalling envelope, rather it is associated with the outflow as previously seen in C34S. From the possible deuterium fractionation, we speculate that the gas phase formation of deuterated formaldehyde is active in the central hot region of the low-mass protostar system, HH212.

Synthesis of α-MoC 1-x Nanoparticles with a Surface-Modified SBA-15 Hard Template: Determination of Structure-Function Relationships in Acetic Acid Deoxygenation

DOE PAGES

Baddour, Frederick G.; Nash, Connor P.; Schaidle, Joshua A.; ...

2016-06-07

Surface modification of mesoporous SBA-15 silica generated a hydrophobic environment for a molybdenum diamine (Mo-diamine) precursor solution, enabling direct growth of isolated 1.9 ± 0.4 nm α-MoC 1-x nanoparticles (NPs) inside the pores of the support. The resulting NP catalysts are bifunctional, and compared to bulk α-MoC 1-x and β-Mo 2C, the NPs exhibit a greater acid-site:H-site ratio and a fraction of stronger acid sites. The greater acid-site:H-site ratio results in higher decarbonylation (DCO) selectivity during acetic acid hydrodeoxygenation (HDO) reactions, and the stronger acid sites lead to higher activity and ketonization (KET) selectivity at high temperatures. Lastly, the hard-templatingmore » synthetic method could be a versatile route toward carbide NPs of varying size, composition, and phase, on a range of mesoporous oxide supports.« less

First satellite observations of lower tropospheric ammonia and methanol

NASA Astrophysics Data System (ADS)

Beer, Reinhard; Shephard, Mark W.; Kulawik, Susan S.; Clough, Shepard A.; Eldering, Annmarie; Bowman, Kevin W.; Sander, Stanley P.; Fisher, Brendan M.; Payne, Vivienne H.; Luo, Mingzhao; Osterman, Gregory B.; Worden, John R.

2008-05-01

The Tropospheric Emission Spectrometer (TES) on the EOS Aura satellite makes global measurements of infrared radiances which are used to derive profiles of species such as O3, CO, H2O, HDO and CH4 as routine standard products. In addition, TES has a variety of special modes that provide denser spatial mapping over a limited geographical area. A continuous-coverage mode (called ``transect'', about 460 km long) has now been used to detect additional molecules indicative of regional air pollution. On 10 July 2007 at about 05:37 UTC (13:24 LMST) TES conducted such a transect observation over the Beijing area in northeast China. Examination of the residual spectral radiances following the retrieval of the TES standard products revealed surprisingly strong features attributable to enhanced concentrations of ammonia (NH3) and methanol (CH3OH), well above the normal background levels. This is the first time that these molecules have been detected in space-based nadir viewing measurements that penetrate into the lower atmosphere.

Composition and evolution of the atmosphere of Venus

NASA Technical Reports Server (NTRS)

Donahue, Thomas (Principal Investigator)

1996-01-01

The contract year started by analyzing Jovian atmospheric data acquired by the Galileo Probe Mass Spectrometer (GPMS). Two Venus hydrogen projects got underway as well. The first study strives to understand how to reconcile the standard treatment of the evolution of the H2O and HDO resevoirs on Venus over 4.5 Gyr in the presence of H and D escape and injection by comets. The second study is calculating the charge exchange contribution to hydrogen loss rates, using realistic models for exospheric H, H(+), D, D(+), and ion temperature from PV data. This report includes the following papers as attachments and supporting data: 'The Galileo Probe Mass Spectrometer: Composition of Jupiter's Atmosphere'; 'Chemical Composition Measurements of the Atmosphere of Jupiter with the Galileo Probe Mass Spectrometer'; 'Ion/Neutral Escape of Hydrogen and Deuterium: Evolution of Water'; 'Hydrogen and Deuterium in the Thermosphere of Venus: Solar Cycle Variations and Escape'; and 'Solar Cycle Variations in H(+) and D(+) Densities in the Venus Ionosphere: Implications for Escape'.

Nanoporous Cu–Al–Co Alloys for Selective Furfural Hydrodeoxygenation to 2-Methylfuran

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

Hutchings, Gregory S.; Luc, Wesley; Lu, Qi

By finding new catalysts for selective and efficient conversion of biomass-derived products to industrially relevant chemicals and fuels, a transition from fossil fuel feedstocks may be achieved. Furfural (C 5H 4O 2) is a platform chemical which may be converted to multiple heterocyclic and ring-opening products, but to date there have been few catalysts which enable selective hydrodeoxygenation to 2-methylfuran (2-MF, C 5H 6O). Here, we present a self-supported nanoporous Cu–Al–Co ternary alloy catalyst with high furfural HDO activity toward 2-MF, achieving up to 66.0% selectivity and 98.2% overall conversion at 513 K with only a ~5 atomic % Comore » composition. Some further analysis over multiple temperature conditions and nominal Co concentrations was performed to examine optimal conditions and tune catalyst performance, and operando X-ray absorption spectroscopy experiments were conducted to elucidate the structure of the catalyst in the reaction environment.« less

Detections and Sensitive Upper Limits for Methane and Related Trace Gases on Mars during 2003-2014, and planned extensions in 2016

NASA Astrophysics Data System (ADS)

Mumma, Michael J.; Villanueva, Geronimo L.; Novak, Robert E.

2015-11-01

Five groups report methane detections on Mars; all results suggest local release and high temporal variability [1-7]. Our team searched for CH4 on many dates and seasons and detected it on several dates [1, 9, 10]. TLS (Curiosity rover) reported methane upper limits [6], and then detections [7] that were consistent in size with earlier reports and that also showed rapid modulation of CH4 abundance.[8] argued that absorption features assigned to Mars 12CH4 by [1] might instead be weak lines of terrestrial 13CH4. If not properly removed, terrestrial 13CH4 signatures would appear on the blue wing of terrestrial 12CH4 even when Mars is red-shifted - but they do not (Fig. S6 of [1]), demonstrating that terrestrial signatures were correctly removed. [9] demonstrated that including the dependence of δ13CH4 with altitude did not affect the residual features, nor did taking δ13CH4 as zero. Were δ13CH4 important, its omission would have overemphasized the depth of 13CH4 terrestrial absorption, introducing emission features in the residual spectra [1]. However, the residual features are seen in absorption, establishing their origin as non-terrestrial - [8] now agrees with this view.We later reported results for multiple organic gases (CH4, CH3OH, H2CO, C2H6, C2H2, C2H4), hydroperoxyl (HO2), three nitriles (N2O, NH3, HCN) and two chlorinated species (HCl, CH3Cl) [9]. Most of these species cannot be detected with current space assets, owing to instrumental limitations (e.g., spectral resolving power). However, the high resolution infrared spectrometers (NOMAD, ACS) on ExoMars 2016 (Trace Gas Orbiter) will begin measurements in late 2016. In solar occultation, TGO sensitivities will far exceed prior capabilities.We published detailed hemispheric maps of H2O and HDO on Mars, inferring the size of a lost early ocean [10]. In 2016, we plan to acquire 3-D spatial maps of HDO and H2O with ALMA, and improved maps of organics with iSHELL/NASA-IRTF.References: [1] Mumma et al. Sci09; [2] Formisano et al. Sci04; [3] Krasnopolsky et al. Icar04; [4] Fonti and Marzo A&A10 [5] Krasnopolsky, Icar12; [6] Webster et al. Sci13; [7] Webster et al. Sci15; [8] Zahnle et al. Icar11; [9] Villanueva et al. Icar13; [10] Villanueva et al. Sci15.

Kinematics of the inner thousand AU region around the young massive star AFGL 2591-VLA3: a massive disk candidate?

NASA Astrophysics Data System (ADS)

Wang, K.-S.; van der Tak, F. F. S.; Hogerheijde, M. R.

2012-07-01

Context. Recent detections of disks around young high-mass stars support the idea of massive star formation through accretion rather than coalescence, but the detailed kinematics in the equatorial region of the disk candidates is not well known, which limits our understanding of the accretion process. Aims: This paper explores the kinematics of the gas around a young massive star with millimeter-wave interferometry to improve our understanding of the formation of massive stars though accretion. Methods: We use Plateau de Bure interferometric images to probe the environment of the nearby (~1 kpc) and luminous (~20 000 L⊙) high-mass (10-16 M⊙) young star AFGL 2591-VLA3 in continuum and in lines of HDO, H_218O and SO2 in the 115 and 230 GHz bands. Radiative transfer calculations are employed to investigate the kinematics of the source. Results: At ~0.5″ (500 AU) resolution, the line images clearly resolve the velocity field of the central compact source (diameter of ~800 AU) and show linear velocity gradients in the northeast-southwest direction. Judging from the disk-outflow geometry, the observed velocity gradient results from rotation and radial expansion in the equatorial region of VLA3. Radiative transfer calculations suggest that the velocity field is consistent with sub-Keplerian rotation plus Hubble-law like expansion. The line profiles of the observed molecules suggest a layered structure, with HDO emission arising from the disk mid-plane, H_218O from the warm mid-layer, and SO2 from the upper disk. Conclusions: We propose AFGL 2591-VLA3 as a new massive disk candidate, with peculiar kinematics. The rotation of this disk is sub-Keplerian, probably due to magnetic braking, while the stellar wind may be responsible for the expansion of the disk. The expansion motion may also be an indirect evidence of disk accretion in the very inner region because of the conservation of angular momentum. The sub-Keplerian rotation discovered in our work suggests that AFGL 2591-VLA3 may be a special case linking transition of velocity field of massive disks from pure Keplerian rotation to solid-body rotation though definitely more new detections of circumstellar disks around high-mass YSOs are required to examine this hypothesis. Our results support the idea that early B-type stars could be formed with a circumstellar disk from the point of view of the disk-outflow geometry, though the accretion processes in the disk need to be further investigated.

Structure and dynamics of water in nonionic reverse micelles: a combined time-resolved infrared and small angle x-ray scattering study.

PubMed

van der Loop, Tibert H; Panman, Matthijs R; Lotze, Stephan; Zhang, Jing; Vad, Thomas; Bakker, Huib J; Sager, Wiebke F C; Woutersen, Sander

2012-07-28

We study the structure and reorientation dynamics of nanometer-sized water droplets inside nonionic reverse micelles (water/Igepal-CO-520/cyclohexane) with time-resolved mid-infrared pump-probe spectroscopy and small angle x-ray scattering. In the time-resolved experiments, we probe the vibrational and orientational dynamics of the O-D bonds of dilute HDO:H(2)O mixtures in Igepal reverse micelles as a function of temperature and micelle size. We find that even small micelles contain a large fraction of water that reorients at the same rate as water in the bulk, which indicates that the polyethylene oxide chains of the surfactant do not penetrate into the water volume. We also observe that the confinement affects the reorientation dynamics of only the first hydration layer. From the temperature dependent surface-water dynamics, we estimate an activation enthalpy for reorientation of 45 ± 9 kJ mol(-1) (11 ± 2 kcal mol(-1)), which is close to the activation energy of the reorientation of water molecules in ice.

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

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

Wang, Hongliang; Wang, Huamin; Kuhn, Eric

Super Lewis acids containing the triflate anion (e.g. Hf(OTf)4, Ln(OTf)3, Al(OTf)3) and noble metal catalysts (e.g. Ru/C, Ru/Al2O3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage via selective bonding to etheric oxygens while the noble metal catalysed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt% of the hydrocarbons produced with this catalyticmore » system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates via protonating hydroxyls and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalysed by super Lewis acids.« less

Spatially-Scanned Dual Comb Spectroscopy for Atmospheric Measurements

NASA Astrophysics Data System (ADS)

Cossel, K.; Waxman, E.; Giorgetta, F.; Cermak, M.; Coddington, I.; Hesselius, D.; Ruben, S.; Swann, W.; Rieker, G. B.; Newbury, N.

2017-12-01

Measuring trace gas emissions from sources that are spatially complex and temporally variable, such as leaking natural gas infrastructure, is challenging with current measurement systems. Here, we present a new technique that provides the path-integrated concentrations of multiple gas species between a ground station and a retroreflector mounted on a small quadcopter. Such a system could provide the ability to quantify small area emissions sources as well measure vertical mixing within the boundary layer. The system is based on a near-infrared dual frequency-comb spectroscopy system (DCS) covering 1.58-1.7 microns, which enables rapid, accurate measurements of CO2, CH4, H2O, and HDO. The eye-safe laser light is launched from a telescope on a fast azimuth, elevation gimbal to a small quadcopter carrying a lightweight retroreflector as well as a high-precision real-time kinematic GPS receiver (for real-time cm-level path length measurements) and pressure, temperature and humidity sensors. Here, we show the results of test measurements from controlled releases of CH4 as well as from test vertical profiles.

Effect of Osmolytes on the Conformational Behavior of a Macromolecule in a Cytoplasm-like Crowded Environment: A Femtosecond Mid-IR Pump-Probe Spectroscopy Study.

PubMed

Kundu, Achintya; Verma, Pramod Kumar; Cho, Minhaeng

2018-02-15

Osmolytes found endogenously in almost all living beings play an important role in regulating cell volume under harsh environment. Here, to address the longstanding questions about the underlying mechanism of osmolyte effects, we use femtosecond mid-IR pump-probe spectroscopy with two different IR probes that are the OD stretching mode of HDO and the azido stretching mode of azido-derivatized poly(ethylene glycol) dimethyl ether (PEGDME). Our experimental results show that protecting osmolytes bind strongly with water molecules and dehydrate polymer surface, which results in promoting intramolecular interactions of the polymer. By contrast, urea behaves like water molecules without significantly disrupting water H-bonding network and favors extended and random-coil segments of the polymer chain by directly participating in solvation of the polymer. Our findings highlight the importance of direct interaction between urea and macromolecule, while protecting osmolytes indirectly affect the macromolecule through enhancing the water-osmolyte interaction in a crowded environment, which is the case that is often encountered in real biological systems.

A novel setup for femtosecond pump-repump-probe IR spectroscopy with few cycle CEP stable pulses.

PubMed

Bradler, Maximilian; Werhahn, Jasper C; Hutzler, Daniel; Fuhrmann, Simon; Heider, Rupert; Riedle, Eberhard; Iglev, Hristo; Kienberger, Reinhard

2013-08-26

We present a three-color mid-IR setup for vibrational pump-repump-probe experiments with a temporal resolution well below 100 fs and a freely selectable spectral resolution of 20 to 360 cm(-1) for the pump and repump. The usable probe range without optical realignment is 900 cm(-1). The experimental design employed is greatly simplified compared to the widely used setups, highly robust and includes a novel means for generation of tunable few-cycle pulses with stable carrier-envelope phase. A Ti:sapphire pump system operating with 1 kHz and a modest 150 fs pulse duration supplies the total pump energy of just 0.6 mJ. The good signal-to-noise ratio of the setup allows the determination of spectrally resolved transient probe changes smaller than 6·10(-5) OD at 130 time delays in just 45 minutes. The performance of the spectrometer is demonstrated with transient IR spectra and decay curves of HDO molecules in lithium nitrate trihydrate and ice and a first all MIR pump-repump-probe measurement.

The Unexpectedly Bright Comet C-2012 F6 (Lemmon) Unveiled at Near-Infrared Wavelengths

NASA Technical Reports Server (NTRS)

Paganini, Lucas; Disanti, Michael A.; Mumma, Michael J.; Villanueva, Geronimo L.; Bonev, Boncho P.; Keane, Jacqueline V.; Gibb, Erika L.; Boehnhardt, Hermann; Meech, Karen J.

2013-01-01

We acquired near-infrared spectra of the Oort cloud comet C/2012 F6 (Lemmon) at three different heliocentric distances (R h) during the comet's 2013 perihelion passage, providing a comprehensive measure of the outgassing behavior of parent volatiles and cosmogonic indicators. Our observations were performed pre-perihelion at R h = 1.2 AU with CRIRES (on 2013 February 2 and 4), and post-perihelion at R h = 0.75 AU with CSHELL (on March 31 and April 1) and R h = 1.74 AU with NIRSPEC (on June 20). We detected 10 volatile species (H2O, OH* prompt emission, C2H6, CH3OH, H2CO, HCN, CO, CH4, NH3, and NH2), and obtained upper limits for two others (C2H2 and HDO). One-dimensional spatial profiles displayed different distributions for some volatiles, confirming either the existence of polar and apolar ices, or of chemically distinct active vents in the nucleus. The ortho-para ratio for water was 3.31 +/- 0.33 (weighted mean of CRIRES and NIRSPEC results), implying a spin temperature >37 K at the 95% confidence limit. Our (3s) upper limit for HDO corresponds to D/H < 2.45 × 10-3 (i.e., <16 Vienna Standard Mean Ocean Water, VSMOW). At R h = 1.2 AU (CRIRES), the production rate for water was Q(H2O) = 1.9 +/- 0.1 × 1029 s-1 and its rotational temperature was T rot 69 K. At R h = 0.75 AU (CSHELL), we measured Q(H2O) = 4.6 +/- 0.6 × 1029 s-1 and T rot = 80 K on March 31, and 6.6 +/- 0.9 × 1029 s-1 and T rot = 100 K on April 1. At R h = 1.74 AU (NIRSPEC), we obtained Q(H2O) = 1.1 +/- 0.1 × 1029 s-1 and T rot 50 K. The measured volatile abundance ratios classify comet C/2012 F6 as rather depleted in C2H6 and CH3OH, while HCN, CH4, and CO displayed abundances close to their median values found among comets. H2CO was the only volatile showing a relative enhancement. The relative paucity of C2H6 and CH3OH (with respect to H2O) suggests formation within warm regions of the nebula. However, the normal abundance of HCN and hypervolatiles CH4 and CO, and the enhancement of H2CO, may indicate a possible heterogeneous nucleus of comet C/2012 F6 (Lemmon), possibly as a result of radial mixing within the protoplanetary disk

Characterization of SO2 abundance in Venus' night-side mesosphere from SPICAV/VEX observations

NASA Astrophysics Data System (ADS)

Belyaev, Denis; Fedorova, Anna; Piccialli, Arianna; Marcq, Emmanuel; Montmessin, Franck; Bertaux, Jean-Loup; Evdokimova, Daria

Sulfur dioxide (SO _{2}) is a key component of Venus’ atmosphere since the planet is totally covered by H _{2}SO _{4} droplets clouds at altitudes 50-70 km. Any significant change in the SO _{x} oxides above and within the clouds affects the photochemistry in the mesosphere (70-120 km). Recent continuous observations from the Venus Express orbiter (Belyaev et al., 2012; Marcq et al., 2013) and ground-based telescopes (Sandor et al., 2010; Krasnopolsky, 2010; Encrenaz et al., 2012) showed high variability of SO _{2} abundance with years, diurnal time and latitude on the day-side and terminators (commonly from 20 to 500 ppbv above the clouds). In the night-side mesosphere SO _{2} is not photo dissociative but, so far, its behavior has never been explored in details. In this paper we present first results from sulfur dioxide observations made by SPICAV UV spectrometer onboard Venus Express orbiter in regime of stellar occultation (Bertaux et al., 2007). In this mode the instrument observes night-side mesosphere and can register SO _{2} absorption bands in 190-220 nm and CO _{2} bands in 120-200 nm at altitudes from 85 to 110 km (spectral resolution is ˜2 nm). As a result, vertical distribution of SO _{2} and CO _{2} concentrations has been retrieved in observation period from June 2006 to April 2012, at latitude range 60(°) S-60(°) N and Venus local time 20:00-04:00. On the average, mixing ratio of sulfur dioxide fluctuates around ˜100 ppbv along altitude range 90-100 km. Our work is supported by the Program No.22 of RAS and grant of the Russian Government to MIPT. References: Belyaev D. et al., 2012. Vertical profiling of SO _{2} and SO above Venus' clouds by SPICAV/SOIR solar occultations. Icarus 217, 740-751. Bertaux J.-L. et al., 2007. SPICAV on Venus Express: three spectrometers to study the global structure and composition of Venus atmosphere. Planet. Space Sci. 55, 1673-1700. Encrenaz T. et al., 2012. HDO and SO _{2} thermal mapping on Venus: evidence for strong SO _{2} variability. A&A 543, A153. Krasnopolsky V.A., 2010. Spatially-resolved high-resolution spectroscopy of Venus. 2. Variations of HDO, OCS, and SO _{2} at the cloud tops. Icarus 209, 314-322. Marcq E. et al., 2013. Variations of sulphur dioxide at the cloud top of Venus’s dynamic atmosphere. Nature Geoscience, vol. 6, 25-28. DOI: 10.1038/NGEO1650. Sandor B.J. et al., 2010. Sulfur chemistry in the Venus mesosphere from SO _{2} and SO microwave spectra. Icarus 208, 49-60.

A Hollow-Waveguide Gas Correlation Radiometer for Ultra-Precise Column Measurements of Formaldehyde on Mars

NASA Technical Reports Server (NTRS)

Wilson, Emily L.; Neveu, Marc; Riris, Haris; Georgieva, Elena M.; Heaps, William S.

2011-01-01

We present preliminary results in the development of a miniaturized gas correlation radiometer that implements a hollow-core optical fiber (hollow waveguide) gas correlation cell. The substantial reduction in mass and volume of the gas correlation cell makes this technology appropriate for an orbital mission -- capable of pinpointing sources of trace gases in the Martian atmosphere. Here we demonstrate a formaldehyde (H2CO) sensor and report a detection limit equivalent to approximately 30 ppb in the Martian atmosphere. The relative simplicity of the technique allows it to be expanded to measure a range of atmospheric trace gases of interest on Mars such as methane (CH4), water vapour (H2O), deuterated water vapour (HDO), and methanol (CH3OH). Performance of a formaldehyde instrument in a Mars orbit has been simulated assuming a 3 meter long, 1000 micron inner diameter hollow-core fiber gas correlation cell, a 92.8 degree sun-synchronous orbit from 400 km with a horizontal sampling scale of 10 km x 10 km. Initial results indicate that for one second of averaging, a detection limit of 1 ppb is possible.

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

DOE PAGES

Wang, Hongliang; Wang, Huamin; Kuhn, Eric; ...

2017-11-14

Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4, Ln(OTf) 3, In(OTf) 3, Al(OTf) 3] and noble metal catalysts (e.g., Ru/C, Ru/Al2O 3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt %more » of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalyzed by super Lewis acids.« less

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

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

Wang, Hongliang; Wang, Huamin; Kuhn, Eric

Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4, Ln(OTf) 3, In(OTf) 3, Al(OTf) 3] and noble metal catalysts (e.g., Ru/C, Ru/Al2O 3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt %more » of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalyzed by super Lewis acids.« less

Fluorinated benzothiadiazole-based conjugated polymers for high-performance polymer solar cells without any processing additives or post-treatments.

PubMed

Wang, Ning; Chen, Zheng; Wei, Wei; Jiang, Zhenhua

2013-11-13

Thanks to their many favorable advantages, polymer solar cells exhibit great potential for next-generation clean energy sources. Herein, we have successfully designed and synthesized a series of new fluorinated benzothiadiazole-based conjugated copolymers PBDT(TEH)-DT(H)BTff (P1), PBDT(TEH)-DT(EH)BTff (P2), and PBDT(HDO)-DT(H)BTff (P3). The power conversion efficiencies of 4.46, 6.20, and 8.30% were achieved for P1-, P2-, and P3-based devices within ~100 nm thickness active layers under AM 1.5G illumination without any processing additives or post-treatments, respectively. The PCE of 8.30% for P3 is the highest value for the reported traditional single-junction polymer solar cells via a simple fabrication architecture without any additives or post-treatments. In addition, it is noteworthy that P3 also allows making high efficient polymer solar cells with high PCEs of 7.27 and 6.56% under the same condition for ~200 and ~300 nm thickness active layers, respectively. Excellent photoelectric properties and good solubility make polymer P3 become an alternative material for high-performance polymer solar cells.

Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts.

PubMed

Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P; Yang, Bin

2018-01-10

Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4 , Ln(OTf) 3 , In(OTf) 3 , Al(OTf) 3 ] and noble metal catalysts (e.g., Ru/C, Ru/Al 2 O 3 ) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf) 4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote deoxygenation reactions catalyzed by super Lewis acids. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coherent cavity-enhanced dual-comb spectroscopy

PubMed Central

Fleisher, Adam J.; Long, David A.; Reed, Zachary D.; Hodges, Joseph T.; Plusquellic, David F.

2016-01-01

Dual-comb spectroscopy allows for the rapid, multiplexed acquisition of high-resolution spectra without the need for moving parts or low-resolution dispersive optics. This method of broadband spectroscopy is most often accomplished via tight phase locking of two mode-locked lasers or via sophisticated signal processing algorithms, and therefore, long integration times of phase coherent signals are difficult to achieve. Here we demonstrate an alternative approach to dual-comb spectroscopy using two phase modulator combs originating from a single continuous-wave laser capable of > 2 hours of coherent real-time averaging. The dual combs were generated by driving the phase modulators with step-recovery diodes where each comb consisted of > 250 teeth with 203 MHz spacing and spanned > 50 GHz region in the near-infrared. The step-recovery diodes are passive devices that provide low-phase-noise harmonics for efficient coupling into an enhancement cavity at picowatt optical powers. With this approach, we demonstrate the sensitivity to simultaneously monitor ambient levels of CO2, CO, HDO, and H2O in a single spectral region at a maximum acquisition rate of 150 kHz. Robust, compact, low-cost and widely tunable dual-comb systems could enable a network of distributed multiplexed optical sensors. PMID:27409866

Neutral atmosphere composition from SOIR measurements on board Venus Express

NASA Astrophysics Data System (ADS)

Mahieux, A.; Drummond, R.; Wilquet, V.; Vandaele, A. C.; Federova, A.; Belyaev, D.; Korablev, O.; Villard, E.; Montmessin, F.; Bertaux, J.-L.

2009-04-01

The SOIR instrument performs solar occultation measurements in the IR region (2.2 - 4.3 m) at a resolution of 0.12 cm-1, the highest on board Venus Express. It combines an echelle spectrometer and an AOTF (Acousto-Optical Tunable Filter) for the order selection [1,2]. The wavelength range probed by SOIR allows a detailed chemical inventory of the Venus atmosphere above the cloud layer with an emphasis on vertical distribution of the gases. Measurements of HDO, H2O, HCl, HF, CO and CO2 vertical profiles have been routinely performed, as well as those of their isotopologues [3,4]. We will discuss the improvements introduced in the analysis algorithm of the SOIR spectra. This discussion will be illustrated by presenting new results of retrievals of minor constituents of the Venus mesosphere, in terms of vertical profiles and geographical distribution. CO2 is the major constituent of the Venus atmosphere and was therefore observed in many solar occultations, leading to a good geographical coverage, although limited by the geometry of the orbit. Depending on the abundance of the absorbing isotopologue and on the intensity of the band measured, we will show that the SOIR instrument is able to furnish CO2 vertical profiles ranging typically from 65 to 150 km, reaching in some conditions 185 km altitude. This information is important in the frame of compiling, in collaboration with other teams, a new Venus Atmosphere Model. 1. A. Mahieux, S. Berkenbosch, R. Clairquin, D. Fussen, N. Mateshvili, E. Neefs, D. Nevejans, B. Ristic, A. C. Vandaele, V. Wilquet, D. Belyaev, A. Fedorova, O. Korablev, E. Villard, F. Montmessin and J.-L. Bertaux, "In-Flight performance and calibration of SPICAV SOIR on board Venus Express", Applied Optics 47 (13), 2252-65 (2008). 2. D. Nevejans, E. Neefs, E. Van Ransbeeck, S. Berkenbosch, R. Clairquin, L. De Vos, W. Moelans, S. Glorieux, A. Baeke, O. Korablev, I. Vinogradov, Y. Kalinnikov, B. Bach, J.-P. Dubois and E. Villard, "Compact high-resolution space-borne echelle grating spectrometer with AOTF based on order sorting for the infrared domain from 2.2 to 4.3 micrometer", Applied Optics 45 (21), 5191-5206 (2006). 3. A. Fedorova, O. Korablev, A. C. Vandaele, J.-L. Bertaux, D. Belyaev, A. Mahieux, E. Neefs, V. Wilquet, R. Drummond, F. Montmessin and E. Villard, "HDO and H2O vertical distribution and isotopic ratio in the Venus mesosphere by SOIR spectrometer on board Venus Express", JGR, doi:10.1029/2008JE003146 (2008). 4. A. C. Vandaele, M. De Mazière, R. Drummond, A. Mahieux, E. Neefs, V. Wilquet, D. Belyaev, A. Fedorova, O. Korablev, F. Montmessin and J.-L. Bertaux, "Composition of the Venus mesosphere measured by SOIR on board Venus Express", J. Geophysic. Res., doi:10.1029/2008JE003140 (2008).

The structure and function of supported molybdenum nitride and molybdenum carbide hydrotreating catalysts

NASA Astrophysics Data System (ADS)

Dolce, Gregory Martin

1997-11-01

A series of gamma-Alsb2Osb3 supported molybdenum nitrides and carbides were prepared by the temperature programmed reaction of supported molybdates with ammonia and methane/hydrogen mixtures, respectively. In the first part of this research, the effects of synthesis heating rates and molybdenum loading on the catalytic properties of the materials were examined. A significant amount of excess carbon was deposited on the surface of the carbides during synthesis. The materials consisted of small particles which were very highly dispersed. Oxygen chemisorption indicated that the nitride particles may have been two-dimensional. The dispersion of the carbides, however, appeared to decrease as the loading increased. The catalysts were evaluated for hydrodenitrogenation (HDN), hydrodesulfurization (HDS), and hydrodeoxygenation (HDO). The molybdenum loading had the largest effect on the activity of the materials. For the nitrides, the HDN and HDS activities were inverse functions of the loading. This suggested that the most active HDN and HDS sites were located at the perimeter of the two-dimensional particles. The HDN and HDS activities of the carbides followed the same trend as the oxygen uptake. This result suggested that oxygen titrated the active sites on the supported carbides. Selected catalysts were evaluated for methylcarbazole HDN, dibenzothiophene HDS, and dibenzofuran HDO. The activity and selectivity of the nitrides and carbides were competitive with a presulfided commercial catalyst. In the second part of this work, a series of supported nitrides and carbides were prepared using a wider range of loadings (5-30 wt% Mo). Thermogravimetric analysis was used to determine the temperature at which excess carbon was deposited on the carbides. By modifying the synthesis parameters, the deposition of excess carbon was effectively inhibited. The dispersions of the supported nitrides and carbides were constant and suggested that the materials consisted of two-dimensional raft-like particles. The HDN activity of the nitrides decreased as the loading increased, while that of the carbides was relatively constant. Carbon monoxide and methylamine adsorbed on the same types of sites on the nitrides and carbides. Infrared spectroscopy and temperature programmed desorption revealed that some methylamine underwent HDN on the nitrides and carbides. Carbon monoxide appeared to adsorb on two types of sites. One type of site adsorbed CO which desorbed upon heating while the other type of site adsorbed CO which dissociated when the material was heated. The relative amounts of desorbed CO and methylamine scaled with the activity of the nitrides suggesting that CO and methylamine titrated the active sites. It appeared that the active sites of the supported carbides were different from those on the supported nitrides. It was proposed that the active sites on the supported nitrides were at the perimeter of the two-dimensional particles while the active sites of the carbides were "on top" of the particles.

New measurements of D/H on Mars using EXES aboard SOFIA

NASA Astrophysics Data System (ADS)

Encrenaz, T.; DeWitt, C.; Richter, M. J.; Greathouse, T. K.; Fouchet, T.; Montmessin, F.; Lefèvre, F.; Bézard, B.; Atreya, S. K.; Aoki, S.; Sagawa, H.

2018-05-01

The global D/H ratio on Mars is an important measurement for understanding the past history of water on Mars; locally, through condensation and sublimation processes, it is a possible tracer of the sources and sinks of water vapor on Mars. Measuring D/H as a function of longitude, latitude and season is necessary for determining the present averaged value of D/H on Mars. Following an earlier measurement in April 2014, we used the Echelon Cross Echelle Spectrograph (EXES) instrument on board the Stratospheric Observatory for Infrared Astronomy (SOFIA) facility to map D/H on Mars on two occasions, on March 24, 2016 (Ls = 127°), and January 24, 2017 (Ls = 304°), by measuring simultaneously the abundances of H2O and HDO in the 1383-1391 cm-1 range (7.2 μm). The D/H disk-integrated values are 4.0 (+0.8, -0.6) × Vienna Standard Mean Ocean Water (VSMOW) and 4.5 (+0.7, -0.6) × VSMOW, respectively, in agreement with our earlier result. The main result of this study is that there is no evidence of strong local variations in the D/H ratio nor for seasonal variations in the global D/H ratio between northern summer and southern summer.

Conceptual Study of A Hetrodyne Receiver for the Origins Space Telescope

NASA Astrophysics Data System (ADS)

Wiedner, Martina

2018-01-01

The Origins Space Telescope (OST) is a mission concept of an extremely versatile observatory with 5 science instruments, of which the HEterodyne Receivers for OST (HERO) is one. HERO's main targets are high spectral resolution observations (Δλ/λ up to 107 or Δv = 0.03km/s) of water to follow its trail from cores to YSOs as well as H2O and HDO observations on comets. HERO will probe all neutral ISM phases using cooling lines ([CII], [OI]) and hydrides as probes of CO-dark H2 (CH, HF). HERO will reveal how molecular clouds and filaments form in the local ISM up to nearby galaxies. In order to achieve these observational goals, HERO will cover an extremely wide frequency range from 468 to 2700 GHz and a window around the OI line at 4563 to 4752GHz. It will consist of very large focal plane arrays of 128 pixels between 900 - 2700 GHz and at 4.7 THz, and 32 pixels for the 468 to 900 GHz range. The instrument is exploiting Herschel/HIFI heritage. HERO's large arrays require low dissipation and low power components. The HERO concept makes use of the latest cryogenic SiGe amplifier technology, as well as CMOS technology for the backends with 2 orders of magnitude lower power.

Coherent cavity-enhanced dual-comb spectroscopy.

PubMed

Fleisher, Adam J; Long, David A; Reed, Zachary D; Hodges, Joseph T; Plusquellic, David F

2016-05-16

Dual-comb spectroscopy allows for the rapid, multiplexed acquisition of high-resolution spectra without the need for moving parts or low-resolution dispersive optics. This method of broadband spectroscopy is most often accomplished via tight phase locking of two mode-locked lasers or via sophisticated signal processing algorithms, and therefore, long integration times of phase coherent signals are difficult to achieve. Here we demonstrate an alternative approach to dual-comb spectroscopy using two phase modulator combs originating from a single continuous-wave laser capable of > 2 hours of coherent real-time averaging. The dual combs were generated by driving the phase modulators with step-recovery diodes where each comb consisted of > 250 teeth with 203 MHz spacing and spanned > 50 GHz region in the near-infrared. The step-recovery diodes are passive devices that provide low-phase-noise harmonics for efficient coupling into an enhancement cavity at picowatt optical powers. With this approach, we demonstrate the sensitivity to simultaneously monitor ambient levels of CO₂, CO, HDO, and H₂O in a single spectral region at a maximum acquisition rate of 150 kHz. Robust, compact, low-cost and widely tunable dual-comb systems could enable a network of distributed multiplexed optical sensors.

Air exposure and sample storage time influence on hydrogen release from tungsten

NASA Astrophysics Data System (ADS)

Moshkunov, K. A.; Schmid, K.; Mayer, M.; Kurnaev, V. A.; Gasparyan, Yu. M.

2010-09-01

In investigations of hydrogen retention in first wall components the influence of the conditions of the implanted target storage prior to analysis and the storage time is often neglected. Therefore we have performed a dedicated set of experiments. The release of hydrogen from samples exposed to ambient air after irradiation was compared to samples kept in vacuum. For air exposed samples significant amounts of HDO and D 2O are detected during TDS. Additional experiments have shown that heavy water is formed by recombination of releasing D and H atoms with O on the W surface. This water formation can alter hydrogen retention results significantly, in particular - for low retention cases. In addition to the influence of ambient air exposure also the influence of storage time in vacuum was investigated. After implantation at 300 K the samples were stored in vacuum for up to 1 week during which the retained amount decreased significantly. The subsequently measured TDS spectra showed that D was lost from both the high and low energy peaks during storage at ambient temperature of ˜300 K. An attempt to simulate this release from both peaks during room temperature storage by TMAP 7 calculations showed that this effect cannot be explained by conventional diffusion/trapping models.

Adiabatic corrections to density functional theory energies and wave functions.

PubMed

Mohallem, José R; Coura, Thiago de O; Diniz, Leonardo G; de Castro, Gustavo; Assafrão, Denise; Heine, Thomas

2008-09-25

The adiabatic finite-nuclear-mass-correction (FNMC) to the electronic energies and wave functions of atoms and molecules is formulated for density-functional theory and implemented in the deMon code. The approach is tested for a series of local and gradient corrected density functionals, using MP2 results and diagonal-Born-Oppenheimer corrections from the literature for comparison. In the evaluation of absolute energy corrections of nonorganic molecules the LDA PZ81 functional works surprisingly better than the others. For organic molecules the GGA BLYP functional has the best performance. FNMC with GGA functionals, mainly BLYP, show a good performance in the evaluation of relative corrections, except for nonorganic molecules containing H atoms. The PW86 functional stands out with the best evaluation of the barrier of linearity of H2O and the isotopic dipole moment of HDO. In general, DFT functionals display an accuracy superior than the common belief and because the corrections are based on a change of the electronic kinetic energy they are here ranked in a new appropriate way. The approach is applied to obtain the adiabatic correction for full atomization of alcanes C(n)H(2n+2), n = 4-10. The barrier of 1 mHartree is approached for adiabatic corrections, justifying its insertion into DFT.

Laser-based sensor for a coolant leak detection in a nuclear reactor

NASA Astrophysics Data System (ADS)

Kim, T.-S.; Park, H.; Ko, K.; Lim, G.; Cha, Y.-H.; Han, J.; Jeong, D.-Y.

2010-08-01

Currently, the nuclear industry needs strongly a reliable detection system to continuously monitor a coolant leak during a normal operation of reactors for the ensurance of nuclear safety. In this work, we propose a new device for the coolant leak detection based on tunable diode laser spectroscopy (TDLS) by using a compact diode laser. For the feasibility experiment, we established an experimental setup consisted of a near-IR diode laser with a wavelength of about 1392 nm, a home-made multi-pass cell and a sample injection system. The feasibility test was performed for the detection of the heavy water (D2O) leaks which can happen in a pressurized heavy water reactor (PWHR). As a result, the device based on the TDLS is shown to be operated successfully in detecting a HDO molecule, which is generated from the leaked heavy water by an isotope exchange reaction between D2O and H2O. Additionally, it is suggested that the performance of the new device, such as sensitivity and stability, can be improved by adapting a cavity enhanced absorption spectroscopy and a compact DFB diode laser. We presume that this laser-based leak detector has several advantages over the conventional techniques currently employed in the nuclear power plant, such as radiation monitoring, humidity monitoring and FT-IR spectroscopy.

Functional Analysis of the Trichoderma harzianum nox1 Gene, Encoding an NADPH Oxidase, Relates Production of Reactive Oxygen Species to Specific Biocontrol Activity against Pythium ultimum▿†

PubMed Central

Montero-Barrientos, M.; Hermosa, R.; Cardoza, R. E.; Gutiérrez, S.; Monte, E.

2011-01-01

The synthesis of reactive oxygen species (ROS) is one of the first events following pathogenic interactions in eukaryotic cells, and NADPH oxidases are involved in the formation of such ROS. The nox1 gene of Trichoderma harzianum was cloned, and its role in antagonism against phytopathogens was analyzed in nox1-overexpressed transformants. The increased levels of nox1 expression in these transformants were accompanied by an increase in ROS production during their direct confrontation with Pythium ultimum. The transformants displayed an increased hydrolytic pattern, as determined by comparing protease, cellulase, and chitinase activities with those for the wild type. In confrontation assays against P. ultimum the nox1-overexpressed transformants were more effective than the wild type, but not in assays against Botrytis cinerea or Rhizoctonia solani. A transcriptomic analysis using a Trichoderma high-density oligonucleotide (HDO) microarray also showed that, compared to gene expression for the interaction of wild-type T. harzianum and P. ultimum, genes related to protease, cellulase, and chitinase activities were differentially upregulated in the interaction of a nox1-overexpressed transformant with this pathogen. Our results show that nox1 is involved in T. harzianum ROS production and antagonism against P. ultimum. PMID:21421791

Effects of outgassing of loader chamber walls on hydriding of thin films for commercial applications

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

Provo, James L., E-mail: jlprovo@verizon.net

2014-07-01

An important aspect of understanding industrial processing is to know the characteristics of the materials used in such processes. A study was performed to determine the effects of hydriding chamber material on the degree of hydriding for the commercial production of thin film hydride targets for various research universities, commercial companies, and government national laboratories. The goal was to increase the degree of hydriding of various thin film hydrides and to study the vacuum environment during air-exposure hydriding. For this purpose, dynamic residual gas analysis during deuterium gas hydride processing was utilized with erbium thin films, employing a special set-upmore » for direct dynamic hydride gas sampling during processing at elevated temperature and full loading gas pressure. Complete process data for (1) a copper–(1.83 wt. %)beryllium wet hydrogen fired passivated (600 °C–1 h) externally heated pipe hydriding chamber are reported. Dynamic residual gas analysis comparisons during hydriding are presented for hydriding chambers made from (2) alumina (99.8 wt. %), (3) copper (with an interior aluminum coating ∼10 k Å thick, and (4) for a stainless-steel air-fired passivated (900 °C–1 h) chamber. Dynamic data with deuterium gas in the chamber at the hydriding temperature (450 °C) showed the presence and growth of water vapor (D{sub 2}O) and related mixed ion species(H{sub 2}O{sup +}, HDO{sup +}, D{sub 2}O{sup +}, and OD{sup +}) from hydrogen isotope exchange reactions during the 1 h process time. Peaks at mass-to-charge ratios (i.e., m/e) of 12(C{sup +}), 16(CD{sub 2}{sup +}), 17(CHD{sub 2}{sup +}), and 18(CD{sub 3}{sup +}, OD{sup +}) increased for approximately the first half hour of a 1 h hydriding process and then approach steady state. Mass-to-charge peaks at 19(HDO{sup +}) and 20(D{sub 2}O{sup +}) continue to increase throughout the process cycle. Using the m/e = 20 (D{sub 2}O{sup +}) peak intensity from chamber (1)–Cu(1.83 wt. %)Be as a standard, the peak intensity from chamber (4)—stainless-steel (air-fired) was 7.1× higher, indicating that the surface of stainless-steel had a larger concentration of reactive oxygen and/or water than hydrogen. The (D{sub 2}O{sup +}) peak intensity from chamber (3)—Cu (interior Al coating) was 1.55× larger and chamber (2)—alumina(99.8%) was 1.33× higher than Cu(1.83 wt. %)Be. Thus copper–(1.83 wt. %)beryllium was the best hydriding chamber material studied followed closely by the alumina (99.8 wt. %) chamber. Gas take-up by Er occluder targets processed in Cu(1.83 wt. %)Be hydriding chambers (i.e., gas/metal atomic ratios) correlate with the dynamic RGA data.« less

The unexpectedly bright comet C/2012 F6 (Lemmon) unveiled at near-infrared wavelengths

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

Paganini, Lucas; DiSanti, Michael A.; Mumma, Michael J.

2014-01-01

We acquired near-infrared spectra of the Oort cloud comet C/2012 F6 (Lemmon) at three different heliocentric distances (R {sub h}) during the comet's 2013 perihelion passage, providing a comprehensive measure of the outgassing behavior of parent volatiles and cosmogonic indicators. Our observations were performed pre-perihelion at R {sub h} = 1.2 AU with CRIRES (on 2013 February 2 and 4), and post-perihelion at R {sub h} = 0.75 AU with CSHELL (on March 31 and April 1) and R {sub h} = 1.74 AU with NIRSPEC (on June 20). We detected 10 volatile species (H{sub 2}O, OH* prompt emission, C{submore » 2}H{sub 6}, CH{sub 3}OH, H{sub 2}CO, HCN, CO, CH{sub 4}, NH{sub 3}, and NH{sub 2}), and obtained upper limits for two others (C{sub 2}H{sub 2} and HDO). One-dimensional spatial profiles displayed different distributions for some volatiles, confirming either the existence of polar and apolar ices, or of chemically distinct active vents in the nucleus. The ortho-para ratio for water was 3.31 ± 0.33 (weighted mean of CRIRES and NIRSPEC results), implying a spin temperature >37 K at the 95% confidence limit. Our (3σ) upper limit for HDO corresponds to D/H < 2.45 × 10{sup –3} (i.e., <16 Vienna Standard Mean Ocean Water, VSMOW). At R {sub h} = 1.2 AU (CRIRES), the production rate for water was Q(H{sub 2}O) = 1.9 ± 0.1 × 10{sup 29} s{sup –1} and its rotational temperature was T {sub rot} ∼ 69 K. At R {sub h} = 0.75 AU (CSHELL), we measured Q(H{sub 2}O) = 4.6 ± 0.6 × 10{sup 29} s{sup –1} and T {sub rot} = 80 K on March 31, and 6.6 ± 0.9 × 10{sup 29} s{sup –1} and T {sub rot} = 100 K on April 1. At R {sub h} = 1.74 AU (NIRSPEC), we obtained Q(H{sub 2}O) = 1.1 ± 0.1 × 10{sup 29} s{sup –1} and T {sub rot} ∼ 50 K. The measured volatile abundance ratios classify comet C/2012 F6 as rather depleted in C{sub 2}H{sub 6} and CH{sub 3}OH, while HCN, CH{sub 4}, and CO displayed abundances close to their median values found among comets. H{sub 2}CO was the only volatile showing a relative enhancement. The relative paucity of C{sub 2}H{sub 6} and CH{sub 3}OH (with respect to H{sub 2}O) suggests formation within warm regions of the nebula. However, the normal abundance of HCN and hypervolatiles CH{sub 4} and CO, and the enhancement of H{sub 2}CO, may indicate a possible heterogeneous nucleus of comet C/2012 F6 (Lemmon), possibly as a result of radial mixing within the protoplanetary disk.« less

Comet 67P Through the Lens of Art

NASA Astrophysics Data System (ADS)

Smirnova, Ekaterina

2017-04-01

My proposal is to share my artistic exploration of a comet through the bodily senses, while finding inspiration in scientific data. I will present my artwork as a slideshow, showcasing: large scale paintings, ceramic sculptures, music and interactive augmented reality. The Rosetta mission of the European Space Agency (ESA) to comet 67P/ Churyumov-Gerasimenko is remarkable. The scientific investigation of the comet's composition, atmosphere, dust, vapor, surface and internal structure are crucial to help researchers understand the origin of the solar system and our own planet. Sight: Paintings Rosetta mission discovered that the water on the comet is different from the water on Earth; as measured with the ROSINA-DFMS instrument on Rosetta, water on 67P contains approximately 3 times more hydrogen­deuterium oxide - HDO, than found in Earth's oceans. In the art studio I re-create water that is close in composition to the water on the comet, by concentrating the level of HDO. With this water I paint large scale watermedia paintings, based on the photographs by Rosetta (OSIRIS, Nav. Cam.). Touch: Sculptures While exploring the comet's three-dimensional form, I focus more deeply on the composition of the comet. Stoneware clay and my choice of a glaze both include iron oxide, a common constituent of meteorites and comets. Hearing: Music An audio piece "A Singing Comet", by Manuel Senfft, based on the Rosetta Plasma Consortium data, inspired me to make a musical piece. In collaboration with clarinetist Lee Mottram (Wales) and composer Takuto Fukuda (Japan) we created an electro­acoustic composition in which we tell the story of comets visiting our Solar System, repeating their cycle, curving around the sun and releasing water, carrying away dust to form their tails. Smell In collaboration with The Open University, UK, postcards with a smell of the comet were created, introducing the chemical components of the comet. The smell was recreated by combining several molecules that were found in the comet's coma with the ROSINA instrument: in particular, hydrogen cyanide, ammonia and hydrogen sulphide. Interactive: Augmented Reality (AR) Inspired by spectroscopic data from OSIRIS, I introduce AR to reveal a "hidden" layer. I am highlighting that some scientific information can only be viewed by using special instruments, in this case - instruments on board the Rosetta spacecraft. Viewers can see a virtual layer on top of my paintings using a readily available instrument - ones cellphone. RGB colors, of a particular wavelength, will be introduced to the generally monochromatic paintings. Through my art I study the relationship between humans and the Universe, understanding the connection, the influence and the effect they have on each other. ESA's example of human scientists ambitiously exploring a distant cosmic object empowers me to create and share my personal exploration. This is the way I would like to share comet 67P with the world. I invite you to look through an artist's eyes and see science with renewed beauty and wonder. To view the artwork: http://www.ekaterina-smirnova.com/67p/ http://www.ekaterina-smirnova.com/67p-sculptures/

Solid deuterated water in space: detection constraints from laboratory experiments

NASA Astrophysics Data System (ADS)

Urso, R. G.; Palumbo, M. E.; Baratta, G. A.; Scirè, C.; Strazzulla, G.

2018-06-01

The comparison between astronomical spectra and laboratory experiments is fundamental to spread light on the structure and composition of ices found in interstellar dense molecular clouds and in Solar System bodies. Water is among the most abundant solid-phase species observed in these environments, and several attempts have been made to investigate the presence of its solid-phase isotopologues. In particular, the detection of the O-D stretching mode band at 4.1 μm due to both D2O and HDO within icy grain mantles is still under debate, and no detection have been reported about the presence of these species within icy bodies in the Solar System yet. In the near future, an important contribution could derive from the data acquired in the O-D stretching mode spectral range by the sensitive instruments on board the James Webb Space Telescope. With this in mind, we performed several laboratory experiments to study the O-D stretching mode band in solid mixtures containing water and deuterated water deposited in the temperature range between 17 and 155 K, in order to simulate astrophysical relevant conditions. Furthermore, samples have been studied at various temperature and irradiated with energetic ions (200 keV H+) in order to study the effects induced by both thermal and energetic processing. Our results provide some constraints on the detection of the 4.1 μm band in astronomical environments.

GreenHouse Observations of the Stratosphere and Troposphere (GHOST): a novel shortwave infrared spectrometer developed for the Global Hawk unmanned aerial vehicle

NASA Astrophysics Data System (ADS)

Humpage, Neil; Bösch, Hartmut; Palmer, Paul I.; Parr-Burman, Phil M.; Vick, Andrew J. A.; Bezawada, Naidu N.; Black, Martin; Born, Andrew J.; Pearson, David; Strachan, Jonathan; Wells, Martyn

2014-10-01

The tropospheric distribution of greenhouse gases (GHGs) depends on surface flux variations, atmospheric chemistry and transport processes over a range of spatial and temporal scales. Accurate and precise atmospheric concentration observations of GHGs can be used to infer surface flux estimates, though their interpretation relies on unbiased atmospheric transport models. GHOST is a novel, compact shortwave infrared spectrometer which will observe tropospheric columns of CO2, CO, CH4 and H2O (along with the HDO/H2O ratio) during deployment on board the NASA Global Hawk unmanned aerial vehicle. The primary science objectives of GHOST are to: 1) test atmospheric transport models; 2) evaluate satellite observations of GHG column observations over oceans; and 3) complement in-situ tropopause transition layer observations from other Global Hawk instruments. GHOST comprises a target acquisition module (TAM), a fibre slicer and feed system, and a multiple order spectrograph. The TAM is programmed to direct solar radiation reflected by the ocean surface into a fibre optic bundle. Incoming light is then split into four spectral bands, selected to optimise remote observations of GHGs. The design uses a single grating and detector for all four spectral bands. We summarise the GHOST concept and its objectives, and describe the instrument design and proposed deployment aboard the Global Hawk platform.

D/H isotopic fractionation effects in the H2-H2O system: An in-situ experimental study at supercritical water conditions

NASA Astrophysics Data System (ADS)

Foustoukos, D.; Mysen, B. O.

2011-12-01

Understanding the effect of temperature on the relative distribution of volatiles in supercritical aqueous solutions is important to constrain elemental and isotopic partitioning/fractionation effects in systems applicable to planetary interiors where the temperature-pressure conditions are often beyond existing experimental or theoretical datasets. For example, very little exists for the fundamental equilibria between H2, D2 and HD (H2 + D2 = 2HD), which, in turn, constrains the internal D/H isotope exchange and the evolution of HD in H2-containing systems such as H2-CH4 and H2-H2O. Theoretical calculations considering the partition functions of the molecules predict that with temperature increase, the equilibrium constant of this reaction approximates values that correspond to the stochastic distribution of species. These calculations consider pure harmonic vibrational frequencies, which, however, do not apply to the diatomic molecule of hydrogen, especially because anharmonic oscillations are anticipated to become stronger at high temperatures. Published experimental data have been limited to conditions lower than 468°C with large uncertainties at elevated temperatures. To address the lack of experimental data, a series of hydrothermal diamond anvil experiments has been conducted utilizing vibrational spectroscopy as a novel quantitative method to explore the relative distribution of H- and D-bearing volatiles in the H2-D2-D2O-H2O-Ti-TiO2 system. The fundamentals of this methodology are based on the distinct Raman frequency shift resulting from deuterium substitution in the H-H and O-H bonds. In detail, H2O-D2O solutions (1:1) were reacted with Ti metal (for 3-9hrs) at 600-800°C and pressures of 0.5-1 GPa, leading to formation of H2, D2, HD and HDO species through Ti oxidation and H-D isotope exchange reactions. Experimental results obtained in-situ and in the quenched gas phase, indicate a significant deviation from the theoretical estimate of the equilibrium thermodynamic properties of the H-D exchange reactions. In fact, the estimated enthalpy change for the 2HD=D2+H2 reaction, ΔHrx, approximates -3.1 kcal/mol, which differs greatly from the +0.2 kcal/mol predicted by statistical mechanics models. Similar differences in ΔHrx are observed for the isotope equilibrium reaction of 2HDO=H2O + D2O. The establishment of negative ΔHrx and the decrease of equilibrium constants with temperature increase are possibly triggered by dominant contribution of anharmonic vibrations or differences on the Henry Law constant between the H- and D-bearing species dissolved in supercritical fluids. The distinct Raman frequency shift due to deuterium isotopic substitutions demonstrated for H2 and H2O, would also be expected for other H-containing compounds such as, for example, CH4 and NH3. This approach to the experimental determination of isotopic equilibria may, therefore, provide ways to describe the equilibrium of isotope exchange reactions for which theoretical or experimental measurements are lacking and which are critical for evaluation of COHN fluid behavior in metamorphic and magmatic processes in the planetary interiors.

Millimeter Wave Spectroscopy in a Semi-Confocal Fabry-Perot Cavity

NASA Astrophysics Data System (ADS)

Drouin, Brian; Tang, Adrian; Reck, Theodore J.; Nemchick, Deacon J.; Cich, Matthew J.; Crawford, Timothy J.; Raymond, Alexander W.; Chang, M.-C. Frank; Kim, Rod M.

2017-06-01

A new generation of CMOS circuits operating at 89-104 GHz with improved output power and pulse switch isolation have enhanced the performance of the miniaturized pulsed-echo Fourier transform spectrometer under development for planetary exploration at the Jet Propulsion laboratory. Additional progress has been made by creating a waveguide-fed structure for the novel planar coupler design. This structure has enabled characterization of each component in the system and enabled spectroscopy to be done with conventional millimeter hardware that enables (1) direct comparisons to the CMOS components, (2) enhanced bandwidth of 74-109 GHz, and (3) amplification of the transmitter prior to cavity injection. We have now demonstrated the technique with room temperature detections on multiple species including N_2O, OCS, CH_3CN, CH_3OH, CH_3NH_2, CH_3CHO, CH_3Cl, HDO, D_2O, CH_3CH_2CN and CH_3CH_2OH. Of particular interest to spectroscopic work in the millimeter range is the ongoing incorporation of a ΔΣ radio-frequency source into the millimeter-wave lock-loop - this has improved the phase-noise of the tunable CMOS transceiver to better than the room-temperature Doppler limit and provides a promising source for general use that may replace the high end microwave synthesizers. We are in the process of building a functional interface to the various subsystems. We will present a trade-space study to determine the optimal operating conditions of the pulse-echo system.

Influence of the support of CoMo sulfide catalysts and of the addition of potassium and platinum on the catalytic performances for the hydrodeoxygenation of carbonyl, carboxyl, and guaiacol-type molecules

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

Centeno, A.; Laurent, E.; Delmon, B.

1995-07-01

The present work corresponds to part of a program aimed at upgrading oil obtained by pyrolysis of biomass by hydrotreatment (hydrodeoxygenation HDO). CoMo sulfide catalysts, nonsupported, supported on different supports (alumina, carbon, silica), or modified by K or Pt, were used. The authors used a model reacting mixture containing compounds representative of the molecules that must react to permit a primary stabilisation of the pyrolytic oil: 4-methy lacetophenone (4-MA), diethylsebacate (DES), and guaiacol (GUA). In the reaction of the carbonyl group of the 4-MA it is shown that no important role is played by any acid-base mechanism; dispersion determines themore » activity. Acidity of the support influences the formation of active sites for decarboxylation and hydrogenation of the carboxyl group of DES. It was confirmed that guaiacol-type molecules lead to coking reactions. The role of acidity in the mechanism of these reactions is confirmed, but the modifications made in the catalysts in this work are still not sufficient to control coke deposition. The catalysts supported on carbon lead to the direct elimination of the methoxyl group of the guaiacol. Carbon, on the whole, seems to be a promising support. This work suggests that appropriate modifications of the hydrotreating catalysts can lead to a more effective process for stabilisation of the bio-oils by reaction with hydrogen. 55 refs., 3 figs., 5 tabs.« less

Comparing Global Positioning System (GPS) and Global Navigation Satellite System (GNSS) Measures of Team Sport Movements.

PubMed

Jackson, Benjamin M; Polglaze, Ted; Dawson, Brian; King, Trish; Peeling, Peter

2018-02-21

To compare data from conventional GPS and new GNSS-enabled tracking devices, and to examine the inter-unit reliability of GNSS devices. Inter-device differences between 10 Hz GPS and GNSS devices were examined during laps (n=40) of a simulated game circuit (SGC) and during elite hockey matches (n=21); GNSS inter-unit reliability was also examined during the SGC laps. Differences in distance values and measures in three velocity categories (low <3 m.s -1 ; moderate 3-5 m.s -1 ; high >5 m.s -1 ) and acceleration/deceleration counts (>1.46 m.s -2 and < -1.46 m.s -2 ) were examined using one-way ANOVA. Inter-unit GNSS reliability was examined using the coefficient of variation (CV) and intra-class correlation coefficient (ICC). Inter-device differences (P <0.05) were found for measures of peak deceleration, low-speed distance, % total distance at low speed, and deceleration count during the SGC, and for all measures except total distance and low-speed distance during hockey matches. Inter-unit (GNSS) differences (P <0.05) were not found. The CV was below 5% for total distance, average and peak speeds and distance and % total distance of low-speed running. The GNSS devices had a lower HDoP score than GPS devices in all conditions. These findings suggest that GNSS devices may be more sensitive than GPS in quantifying the physical demands of team sport movements, but further study into the accuracy of GNSS devices is required.

Airborne in situ vertical profiling of HDO/H216O in the subtropical troposphere during the MUSICA remote sensing validation campaign

NASA Astrophysics Data System (ADS)

Dyroff, C.; Sanati, S.; Christner, E.; Zahn, A.; Balzer, M.; Bouquet, H.; McManus, J. B.; González-Ramos, Y.; Schneider, M.

2015-01-01

Vertical profiles of water vapor (H2O) and its isotope ratio D / H expressed as δ D(H2O were measured in situ by the ISOWAT II diode-laser spectrometer during the MUlti-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water (MUSICA) airborne campaign. We present recent modifications of the instrument design. The instrument calibration on the ground as well as in flight is described. Based on the calibration measurements, the humidity-dependent uncertainty of our airborne data is determined. For the majority of the airborne data we achieved an accuracy (uncertainty of the mean) of Δ(δ D) ≈ 10‰. Vertical profiles between 150 and ~7000 m were obtained during 7 days in July and August 2013 over the subtropical North Atlantic Ocean near Tenerife. The flights were coordinated with ground-based (Network for the Detection of Atmospheric Composition Change, NDACC) and space-based (Infrared Atmospheric Sounding Interferometer, IASI) FTIR remote-sensing measurements of δ D(H2O) as a means to validate the remote sensing humidity and δ D(H2O) data products. The results of the validation are presented in detail in a separate paper (Schneider et al., 2014). The profiles were obtained with a high vertical resolution of around 3 m. By analyzing humidity and δ D(H2O) correlations we were able to identify different layers of airmasses with specific isotopic signatures. The results are discussed.

Eu(III) Complex with DO3A-amino-phosphonate Ligand as a Concentration-Independent pH-Responsive Contrast Agent for Magnetic Resonance Spectroscopy (MRS).

PubMed

Krchová, Tereza; Herynek, Vít; Gálisová, Andrea; Blahut, Jan; Hermann, Petr; Kotek, Jan

2017-02-20

A new DOTA-like ligand H 5 do3aNP with a 2-[amino(methylphosphonic acid)]ethyl-coordinating pendant arm was prepared, and its coordinating properties were studied by NMR spectroscopy and potentiometry. The study revealed a rare slow exchange (on the 1 H and 31 P NMR time scale) between protonated and unprotonated complex species with a corresponding acidity constant pK A ∼ 8.0. This unusually slow time scale associated with protonation is caused by a significant geometric change from square-antiprismatic (SA) arrangement observed for protonated complex SA-[Eu(Hdo3aNP)] - to twisted-square-antiprismatic (TSA) arrangement found for deprotonated complex TSA-[Eu(do3aNP)] 2- . This behavior results in simultaneous occurrence of the signals of both species in the 31 P NMR spectra at approximately -118 and +70 ppm, respectively. Such an unprecedented difference in the chemical shifts between species differing by a proton is caused by a significant movement of the principal magnetic axis and by a change of phosphorus atom position in the coordination sphere of the central Eu(III) ion (i.e., by relative movement of the phosphorus atom with respect to the principal magnetic axis). It changes the sign of the paramagnetic contribution to the 31 P NMR chemical shift. The properties discovered can be employed in the measurement of pH by MRS techniques as presented by proof-of-principle experiments on phantoms.

The Sensitivity of Atmospheric Water Isotopes to Entrainment and Precipitation Efficiency in a Bulk Plume Model of Convection

NASA Astrophysics Data System (ADS)

Duan, S.; Wright, J. S.; Romps, D. M.

2016-12-01

Atmospheric water isotopes have been proposed as potentially powerful constraints on the physics of convective clouds and parameterizations of convective processes in models. We have previously derived an analytical model of water vapor (H2O) and one of its heavy isotopes (HDO) in convective environments based on a bulk-plume convective water budget in radiative convective equilibrium. This analytical model provides a useful starting point for examining the joint responses of water vapor and its isotopic composition to changes in convective parameters; however, certain idealistic assumptions are required to make the model analytically solvable. Here, we develop a more flexible numerical framework that enables a wider range of model configurations and includes additional isotopic tracers. This model provides a bridge between Rayleigh distillation, which is simple but inflexible, and more complicated convection schemes and cloud resolving models, which are more realistic but also more difficult to perturb and interpret. Application of realistic in-cloud water profiles in our model produces vertical distributions of δD that qualitatively match satellite observations from the Tropospheric Emission Spectrometer (TES). We test the sensitivity of water vapor and its isotopic composition to a wide range of perturbations in the model parameters and their vertical profiles. In this presentation, we focus especially on establishing constraints for convective entrainment and precipitation efficiency. We conclude by discussing the potential application of this model as part of a larger water isotope toolkit for use with offline diagnostics provided by reanalyses and GCMs.

Water Isotopes in Precipitation: Data/Model Comparison for Present-Day and Past Climates

NASA Technical Reports Server (NTRS)

Jouzel, J.; Hoffmann, G.; Masson, V.

1998-01-01

Variations of HDO and H2O-18 concentrations are observed in precipitation both on a geographical and on a temporal basis. These variations, resulting from successive isotopic fractionation processes at each phase change of water during its atmospheric cycle, are well documented through the IAEA/WMO network and other sources. Isotope concentrations are, in middle and high latitudes, linearly related to the annual mean temperature at the precipitation site. Paleoclimatologists have used this relationship to infer paleotemperatures from isotope paleodata extractable from ice cores, deep groundwater and other such sources. For this application to be valid, however, the spatial relationship must also hold in time at a given location as the location undergoes a series of climatic changes. Progress in water isotope modeling aimed at examining and evaluating this assumption has been recently reviewed with a focus on polar regions and, more specifically, on Greenland. This article was largely based on the results obtained using the isotopic version of the NASA/GISS Atmospheric General Circulation Model (AGCM) fitted with isotope tracer diagnostics. We extend this review in comparing the results of two different isotopic AGCMs (NASA/GISS and ECHAM) and in examining, with a more global perspective, the validity of the above assumption, i.e. the equivalence of the spatial and temporal isotope-temperature relationship. We also examine recent progress made in modeling the relationship between the conditions prevailing in moisture source regions for precipitation and the deuterium-excess of that precipitation.

The 2015 edition of the GEISA spectroscopic database

NASA Astrophysics Data System (ADS)

Jacquinet-Husson, N.; Armante, R.; Scott, N. A.; Chédin, A.; Crépeau, L.; Boutammine, C.; Bouhdaoui, A.; Crevoisier, C.; Capelle, V.; Boonne, C.; Poulet-Crovisier, N.; Barbe, A.; Chris Benner, D.; Boudon, V.; Brown, L. R.; Buldyreva, J.; Campargue, A.; Coudert, L. H.; Devi, V. M.; Down, M. J.; Drouin, B. J.; Fayt, A.; Fittschen, C.; Flaud, J.-M.; Gamache, R. R.; Harrison, J. J.; Hill, C.; Hodnebrog, Ø.; Hu, S.-M.; Jacquemart, D.; Jolly, A.; Jiménez, E.; Lavrentieva, N. N.; Liu, A.-W.; Lodi, L.; Lyulin, O. M.; Massie, S. T.; Mikhailenko, S.; Müller, H. S. P.; Naumenko, O. V.; Nikitin, A.; Nielsen, C. J.; Orphal, J.; Perevalov, V. I.; Perrin, A.; Polovtseva, E.; Predoi-Cross, A.; Rotger, M.; Ruth, A. A.; Yu, S. S.; Sung, K.; Tashkun, S. A.; Tennyson, J.; Tyuterev, Vl. G.; Vander Auwera, J.; Voronin, B. A.; Makie, A.

2016-09-01

The GEISA database (Gestion et Etude des Informations Spectroscopiques Atmosphériques: Management and Study of Atmospheric Spectroscopic Information) has been developed and maintained by the http://ara.abct.lmd.polytechnique.fr. The "line parameters database" contains 52 molecular species (118 isotopologues) and transitions in the spectral range from 10-6 to 35,877.031 cm-1, representing 5,067,351 entries, against 3,794,297 in GEISA-2011. Among the previously existing molecules, 20 molecular species have been updated. A new molecule (SO3) has been added. HDO, isotopologue of H2O, is now identified as an independent molecular species. Seven new isotopologues have been added to the GEISA-2015 database. The "cross section sub-database" has been enriched by the addition of 43 new molecular species in its infrared part, 4 molecules (ethane, propane, acetone, acetonitrile) are also updated; they represent 3% of the update. A new section is added, in the near-infrared spectral region, involving 7 molecular species: CH3CN, CH3I, CH3O2, H2CO, HO2, HONO, NH3. The "microphysical and optical properties of atmospheric aerosols sub-database" has been updated for the first time since 2003. It contains more than 40 species originating from NCAR and 20 from the http://eodg.atm.ox.ac.uk/ARIA/introduction_nocol.html. As for the previous versions, this new release of GEISA and associated management software facilities are implemented and freely accessible on the http://cds-espri.ipsl.fr/etherTypo/?id=950.

A novel Hessian based algorithm for rat kidney glomerulus detection in 3D MRI

NASA Astrophysics Data System (ADS)

Zhang, Min; Wu, Teresa; Bennett, Kevin M.

2015-03-01

The glomeruli of the kidney perform the key role of blood filtration and the number of glomeruli in a kidney is correlated with susceptibility to chronic kidney disease and chronic cardiovascular disease. This motivates the development of new technology using magnetic resonance imaging (MRI) to measure the number of glomeruli and nephrons in vivo. However, there is currently a lack of computationally efficient techniques to perform fast, reliable and accurate counts of glomeruli in MR images due to the issues inherent in MRI, such as acquisition noise, partial volume effects (the mixture of several tissue signals in a voxel) and bias field (spatial intensity inhomogeneity). Such challenges are particularly severe because the glomeruli are very small, (in our case, a MRI image is ~16 million voxels, each glomerulus is in the size of 8~20 voxels), and the number of glomeruli is very large. To address this, we have developed an efficient Hessian based Difference of Gaussians (HDoG) detector to identify the glomeruli on 3D rat MR images. The image is first smoothed via DoG followed by the Hessian process to pre-segment and delineate the boundary of the glomerulus candidates. This then provides a basis to extract regional features used in an unsupervised clustering algorithm, completing segmentation by removing the false identifications occurred in the pre-segmentation. The experimental results show that Hessian based DoG has the potential to automatically detect glomeruli,from MRI in 3D, enabling new measurements of renal microstructure and pathology in preclinical and clinical studies.

The Chemistry of Multiply Deuterated Molecules in Protoplanetary Disks: I. The Outer Disk

NASA Technical Reports Server (NTRS)

Willacy, K.

2007-01-01

We present new models of the deuterium chemistry in protoplanetary disks, including, for the first time, multiply deuterated species. We use these models to explore whether observations in combination with models can give us clues as to which desorption processes occur in disks.We find, in common with other authors, that photodesorption can allow strongly bound molecules such as HDO to exist in the gas phase in a layer above the midplane. Models including this process give the best agreement with the observations. In the midplane, cosmic-ray heating can desorb weakly bound molecules such as CO and N2. We find the observations suggest that N2 is gaseous in this region, but that CO must be retained on the grains to account for the observed DCO+/HCO+. This could be achieved by CO having a higher binding energy than N2 (as may be the case when these molecules are accreted onto water ice) or by a smaller cosmic-ray desorption rate for CO than assumed here, as suggested by recent theoretical work. For gaseous molecules the calculated deuteration can be greatly changed by chemical processing in the disk from the input molecular cloud values. On the grains singly deuterated species tend to retain the D/H ratio set in the molecular cloud, whereas multiply deuterated species are more affected by the disk chemistry. Consequently, the D/H ratios observed in comets may be partly set in the parent cloud and partly in the disk, depending on the molecule.

Airborne in situ vertical profiling of HDO / H216O in the subtropical troposphere during the MUSICA remote sensing validation campaign

NASA Astrophysics Data System (ADS)

Dyroff, C.; Sanati, S.; Christner, E.; Zahn, A.; Balzer, M.; Bouquet, H.; McManus, J. B.; Gonzalez-Ramos, Y.; Schneider, M.

2015-05-01

Vertical profiles of water vapor (H2O) and its isotope ratio D / H expressed as δD(H2O) were measured in situ by the ISOWAT II diode-laser spectrometer during the MUlti-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water (MUSICA) airborne campaign. We present recent modifications of the instrument design. The instrument calibration on the ground as well as in flight is described. Based on the calibration measurements, the humidity-dependent uncertainty of our airborne data is determined. For the majority of the airborne data we achieved an accuracy (uncertainty of the mean) of Δ(δD) ≈10‰. Vertical profiles between 150 and ~7000 m were obtained during 7 days in July and August 2013 over the subtropical North Atlantic Ocean near Tenerife. The flights were coordinated with ground-based (Network for the Detection of Atmospheric Composition Change, NDACC) and space-based (Infrared Atmospheric Sounding Interferometer, IASI) FTIR remote sensing measurements of δD(H2O) as a means to validate the remote sensing humidity and δD(H2O) data products. The results of the validation are presented in detail in a separate paper (Schneider et al., 2014). The profiles were obtained with a high vertical resolution of around 3 m. By analyzing humidity and δD(H2O) correlations we were able to identify different layers of air masses with specific isotopic signatures. The results are discussed.

Lamellar zirconium phosphates to host metals for catalytic purposes.

PubMed

Ballesteros-Plata, Daniel; Infantes-Molina, Antonia; Rodríguez-Aguado, Elena; Braos-García, Pilar; Rodríguez-Castellón, Enrique

2018-02-27

In the present study a porous lamellar zirconium phosphate heterostructure (PPH) formed from zirconium(iv) phosphate expanded with silica galleries (P/Zr molar ratio equal to 2 and (Si + Zr)/P equal to 3) was prepared to host noble metals. Textural and structural characterization of PPH-noble metal materials was carried out in order to elucidate the location and dispersion of the metallic particles and the properties of the resulting material to be used in catalytic processes. In the present paper, their activity in the catalytic hydrodeoxygenation (HDO) reaction of dibenzofuran (DBF) was evaluated. X-ray diffraction (XRD), solid state nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) evidenced that the structure of the pillared zirconium phosphate material was not modified by the incorporation of Pt and Pd. Moreover, transmission electron microscopy (TEM) showed a different dispersion of the noble metal. The acidity of the resulting PPH-noble metal materials also changed, although in all cases the acidity was of weak nature, and the incorporation of noble metals affected Brønsted acid sites as observed from 31 P NMR spectra. In general, the textural, structural and acidic properties of the resulting materials suggest that PPH can be considered a good candidate to be used as a catalytic support. Thus, the catalytic results of the PPH-noble metal samples indicated that the Pd sample showed a stable behavior probably ascribed to a high dispersion of the active phase. However, the Pt sample suffered from fast deactivation. The selectivity to the reaction products was strongly dependent on the noble metal employed.

High-throughput continuous flow synthesis of nickel nanoparticles for the catalytic hydrodeoxygenation of guaiacol

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

Roberts, Emily J.; Habas, Susan E.; Wang, Lu

2016-11-07

The translation of batch chemistries to high-throughput continuous flow methods dresses scaling, automation, and reproducibility concerns associated with the implementation of colloidally prepared nanoparticle (NP) catalysts for industrial catalytic processes. Nickel NPs were synthesized by the high-temperature amine reduction of a Ni2+ precursor using a continuous millifluidic (mF) flow method, achieving yields greater than 60%. The resulting Ni NP catalysts were compared against catalysts prepared in a batch reaction under conditions analogous to the continuous flow conditions with respect to total reaction volume, time, and temperature and by traditional incipient wetness (IW) impregnation for the hydrodeoxygenation (HDO) of guaiacol undermore » ex situ catalytic fast pyrolysis conditions. Compared to the IW method, the colloidally prepared NPs displayed increased morphological control and narrowed size distributions, and the NPs prepared by both methods showed similar size, shape, and crystallinity. The Ni NP catalyst synthesized by the continuous flow method exhibited similar H-adsorption site densities, site-time yields, and selectivities towards deoxygenated products as compared to the analogous batch reaction, and outperformed the IW catalyst with respect to higher selectivity to lower oxygen content products and a 6.9-fold slower deactivation rate. These results demonstrate the utility of synthesizing colloidal Ni NP catalysts using continuous flow methods while maintaining the catalytic properties displayed by the batch equivalent. Finally, this methodology can be extended to other catalytically relevant base metals for the high-throughput synthesis of metal NPs for the catalytic production of biofuels.« less

DYNAMIC DEUTERIUM ENRICHMENT IN COMETARY WATER VIA ELEY–RIDEAL REACTIONS

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

Yao, Yunxi; Giapis, Konstantinos P., E-mail: giapis@cheme.caltech.edu

2017-01-20

The deuterium-to-hydrogen ratio (D/H) in water found in the coma of Jupiter family comet (JFC) 67P/Churyumov–Gerasimenko was reported to be (5.3 ± 0.7) × 10{sup −4}, the highest among comets and three times the value for other JFCs with an ocean-like ratio. This discrepancy suggests the diverse origins of JFCs and clouds the issue of the origin of Earth’s oceanic water. Here we demonstrate that Eley–Rideal reactions between accelerated water ions and deuterated cometary surface analogs can lead to instantaneous deuterium enrichment in water scattered from the surface. The reaction proceeds with H{sub 2}O{sup +} abstracting adsorbed D atoms, formingmore » an excited H{sub 2}DO* state, which dissociates subsequently to produce energetic HDO. Hydronium ions are also produced readily by the abstraction of H atoms, consistent with H{sub 3}O{sup +} detection and abundance in various comets. Experiments with water isotopologs and kinematic analysis on deuterated platinum surfaces confirmed the dynamic abstraction mechanism. The instantaneous fractionation process is independent of the surface temperature and may operate on the surface of cometary nuclei or dust grains, composed of deuterium-rich silicates and carbonaceous chondrites. The requisite energetic water ions have been detected in the coma of 67P in two populations. This dynamic fractionation process may temporarily increase the water D/H ratio, especially as the comet gets closer to the Sun. The magnitude of the effect depends on the water ion energy-flux and the deuterium content of the exposed cometary surfaces.« less

Structure and spectra of H/sub 2/O in hydrated. beta. -alumina

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

Bates, J.B.; Dudney, N.J.; Brown, G.M.

1982-11-15

The structure and spectra of hydrated Li and Na ..beta..-alumina were investigated using neutron diffraction, infrared absorption, and Raman scattering. The dimensions of the hexagonal unit cell of a hydrated Li ..beta..-alumina crystal containing 1.55 H/sub 2/O molecules per unit cell are a = 5.591 A and c = 22.715 A. The oxygen atoms of the water molecules are located in the conduction plane between the mO, and the aBR sites; the protons, located above the below the plane, form bent hydrogen bonds with the O(4) oxygen ions. The HOH bond angle of water in Li ..beta..-alumina is 114/sup 0/more » and the Vertical BarO--HVertical Bar bond distance is 0.992 A. Based on polarized infrared spectra, H/sub 2/O adopts a similar structure and orientation in Na ..beta..-alumina. Spectra of absorbed H/sub 2/O, D/sub 2/O, and HDO species show that water molecules dissociate in Li ..beta..-alumina to form OH/sup -/ and H(H/sub 2/O)/sup +//sub n/ species. No evidence was found for the dissociation of water in Na ..beta..-alumina. The absorption coefficients determined for OH/sup -/ and H/sub 2/O in Li ..beta..-alumina include local field corrections. A large local field anisotropy at the protons of H/sub 2/O is responsible for the large ratio of the intensities of ..nu../sub 3/ and ..nu../sub 1/ observed for water in Li and Na ..beta..-alumina.« less

Observations of D/H ratios in H2O, HCl, and HF on Venus and new DCl and DF line strengths

NASA Astrophysics Data System (ADS)

Krasnopolsky, V. A.; Belyaev, D. A.; Gordon, I. E.; Li, G.; Rothman, L. S.

2013-05-01

Intensities of the spectral lines in the fundamental bands of D35Cl and DF were calculated using the semi-empirical dipole moment functions derived from the most accurate and precise measurements of intensities of the ro-vibrational lines of H35Cl and HF. Values obtained in this way for the deuterated species are superior to any available measured or calculated data to date. Our study of the D/H ratios in H2O, HCl, and HF on Venus is based on spatially-resolved high-resolution spectroscopy using the CSHELL spectrograph at NASA IRTF. Search for DF on Venus using its R5 (1-0) line at 3024.054 cm-1 results in a DF mixing ratio of 0.23 ± 0.11 ppb that corresponds to (D/H)HF = 420 ± 200 times that in the Standard Mean Ocean Water (SMOW). H2O abundances on Venus were retrieved using lines at 3022.366 and 3025.761 cm-1 that were observed at an exceptionally low overhead telluric water abundance of 0.3 pr. mm. The measured H2O mixing ratios at 74 km vary insignificantly between 55°S and 55°N with a mean value of 3.2 ppm. When compared with simultaneous observations of HDO near 2722 cm-1, this results in (D/H)H2O = 95 ± 15 times SMOW. Reanalysis of the observation of the D35Cl R4 (1-0) line at 2141.540 cm-1 (Krasnopolsky, V.A. [2012b]. Icarus 219, 244-249) using the improved line strength and more thorough averaging of the spectra gives (D/H)HCl = 190 ± 50 times SMOW. The similarity of the measured (D/H)H2O = 95 ± 15 at 74 km with 120 ± 40 observed by De Bergh et al. (De Bergh, C., Bezard, B., Owen, T., Crisp, D., Maillard, J.P., Lutz, B.L. [1991]. Science 251, 547-549) below the clouds favors the constant (D/H)H2O from the surface to the mesosphere, in accord with the prediction by theory. D/H ≈ 100 removes a difference of a factor of 2 between H2O abundances in the observations by Krasnopolsky (Krasnopolsky, V.A. [2010b]. Icarus 209, 314-322) and the Venus Express nadir observations (Cottini, V., Ignatiev, N.I., Piccioni, G., Drossart, P., Grassi, D., Markiewicz, W.J. [2012]. Icarus 217, 561-569). Equivalent widths of the HDO and H2O lines are similar in our observations; therefore some errors cancel out in their ratios. Photochemistry of HCl in the mesosphere tends to enrich D in HCl and deplete it in H2O. This may be an explanation of the twofold difference between the observed D/H in HCl and H2O. An alternative explanation is based on (D/H)H2O ≈ 200 observed in the mesosphere by Bjoraker et al. (Bjoraker, G.L., Larson, H.P., Mumma, M.J., Timmermann, R., Montani, J.L. [1992]. Bull. Am. Astron. Soc. 24, 995) and Fedorova et al. (Fedorova, A. et al. J. Geophys. Res. 113, E00B22). This means an effective exchange of D between H2O and HCl and almost equal D/H in both species. However, this requires a twofold increase in D/H from the lower atmosphere to the mesosphere. This increase is not supported by theory; furthermore, condensation processes usually deplete D/H above the clouds. Photochemistry of HF has not been studied; it proceeds mostly in the lower thermosphere, and D/H in HF may be very different from that in H2O. Overall, the observational data on D/H in all hydrogen-bearing species on Venus are helpful to solve the problem of deuterium fractionation on Venus.

A novel bioactive derivative of eicosapentaenoic acid (EPA) suppresses intestinal tumor development in ApcΔ14/+ mice.

PubMed

Nakanishi, Masako; Hanley, Matthew P; Zha, Ruochen; Igarashi, Yuichi; Hull, Mark A; Mathias, Gary; Sciavolino, Frank; Grady, James J; Rosenberg, Daniel W

2018-03-08

Familial adenomatous polyposis (FAP) is a genetic disorder characterized by the development of hundreds of polyps throughout the colon. Without prophylactic colectomy, most individuals with FAP develop colorectal cancer at an early age. Treatment with EPA in the free fatty acid form (EPA-FFA) has been shown to reduce polyp burden in FAP patients. Since high-purity EPA-FFA is subject to rapid oxidation, a stable form of EPA compound has been developed in the form of magnesium l-lysinate bis-eicosapentaenoate (TP-252). We assessed the chemopreventive efficacy of TP-252 on intestinal tumor formation using ApcΔ14/+ mice and compared it with EPA-FFA. TP-252 was supplemented in a modified AIN-93G diet at 1, 2 or 4% and EPA-FFA at 2.5% by weight and administered to mice for 11 weeks. We found that administration of TP-252 significantly reduced tumor number and size in the small intestine and colon in a dose-related manner and as effectively as EPA-FFA. To gain further insight into the cancer protection afforded to the colon, we performed a comprehensive lipidomic analysis of total fatty acid composition and eicosanoid metabolites. Treatment with TP-252 significantly decreased the levels of arachidonic acid (AA) and increased EPA concentrations within the colonic mucosa. Furthermore, a classification and regression tree (CART) analysis revealed that a subset of fatty acids, including EPA and docosahexaenoic acid (DHA), and their downstream metabolites, including PGE3 and 14-hydroxy-docosahexaenoic acid (HDoHE), were strongly associated with antineoplastic activity. These results indicate that TP-252 warrants further clinical development as a potential strategy for delaying colectomy in adolescent FAP patients.

New measurements of vertical thermal structure and wind velocities in the Venusian mesosphere

NASA Astrophysics Data System (ADS)

Widemann, T.; Sandor, B. J.; Clancy, R. T.; Lellouch, E.

2009-04-01

The Venus mesosphere is a highly variable transition region, in latitude, local time and over short time scales, between the zonal circulation of the lower atmosphere and the diurnal, sub-solar to anti-solar circulation in the upper atmosphere. In the framework of European Space Agency's second campaign of ground-based observations (Feb 8-22, 2009) in support of the Venus-Express mission, we coordinated new observations sampling a large range of altitudes in the Venus mesosphere on Feb. 7-8 and Feb. 14-15 : (1) James Clerk Maxwell Submillimeter Telescope (JCMT) submillimeter lines observations of mesospheric CO spectral lines measurements of temperature, CO mixing ratio and winds over the 95-115 km altitude range (Clancy et al., 2008), while SO2, SO and HDO observations were also probed in the 70-100 km range ; (2) Canada-France-Hawaii Telescope (CFHT) optical spectropolarimeter ESPaDOnS observations of visible Solar Fraunhofer lines measuring the winds at cloud tops near 70 km and visible CO2 lines 1-2 scale heights above (Widemann et al., 2007, 2008). Synchronization of wind measurements helps characterize possible correlation patterns between wind variations in the lower and middle mesosphere over a day time scale. Preliminary results will be presented at the meeting. Clancy, R.T., Sandor, B.J., and Moriarty-Schieven, G.H. 2008, Planet. Space Sci. 56, 1320-1334. Widemann, T., Lellouch, E., and Campargue, A. 2007, New Wind Measurements in Venus' Lower Mesosphere From Visible Spectroscopy, Planet. Space Sci. 55, 1741-1756 Widemann, T., Lellouch, E., Donati, J.-F., 2008, Venus Doppler winds at Cloud Tops Observed with ESPaDOnS at CFHT, Planet. Space Sci. 56, 1320-133 --

Distributions of δD observations from IASI/MetOp across the globe and intercomparison with other instruments/measurements

NASA Astrophysics Data System (ADS)

Lacour, Jean-Lionel; Clarisse, Lieven; Hurtmans, Daniel; Clerbaux, Cathy; Worden, John; Schneider, Matthias; Risi, Camille; Coheur, Pierre-François

2014-05-01

The Infrared Atmospheric Sounding Interferometer (IASI) onboard MetOp, through its observations of the water isotopologues, has great potential to support research on hydrological processes responsible for the moistening/drying of the atmosphere. The instrumental characteristics of the spectrometer (low radiometric noise and good spectral resolution) combined with its high sampling (global coverage twice a day) make it particularly suitable for providing numerous observations of the isotopologues ratio (δD) of water vapour in the troposphere. Retrieving isotopologues ratios at the required accuracy is, however, a challenging task. To get meaningful results, the retrieval needs to be well constrained. This can be achieved, with the optimal estimation method, by using an a priori probability density function containing correlation information between HDO and H2O. In this presentation, first, we will show that the measurements are mainly sensitive to δD in the troposphere between 3 and 6 km. We will illustrate the capabilities of IASI to provide δD observations at high spatio-temporal resolution with some distributions across the globe and we will discuss their added values to constrain hydrological processes. Second, we will document how IASI observations compare to other remote sounding observations of δD in the troposphere. Comparisons of IASI observations with the TES sounder and with three ground-based NDACC FTIR (Izaña, Kalsruhe and Kiruna, data generated within the project MUSICA) will be presented. The differences between the instruments as well as the methodology to compare them will be exposed. We will show that the different instruments agree within their own uncertainties and vertical sensitivities, asserting the use of IASI δD observations for scientific purposes.

Intercomparison of TCCON and MUSICA Water Vapour Products

NASA Astrophysics Data System (ADS)

Weaver, D.; Strong, K.; Deutscher, N. M.; Schneider, M.; Blumenstock, T.; Robinson, J.; Notholt, J.; Sherlock, V.; Griffith, D. W. T.; Barthlott, S.; García, O. E.; Smale, D.; Palm, M.; Jones, N. B.; Hase, F.; Kivi, R.; Ramos, Y. G.; Yoshimura, K.; Sepúlveda, E.; Gómez-Peláez, Á. J.; Gisi, M.; Kohlhepp, R.; Warneke, T.; Dohe, S.; Wiegele, A.; Christner, E.; Lejeune, B.; Demoulin, P.

2014-12-01

We present an intercomparison between the water vapour products from the Total Carbon Column Observing Network (TCCON) and the MUlti-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water (MUSICA), two datasets from ground-based Fourier Transform InfraRed (FTIR) spectrometers with good global representation. Where possible, comparisons to radiosondes are also included. The near-infrared TCCON measurements are optimized to provide precise monitoring of greenhouse gases for carbon cycle studies; however, TCCON's retrievals also produce water vapour products. The mid-infrared MUSICA products result from retrievals optimized to give precise and accurate information about H2O, HDO, and δD. The MUSICA water vapour products have been validated by extensive intercomparisons with H2O and δD in-situ measurements made from ground, radiosonde, and aircraft (Schneider et al. 2012, 2014), as well as by intercomparisons with satellite-based H2O and δD remote sensing measurements (Wiegele et al., 2014). This dataset provides a valuable reference point for other measurements of water vapour. This study is motivated by the limited intercomparisons performed for TCCON water vapour products and limited characterisation of their uncertainties. We compare MUSICA and TCCON products to assess the potential for TCCON measurements to contribute to studies of the water cycle, water vapour's role in climate and use as a tracer for atmospheric dynamics, and to evaluate the performance of climate models. The TCCON and MUSICA products result from measurements taken using the same FTIR instruments, enabling a comparison with constant instrumentation. The retrieval techniques differ, however, in their method and a priori information. We assess the impact of these differences and characterize the comparability of the TCCON and MUSICA datasets.

CO2 profile retrievals from TCCON spectra

NASA Astrophysics Data System (ADS)

Dohe, Susanne; Hase, Frank; Sepúlveda, Eliezer; García, Omaira; Wunch, Debra; Wennberg, Paul; Gómez-Peláez, Angel; Abshire, James B.; Wofsy, Steven C.; Schneider, Matthias; Blumenstock, Thomas

2014-05-01

The Total Carbon Column Observing Network (TCCON) is a global network of ground-based Fourier Transform Spectrometers recording direct solar spectra in the near-infrared spectral region. With stringent requirements on the instrumentation, data processing and calibration, accurate and precise column-averaged abundances of CO2, CH4, N2O, HF, CO, H2O, and HDO are retrieved being an essential contribution for the validation of satellite data (e.g. GOSAT, OCO-2) and carbon cycle research (Olsen and Randerson, 2004). However, the determined column-averaged dry air mole fraction (DMF) contains no information about the vertical CO2 profile, due to the use of a simple scaling retrieval within the common TCCON analysis, where the fitting algorithm GFIT (e.g. Yang et al., 2005) is used. In this presentation we will apply a different procedure for calculating trace gas abundances from the measured spectra, the fitting algorithm PROFFIT (Hase et. al., 2004) which has been shown to be in very good accordance with GFIT. PROFFIT additionally offers the ability to perform profile retrievals in which the pressure broadening effect of absorption lines is used to retrieve vertical gas profiles, being of great interest especially for the CO2 modelling community. A new analyzing procedure will be shown and retrieved vertical CO2 profiles of the TCCON sites Izaña (Tenerife, Canary Islands, Spain) and Lamont (Oklahoma, USA) will be presented and compared with simultaneously performed surface in-situ measurements and CO2 profiles from different aircraft campaigns. References: - Hase, F. et al., J.Q.S.R.T. 87, 25-52, 2004. - Olsen, S.C. and Randerson, J.T., J.G.Res., 109, D023012, 2004. - Yang, Z. et al., J.Q.S.R.T., 90, 309-321, 2005.

Ring-opening of {sigma}-thienyl and {sigma}-furyl ligands at ditungsten (M=M) centers

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

Chisholm, M.H.; Haubrich, S.T.; Huffman, J.C.

1997-02-19

A series of compounds of formula 1,2-M{sub 2}({sigma}-Th){sub 2}(NMe{sub 2}){sub 4}, 1,has been prepared, where M = Mo and/or W and Th = 2-thienyl[2-Th], 3-thienyl[3-Th], 5-methyl-2-thienyl[2,5-MeTh], and 2-benzothienyl[2-BTh]. Addition of {sup t}BuOH or CF{sub 3}Me{sub 2}COH to hydrocarbon solutions of 1, where M = W, lead to ring-opened products, 2, when the thienyl ligand is attached via the 2-carbon position. No ring-opening occurs for 3-thienyl derivatives. W{sub 2}(OR){sub 5}({mu}-CCH{sub 2}CHCHS)({sigma}-2-Th), 2, where one of the 2-thienyl rings has been opened, has been fully characterized and shown to be derived from a ring-opened {mu}-vinylidene intermediate W{sub 24}/(O{sup t}Bu){sub 4}({mu}-CCHCHCHS)({sigma}-2-Th). The compoundmore » W{sub 2}({sigma}-2-Fu){sub 2}(NMe{sub 2}){sub 4} was prepared and characterized (2-Fu = 2-furyl) and shown to undergo ring-opening in its reaction with {sup t}BuOH to give W{sub 2}(O{sup t}Bu){sub 5}({mu}-CCH{sub 2}CHCHO)({sigma}-2-Fu), 4, in an analogous manner to the 2-Th complex. The complexes 1 (M = W, 2-Th), 2, 3, and 4 have been characterized by single crystal X-ray studies. The results described herein are compared to other ring-opening reactions of S, N, and O organic heterocyclic compounds as models for the activation of S, N, and O containing fossil fuels in hydrodesulfurization (HDS), hydrodenitrogenation (HDN), and hydrodeoxygenation (HDO) processes. 36 refs., 7 figs., 5 tabs.« less

Time-domain calculations of the polarized Raman spectra, the transient infrared absorption anisotropy, and the extent of delocalization of the OH stretching mode of liquid water.

PubMed

Torii, Hajime

2006-08-03

The polarized Raman spectrum and the time dependence of the transient infrared (TRIR) absorption anisotropy are calculated for the OH stretching mode of liquid water (neat liquid H2O) by using time-domain formulations, which include the effects of both the diagonal frequency modulations (of individual oscillators) induced by the interactions between the dipole derivatives and the intermolecular electric field, and the off-diagonal (intermolecular) vibrational coupling described by the transition dipole coupling (TDC) mechanism. The IR spectrum of neat liquid H2O and the TRIR anisotropy of a liquid mixture of H2O/HDO/D2O are also calculated. It is shown that the calculated features of these optical signals, including the temperature dependence of the polarized Raman and IR spectra, are in reasonable agreement with the experimental results, indicating that the frequency separation between the isotropic and anisotropic components of the polarized Raman spectrum and the rapid decay (approximately 0.1 ps) of the TRIR anisotropy of the OH stretching mode of neat liquid H2O are mainly controlled by the resonant intermolecular vibrational coupling described by the TDC mechanism. Comparing with the time evolution of vibrational excitations, it is suggested that the TRIR anisotropy decays in the time needed for the initially localized vibrational excitations to delocalize over a few oscillators. It is also shown that the enhancement of the dipole derivatives by the interactions with surrounding molecules is an important factor in generating the spectral profiles of the OH stretching Raman band. The time-domain behavior of the molecular motions that affect the spectroscopic features is discussed.

Intercomparison of Open-Path Trace Gas Measurements with Two Dual Frequency Comb Spectrometers

PubMed Central

Waxman, Eleanor M.; Cossel, Kevin C.; Truong, Gar-Wing; Giorgetta, Fabrizio R.; Swann, William C.; Coburn, Sean; Wright, Robert J.; Rieker, Gregory B.; Coddington, Ian; Newbury, Nathan R.

2017-01-01

We present the first quantitative intercomparison between two open-path dual comb spectroscopy (DCS) instruments which were operated across adjacent 2-km open-air paths over a two-week period. We used DCS to measure the atmospheric absorption spectrum in the near infrared from 6021 to 6388 cm−1 (1565 to 1661 nm), corresponding to a 367 cm−1 bandwidth, at 0.0067 cm−1 sample spacing. The measured absorption spectra agree with each other to within 5×10−4 without any external calibration of either instrument. The absorption spectra are fit to retrieve concentrations for carbon dioxide (CO2), methane (CH4), water (H2O), and deuterated water (HDO). The retrieved dry mole fractions agree to 0.14% (0.57 ppm) for CO2, 0.35% (7 ppb) for CH4, and 0.40% (36 ppm) for H2O over the two-week measurement campaign, which included 23 °C outdoor temperature variations and periods of strong atmospheric turbulence. This agreement is at least an order of magnitude better than conventional active-source open-path instrument intercomparisons and is particularly relevant to future regional flux measurements as it allows accurate comparisons of open-path DCS data across locations and time. We additionally compare the open-path DCS retrievals to a WMO-calibrated cavity ringdown point sensor located along the path with good agreement. Short-term and long-term differences between the two systems are attributed, respectively, to spatial sampling discrepancies and to inaccuracies in the current spectral database used to fit the DCS data. Finally, the two-week measurement campaign yields diurnal cycles of CO2 and CH4 that are consistent with the presence of local sources of CO2 and absence of local sources of CH4. PMID:29276547

Hydrogen isotope exchanges between water and methanol in interstellar ices

NASA Astrophysics Data System (ADS)

Faure, A.; Faure, M.; Theulé, P.; Quirico, E.; Schmitt, B.

2015-12-01

The deuterium fractionation of gas-phase molecules in hot cores is believed to reflect the composition of interstellar ices. The deuteration of methanol is a major puzzle, however, because the isotopologue ratio [CH2DOH]/[CH3OD], which is predicted to be equal to 3 by standard grain chemistry models, is much larger (~20) in low-mass hot corinos and significantly lower (~1) in high-mass hot cores. This dichotomy in methanol deuteration between low-mass and massive protostars is currently not understood. In this study, we report a simplified rate equation model of the deuterium chemistry occurring in the icy mantles of interstellar grains. We apply this model to the chemistry of hot corinos and hot cores, with IRAS 16293-2422 and the Orion KL Compact Ridge as prototypes, respectively. The chemistry is based on a statistical initial deuteration at low temperature followed by a warm-up phase during which thermal hydrogen/deuterium (H/D) exchanges occur between water and methanol. The exchange kinetics is incorporated using laboratory data. The [CH2DOH]/[CH3OD] ratio is found to scale inversely with the D/H ratio of water, owing to the H/D exchange equilibrium between the hydroxyl (-OH) functional groups of methanol and water. Our model is able to reproduce the observed [CH2DOH]/[CH3OD] ratios provided that the primitive fractionation of water ice [HDO]/[H2O] is ~2% in IRAS 16293-2422 and ~0.6% in Orion KL. We conclude that the molecular D/H ratios measured in hot cores may not be representative of the original mantles because molecules with exchangeable deuterium atoms can equilibrate with water ice during the warm-up phase.

A Tropospheric Emission Spectrometer HDO/H2O Retrieval Simulator for Climate Models

NASA Technical Reports Server (NTRS)

Field, R. D.; Risi, C.; Schmidt, G. A.; Worden, J.; Voulgarakis, A.; LeGrande, A. N.; Sobel, A. H.; Healy, R. J.

2012-01-01

Retrievals of the isotopic composition of water vapor from the Aura Tropospheric Emission Spectrometer (TES) have unique value in constraining moist processes in climate models. Accurate comparison between simulated and retrieved values requires that model profiles that would be poorly retrieved are excluded, and that an instrument operator be applied to the remaining profiles. Typically, this is done by sampling model output at satellite measurement points and using the quality flags and averaging kernels from individual retrievals at specific places and times. This approach is not reliable when the model meteorological conditions influencing retrieval sensitivity are different from those observed by the instrument at short time scales, which will be the case for free-running climate simulations. In this study, we describe an alternative, categorical approach to applying the instrument operator, implemented within the NASA GISS ModelE general circulation model. Retrieval quality and averaging kernel structure are predicted empirically from model conditions, rather than obtained from collocated satellite observations. This approach can be used for arbitrary model configurations, and requires no agreement between satellite-retrieved and model meteorology at short time scales. To test this approach, nudged simUlations were conducted using both the retrieval-based and categorical operators. Cloud cover, surface temperature and free-tropospheric moisture content were the most important predictors of retrieval quality and averaging kernel structure. There was good agreement between the D fields after applying the retrieval-based and more detailed categorical operators, with increases of up to 30 over the ocean and decreases of up to 40 over land relative to the raw model fields. The categorical operator performed better over the ocean than over land, and requires further refinement for use outside of the tropics. After applying the TES operator, ModelE had D biases of 8 over ocean and 34 over land compared to TES D, which were less than the biases using raw model D fields.

The SPICAV-SOIR instrument probing the atmosphere of Venus: an overview

NASA Astrophysics Data System (ADS)

Trompet, Loïc; Mahieux, Arnaud; Wilquet, Valérie; Robert, Séverine; Chamberlain, Sarah; Thomas, Ian; Carine Vandaele, Ann; Bertaux, Jean-Loup

2016-04-01

The Solar Occultation in the Infrared (SOIR) channel mounted on top of the SPICAV instrument of the ESA's Venus Express mission has observed the atmosphere of Venus during more than eight years. This IR spectrometer (2.2-4.3 μm) with a high spectral resolution (0.12 cm-1) combined an echelle grating with an acousto-optic tunable filter for order selection. SOIR performed more than 1500 solar occultation measurements leading to about two millions spectra. The Royal Belgian Institute for Space Aeronomy (BIRA-IASB) was in charge of SOIR's development and operations as well as its data pipeline. BIRA-IASB carried out several studies on the composition of Venus mesosphere and lower thermosphere: carbon dioxide, carbon monoxide, hydrogen halide (HF, HCl, DF, DCl), sulfur dioxide, water (H2O, HDO) as well as sulphuric acid aerosols in the upper haze of Venus. Density and temperature profiles of the upper atmosphere of Venus (60 km to 170 km) at the terminator have been retrieved from SOIR's spectra using different assumptions, wherein the hydrostatic equilibrium and the local thermodynamical equilibrium in the radiative transfer calculations. These results allow us to produce an Atmospheric model of Venus called Venus Atmosphere from SOIR measurements at the Terminator (VAST). Data obtained by SOIR will also contribute to update the Venus International Reference Atmosphere (VIRA). Recently, the treatment of the raw data to transmittance has been optimized, and a new dataset of spectra has been produced. All raw spectra (PSA level 2) as well as calibrated spectra (PSA level 3) have been delivered to ESA's Planetary Science Archive (PDSPSA). Consequently the re-analysis of all spectra has been undergone. We will briefly present the improvements implemented in the data pipeline. We will also show a compilation of results obtained by the instrument considering the complete mission duration.

PIGC™ - A low cost fugitive emissions and methane detection system using advanced gas filter correlation techniques for local and wide area monitoring

NASA Astrophysics Data System (ADS)

Lachance, R. L.; Gordley, L. L.; Marshall, B. T.; Fisher, J.; Paxton, G.; Gubeli, J. F.

2015-12-01

Currently there is no efficient and affordable way to monitor gas releases over small to large areas. We have demonstrated the ability to accurately measure key greenhouse and pollutant gasses with low cost solar observations using the breakthrough sensor technology called the "Pupil Imaging Gas Correlation", PIGC™, which provides size and complexity reduction while providing exceptional resolution and coverage for various gas sensing applications. It is a practical implementation of the well-known Gas Filter Correlation Radiometry (GFCR) technique used for the HALOE and MOPITT satellite instruments that were flown on successful NASA missions in the early 2000s. This strong space heritage brings performance and reliability to the ground instrument design. A methane (CH4) abundance sensitivity of 0.5% or better of ambient column with uncooled microbolometers has been demonstrated with 1 second direct solar observations. These under $10 k sensors can be deployed in precisely balanced autonomous grids to monitor the flow of chosen gasses, and infer their source locations. Measureable gases include CH4, 13CO2, N2O, NO, NH3, CO, H2S, HCN, HCl, HF, HDO and others. A single instrument operates in a dual operation mode, at no additional cost, for continuous (real-time 24/7) local area perimeter monitoring for the detection of leaks for safety & security needs, looking at an artificial light source (for example a simple 60 W light bulb placed 100 m away), while simultaneously allowing solar observation for quasi-continuous wide area total atmospheric column scanning (3-D) for environmental monitoring (fixed and mobile configurations). The second mode of operation continuously quantifies the concentration and flux of specific gases over different ground locations, determined the amount of targeted gas being released from the area or getting into the area from outside locations, allowing better tracking of plumes and identification of sources. This paper reviews the measurement technique, performance demonstration and grid deployment strategy.

Cross-validation of IASI/MetOp derived tropospheric δD with TES and ground-based FTIR observations

NASA Astrophysics Data System (ADS)

Lacour, J.-L.; Clarisse, L.; Worden, J.; Schneider, M.; Barthlott, S.; Hase, F.; Risi, C.; Clerbaux, C.; Hurtmans, D.; Coheur, P.-F.

2014-11-01

The Infrared Atmospheric Sounding Interferometer (IASI) flying on-board MetOpA and MetOpB is able to capture fine isotopic variations of the HDO to H2O ratio (δD) in the troposphere. Such observations at the high spatio temporal resolution of the sounder are of great interest to improve our understanding of the mechanisms controlling humidity in the troposphere. In this study we aim to empirically assess the validity of our error estimation previously evaluated theoretically. To achieve this, we compare IASI δD retrieved profiles with other available profiles of δD, from the TES infrared sounder onboard AURA and from three ground-based FTIR stations produced within the MUSICA project: the NDACC (Network for the Detection of Atmospheric Composition Change) sites Kiruna and Izana, and the TCCON site Karlsruhe, which in addition to near-infrared TCCON spectra also records mid-infrared spectra. We describe the achievable level of agreement between the different retrievals and show that these theoretical errors are in good agreement with empirical differences. The comparisons are made at different locations from tropical to Arctic latitudes, above sea and above land. Generally IASI and TES are similarly sensitive to δD in the free troposphere which allows to compare their measurements directly. At tropical latitudes where IASI's sensitivity is lower than that of TES, we show that the agreement improves when taking into account the sensitivity of IASI in the TES retrieval. For the comparison IASI-FTIR only direct comparisons are performed because of similar sensitivities. We identify a quasi negligible bias in the free troposphere (-3‰) between IASI retrieved δD with the TES one, which are bias corrected, but an important with the ground-based FTIR reaching -47‰. We also suggest that model-satellite observations comparisons could be optimized with IASI thanks to its high spatial and temporal sampling.

The Borden Micrometeorological Experiment 2009 (BMW09): Micrometeorology and Stable Isotopes for Carbon Cycle Studies

NASA Astrophysics Data System (ADS)

Warland, J. S.; Wagner-Riddle, C.; Staebler, R. M.; Lee, X.; Bartlett, P. A.; Brown, S. E.; Kim, K.; Santos, E. A.; Chang, K.

2009-12-01

A large collaborative experiment took place during summer 2009 at the Environment Canada tower site on CFB Borden in southern Ontario. The site is a long-term flux monitoring station, instrumented for eddy covariance measurements of CO2 and H2O, soil respiration, canopy profiles of CO2, H2O and temperature, net radiation, and standard meteorological variables. During BMW09, we brought to the site additional instrumentation to monitor gradients of stable isotopes of CO2 and H2O, turbulence profiles in the canopy and additional soil respiration data. Tunable diode laser trace gas analyzers were used to make continuous, high-frequency measurements of 12CO2, 13CO2 and C16O18O and H216O, HDO and H218O. Measurements were made of gradients of these isotopes above the canopy and in the understory. Profiles of CO2, H2O, temperature and turbulence statistics were measured for inverse Lagrangian analysis, where concentration profiles are used to determine source strength profiles through the canopy, thus separating soil, understory and overstory components of the net exchange made by eddy covariance. The project combines stable isotope measurements with novel micrometeorological techniques with the goal of developing improved operational measurements and gaining new insight into carbon and water cycles through this two-pronged approach. The overall goal of this intensive measurement campaign was to provide detailed data on the carbon and water cycles within this natural ecosystem for use in model testing and improvement. Specifically, the project will use this data with the C&N-CLASS model (the Canadian Land Surface Scheme with additional carbon and nitrogen routines) to improve its ability to predict changes to natural ecosystems under a changing climate when used within GCM simulations. This poster will present an overview of the project, highlight preliminary results, and illustrate how these disparate datasets will be tied together to provide new insight into carbon cycling.

Alcohol Involvement in Sexual Behaviour and Adverse Sexual Health Outcomes from 26 to 38 Years of Age.

PubMed

Connor, Jennie L; Kydd, Robyn M; Dickson, Nigel P

2015-01-01

Research on alcohol and sexual behaviour has focused on young adults or high-risk groups, showing alcohol use contributing to riskier sexual choices. Adults now in their late thirties have been exposed to heavier drinking norms than previously, raising questions about effects on sexual wellbeing. We examined self-reported use and consequences of alcohol in sexual contexts, and its association with usual drinking pattern at age 38, and also associations of heavy drinking occasion (HDO) frequency with number of sexual partners, sexually transmitted infections (STIs), and terminations of pregnancy (TOPs), from 26-32 and 32-38 years of age. Members of the Dunedin Study birth cohort answered computer-presented questions about sexual behaviour and outcomes, and interviewer-administered alcohol consumption questions, at age 26, 32 and 38 years. Response level was >90% at each assessment. At 38, drinking before or during sex in the previous year was common (8.2% of men; 14.6% of women reported "usually/always"), and unwanted consequences were reported by 13.5% of men and 11.9% of women, including regretted sex or failure to use contraception or condoms. Frequent heavy drinkers were more likely to "use alcohol to make it easier to have sex" and regret partner choice, particularly women. Heavy drinking frequency was strongly associated with partner numbers for men and women at 32, but only for women at 38. Significantly higher odds of STIs amongst the heaviest drinking men, and TOPs amongst the heaviest drinking women were seen at 32-38. Alcohol involvement in sex continues beyond young adulthood where it has been well documented, and is common at 38. Women appear to be more affected than men, and heavy drinking is associated with poorer outcomes for both. Improving sexual health and wellbeing throughout the life course needs to take account of the role of alcohol in sexual behaviour.

Alcohol Involvement in Sexual Behaviour and Adverse Sexual Health Outcomes from 26 to 38 Years of Age

PubMed Central

Connor, Jennie L.; Kydd, Robyn M.; Dickson, Nigel P.

2015-01-01

Background Research on alcohol and sexual behaviour has focused on young adults or high-risk groups, showing alcohol use contributing to riskier sexual choices. Adults now in their late thirties have been exposed to heavier drinking norms than previously, raising questions about effects on sexual wellbeing. We examined self-reported use and consequences of alcohol in sexual contexts, and its association with usual drinking pattern at age 38, and also associations of heavy drinking occasion (HDO) frequency with number of sexual partners, sexually transmitted infections (STIs), and terminations of pregnancy (TOPs), from 26–32 and 32–38 years of age. Methods Members of the Dunedin Study birth cohort answered computer-presented questions about sexual behaviour and outcomes, and interviewer-administered alcohol consumption questions, at age 26, 32 and 38 years. Results Response level was >90% at each assessment. At 38, drinking before or during sex in the previous year was common (8.2% of men; 14.6% of women reported “usually/always”), and unwanted consequences were reported by 13.5% of men and 11.9% of women, including regretted sex or failure to use contraception or condoms. Frequent heavy drinkers were more likely to “use alcohol to make it easier to have sex” and regret partner choice, particularly women. Heavy drinking frequency was strongly associated with partner numbers for men and women at 32, but only for women at 38. Significantly higher odds of STIs amongst the heaviest drinking men, and TOPs amongst the heaviest drinking women were seen at 32–38. Conclusions Alcohol involvement in sex continues beyond young adulthood where it has been well documented, and is common at 38. Women appear to be more affected than men, and heavy drinking is associated with poorer outcomes for both. Improving sexual health and wellbeing throughout the life course needs to take account of the role of alcohol in sexual behaviour. PMID:26267272

Human inflammatory and resolving lipid mediator responses to resistance exercise and ibuprofen treatment

PubMed Central

Markworth, James F.; Vella, Luke; Lingard, Benjamin S.; Tull, Dedreia L.; Rupasinghe, Thusitha W.; Sinclair, Andrew J.; Maddipati, Krishna Rao

2013-01-01

Classical proinflammatory eicosanoids, and more recently discovered lipid mediators with anti-inflammatory and proresolving bioactivity, exert a complex role in the initiation, control, and resolution of inflammation. Using a targeted lipidomics approach, we investigated circulating lipid mediator responses to resistance exercise and treatment with the NSAID ibuprofen. Human subjects undertook a single bout of unaccustomed resistance exercise (80% of one repetition maximum) following oral ingestion of ibuprofen (400 mg) or placebo control. Venous blood was collected during early recovery (0–3 h and 24 h postexercise), and serum lipid mediator composition was analyzed by LC-MS-based targeted lipidomics. Postexercise recovery was characterized by elevated levels of cyclooxygenase (COX)-1 and 2-derived prostanoids (TXB2, PGE2, PGD2, PGF2α, and PGI2), lipooxygenase (5-LOX, 12-LOX, and 15-LOX)-derived hydroxyeicosatetraenoic acids (HETEs), and leukotrienes (e.g., LTB4), and epoxygenase (CYP)-derived epoxy/dihydroxy eicosatrienoic acids (EpETrEs/DiHETrEs). Additionally, we detected elevated levels of bioactive lipid mediators with anti-inflammatory and proresolving properties, including arachidonic acid-derived lipoxins (LXA4 and LXB4), and the EPA (E-series) and DHA (D-series)-derived resolvins (RvD1 and RvE1), and protectins (PD1 isomer 10S, 17S-diHDoHE). Ibuprofen treatment blocked exercise-induced increases in COX-1 and COX-2-derived prostanoids but also resulted in off-target reductions in leukotriene biosynthesis, and a diminished proresolving lipid mediator response. CYP pathway product metabolism was also altered by ibuprofen treatment, as indicated by elevated postexercise serum 5,6-DiHETrE and 8,9-DiHETrE only in those receiving ibuprofen. These findings characterize the blood inflammatory lipid mediator response to unaccustomed resistance exercise in humans and show that acute proinflammatory signals are mechanistically linked to the induction of a biological active inflammatory resolution program, regulated by proresolving lipid mediators during postexercise recovery. PMID:24089379

TDLAS a laser diode sensor for the in situ monitoring of H2O, CO2 and their isotopes in the Martian atmosphere

NASA Astrophysics Data System (ADS)

Le Barbu, T.; Vinogradov, I.; Durry, G.; Korablev, O.; Chassefière, E.; Bertaux, J.-L.

2006-01-01

Within the framework of Pasteur-Exomars, we have proposed to measure in situ water vapor (H2O, HDO, H218O, H217O) and carbon dioxide (CO2, 13C16O2, 16O12C18O, 16O12C17O) isotopes and also CO, CH4 and N2O by absorption spectroscopy using near infrared laser diodes. The Service d’Aéronomie has a relevant experience in trace-gas detection with laser diodes. We have developed, with the support of the CNES and the CNRS, the SDLA diode laser spectrometer to measure in situ H2O (at 1.39 μm), CH4 (1.65 μm) and CO2 (at 1.60 μm) in the middle atmosphere from stratospheric balloons. The concentrations are obtained with a precision error of a few percent and with a high temporal resolution that ranges from 10 ms to 1 s. The developed laser probing technique should be also highly efficient to study the Martian atmosphere as there are much higher amounts of water vapor and carbon dioxide in the Martian atmosphere than in the lower stratosphere (H2O: 200 ppmv at 6 hPa on Mars, 5 ppmv at 10 hPa in the low stratosphere (LS); CO2 95% on Mars, 360 ppmv in the LS). Hence, we propose to adapt the laser probing technique to the Martian atmosphere. The main objectives are to determine water vapor and carbon dioxide fluxes and to study boundary layer properties. The sensor will provide in situ daily, diurnally resolved measurements of near-surface H2O and CO2 concentrations over seasonal time scales. The additional isotopic measurements will provide quantitative constraints on the evolution of atmospheric composition and on the history of water on Mars.

Lidar measurements of the column CO2 mixing ratio made by NASA Goddard's CO2 Sounder during the NASA ASCENDS 2014 Airborne campaign.

NASA Astrophysics Data System (ADS)

Ramanathan, A. K.; Mao, J.; Abshire, J. B.; Kawa, S. R.

2015-12-01

Remote sensing measurements of CO2 from space can help improve our understanding of the carbon cycle and help constrain the global carbon budget. However, such measurements need to be sufficiently accurate to detect small (1 ppm) changes in the CO2 mixing ratio (XCO2) against a large background (~ 400 ppm). Satellite measurements of XCO2 using passive spectrometers, such as those from the Japanese GOSAT (Greenhouse gas Observing Satellite) and the NASA OCO-2 (Orbiting Carbon Observatory-2) are limited to daytime sunlit portions of the Earth and are susceptible to biases from clouds and aerosols. For this reason, NASA commissioned the formulation study of ASCENDS a space-based lidar mission. NASA Goddard Space Flight Center's CO2 Sounder lidar is one candidate approach for the ASCENDS mission. The NASA GSFC CO2 Sounder measures the CO2 mixing ratio using a pulsed multi-wavelength integrated path differential absorption (IPDA) approach. The CO2 Sounder has flown in the 2011, 2013 and 2014 ASCENDS airborne campaigns over the continental US, and has produced measurements in close agreement with in situ measurements of the CO2 column. In 2014, the CO2 Sounder upgraded its laser with a precision step-locked diode laser source to improve the lidar wavelength position accuracy. It also improved its optical receiver with a low-noise, high efficiency, HgCdTe avalanche photo diode detector. The combination of these two technologies enabled lidar XCO2 measurements with unprecedented accuracy. In this presentation, we show analysis from the ASCENDS 2014 field campaign, exploring: (1) Horizontal XCO2 gradients measured by the lidar, (2) Comparisons of lidar XCO2 measurements against the Parameterized Chemistry Transport Model (PCTM), and (3) Lidar column water vapor measurements using a HDO absorption line that occurs next to the CO2 absorption line. This can reduce the uncertainty in the dry air column used in XCO2 retrievals.

First measurements of water and D/H on Mars with ExoMars / NOMAD

NASA Astrophysics Data System (ADS)

Villanueva, Geronimo Luis; Liuzzi, Giuliano; Mumma, Michael J.; Carine Vandaele, Ann; Thomas, Ian; Smith, Michael D.; Daerden, Frank; Ristic, Bojan; Patel, Manish; Bellucci, Giancarlo; Lopez-Moreno, Jose; NOMAD Team

2017-10-01

We present preliminary data collected by the high-resolution NOMAD (Nadir and Occultation for MArs Discovery) instrument onboard the ExoMars / Trace Gas Orbiter (TGO) targeting several lines of water (H2O), deuterated water (HDO) and carbon dioxide (CO2). TGO is the first spacecraft on Mars specifically tailored to search for trace constituents, with the NOMAD instrument providing high spectral resolution (λ/dλ~ 20,000) over the 2-5 um spectral region. Such capabilities allow us to probe with unprecedented accuracy and sensitivity a multitude of organic species (e.g., CH4, CH3OH, H2CO, C2H6) and to map isotopic signatures (e.g., D/H, 13C/12C) across the whole planet.In particular, isotopic ratios are among the most valuable indicators for the loss of volatiles from an atmosphere. Because the escape rates for each isotope are slightly different (larger for the lighter forms), over long times the atmosphere becomes enriched in the heavy isotopic forms. By probing the current isotopic ratios, one can then infer the amount of matter lost to space over the planet’s evolution. Deuterium fractionation also reveals information about the cycle of water on the planet and informs us of its stability on short- and long-term scales, including its release from active regions on Mars having a characteristic D/H signature.Upon its successful launch in March/2016, we acquired critical calibration data in Apr/2016 and in June/2016, while during the Mars-Orbit-Capture phase, we also acquired Mars nadir data in Nov/2016 and in Feb-Mar/2017. Full science operations are expected to start upon final orbit insertion in early 2018. In this paper, we report initial retrievals of water and D/H derived during the Mars-Orbit-Capture phase and discuss the prospects for mapping of isotopic signatures during the nominal science phase.

Gas Production at Comet 67P/Churyumov-Gerasimenko as Measured by the ROSINA Instrument: Long Term Trends and Correlations with H2O and CO2

NASA Astrophysics Data System (ADS)

Hansen, K. C.; Altwegg, K.; Berthelier, J. J.; Combi, M. R.; De Keyser, J.; Fiethe, B.; Fougere, N.; Fuselier, S. A.; Gombosi, T. I.; Huang, Z.; Rubin, M.; Tenishev, V.; Toth, G.; Tzou, C. Y.

2017-12-01

The Rosetta Orbiter Spectrometer for Ion and Neutral Analysis (ROSINA) instrument onboard the Rosetta spacecraft measured the in situ gas density of comet 67P/Churyumov-Gerasimenko during the full perihelion passage of the comet within 3.5au. During this time, ROSINA sampled the neutral coma, measuring the broad range of cometary species including both the major constituents such as H2O, CO2, CO as well as many other species that are interesting to the general astrophysical community, such as O2, Xe, Si and even amino acids. Many of these species are hard to detect and therefore measurements are limited to when the spacecraft was close to the comet or the production rate was high. In contrast, in this work we will consider species that are most easily measured due to either their higher production rates or the ease with which their mass peaks are located (H2O, CO2, CO, O2, 18OH, HDO, OCS, SO2, H2S, CN, HCN, NH3, CH4, C2H2, C2H3, CH3OH and F). The advantage of examining these species is that we are able to present measurements over the entire perihelion passage at reasonably high time resolution. In this work we will present two important results. First, we will examine the long-term trend and heliocentric distance dependence of the production of these species over the entire perihelion passage of 67P. Second we will consider the correlation of the production of each species with the production of H2O and CO2. The study will consider both the long term correspondence between production of different species as well as the shorter term correlation.

SMA OBSERVATIONS OF THE W3(OH) COMPLEX: PHYSICAL AND CHEMICAL DIFFERENTIATION BETWEEN W3(H{sub 2}O) AND W3(OH)

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

Qin, Sheng-Li; Schilke, Peter; Sánchez-Monge, Álvaro

2015-04-10

We report on the Submillimeter Array (SMA) observations of molecular lines at 270 GHz toward the W3(OH) and W3(H{sub 2}O) complex. Although previous observations already resolved the W3(H{sub 2}O) into two or three sub-components, the physical and chemical properties of the two sources are not well constrained. Our SMA observations clearly resolved the W3(OH) and W3(H{sub 2}O) continuum cores. Taking advantage of the line fitting tool XCLASS, we identified and modeled a rich molecular spectrum in this complex, including multiple CH{sub 3}CN and CH{sub 3}OH transitions in both cores. HDO, C{sub 2}H{sub 5}CN, O{sup 13}CS, and vibrationally excited lines ofmore » HCN, CH{sub 3}CN, and CH{sub 3}OCHO were only detected in W3(H{sub 2}O). We calculate gas temperatures and column densities for both cores. The results show that W3(H{sub 2}O) has higher gas temperatures and larger column densities than W3(OH) as previously observed, suggesting physical and chemical differences between the two cores. We compare the molecular abundances in W3(H{sub 2}O) to those in the Sgr B2(N) hot core, the Orion KL hot core, and the Orion Compact Ridge, and discuss the chemical origin of specific species. An east–west velocity gradient is seen in W3(H{sub 2}O), and the extension is consistent with the bipolar outflow orientation traced by water masers and radio jets. A north–south velocity gradient across W3(OH) is also observed. However, with current observations we cannot be assured whether the velocity gradients are caused by rotation, outflow, or radial velocity differences of the sub-components of W3(OH)« less

Do birds of like feather flock together? The use of a novel 13C+D combustion isotope analyzer to track bird migration

NASA Astrophysics Data System (ADS)

Saad, N.

2011-12-01

Information on spring migration routes, geographic linkages among winter, spring, and breeding locations, and potential geographic effects on arrival body condition of a variety of avian species is so far little known. Stable isotope ratios are exquisitely sensitive to the biochemistry of living organisms and the nutrients available to them. Isotope ratios provide detailed knowledge useful in a variety of fields, including birds migration, through a combination of stable-isotope measurements of carbon (13C/12C) and hydrogen (D/H) isotopes of flight feathers and breast feathers of tissues representing different periods of dietary integration and body composition analyses. Associations among specific geographic areas, habitat use, and arrival condition can be elucidated through the measurement of these dual isotopes. We report here on the development of a novel laser spectroscopy based system for the simultaneous analysis of the stable isotope ratios of carbon (13C/12C) and hydrogen (D/H) that is robust, easy-to-use, and is the first stable isotope ratio analysis system to combine the measurement of 13C/12C and D/H in one simple analysis from a bulk organic sample with an application to bird migration. The system comprises a combustion module to convert the organic sample into CO2 and H2O and a Cavity Ring-Down Spectrometer (CRDS) that analyzes the combustion species inside an optical cavity based on the molecular absorption of individual isotopomers. This CRDS uses dual lasers to target the four isotpomers of interest: 12CO2, 13CO2, H2O and HDO. The system delivers a typical precision of 0.1 permil for δ13C and 1.5 permil for δD that parallels that achieved by IRMS, but with an unprecedented simplicity that allows ecologists to leverage the science and elucidate the avian migration patterns.

A decadal time series of water vapor and D / H isotope ratios above Zugspitze: transport patterns to central Europe

NASA Astrophysics Data System (ADS)

Hausmann, Petra; Sussmann, Ralf; Trickl, Thomas; Schneider, Matthias

2017-06-01

We present vertical soundings (2005-2015) of tropospheric water vapor (H2O) and its D / H isotope ratio (δD) derived from ground-based solar Fourier transform infrared (FTIR) measurements at Zugspitze (47° N, 11° E, 2964 m a.s.l.). Beside water vapor profiles with optimized vertical resolution (degrees of freedom for signal, DOFS, = 2.8), {H2O, δD} pairs with consistent vertical resolution (DOFS = 1.6 for H2O and δD) applied in this study. The integrated water vapor (IWV) trend of 2.4 [-5.8, 10.6] % decade-1 is statistically insignificant (95 % confidence interval). Under this caveat, the IWV trend estimate is conditionally consistent with the 2005-2015 temperature increase at Zugspitze (1.3 [0.5, 2.1] K decade-1), assuming constant relative humidity. Seasonal variations in free-tropospheric H2O and δD exhibit amplitudes of 140 and 50 % of the respective overall means. The minima (maxima) in January (July) are in agreement with changing sea surface temperature of the Atlantic Ocean. Using extensive backward-trajectory analysis, distinct moisture pathways are identified depending on observed δD levels: low column-based δD values (δDcol < 5th percentile) are associated with air masses originating at higher latitudes (62° N on average) and altitudes (6.5 km)than high δD values (δDcol > 95th percentile: 46° N, 4.6 km). Backward-trajectory classification indicates that {H2O, δD} observations are influenced by three long-range-transport patterns towards Zugspitze assessed in previous studies: (i) intercontinental transport from North America (TUS; source region: 25-45° N, 70-110° W, 0-2 km altitude), (ii) intercontinental transport from northern Africa (TNA; source region: 15-30° N, 15° W-35° E, 0-2 km altitude), and (iii) stratospheric air intrusions (STIs; source region: > 20° N, above zonal mean tropopause). The FTIR data exhibit significantly differing signatures in free-tropospheric {H2O, δD} pairs (5 km a.s.l.) - given as the mean with uncertainty of ±2 standard error (SE) - for TUS (VMRH2O = 2.4 [2.3, 2.6] × 103 ppmv, δD = -315 [-326, -303] ‰), TNA (2.8 [2.6, 2.9] × 103 ppmv, -251 [-257, -246] ‰), and STIs (1.2 [1.1, 1.3] × 103 ppmv, -384 [-397, -372] ‰). For TUS events, {H2O, δD} observations depend on surface temperature in the source region and the degree of dehydration having occurred during updraft in warm conveyor belts. During TNA events (dry convection of boundary layer air) relatively moist and weakly HDO-depleted air masses are imported. In contrast, STI events are associated with import of predominantly dry and HDO-depleted air masses. These long-range-transport patterns potentially involve the import of various trace constituents to the central European free troposphere, i.e., import of pollution from North America (e.g., aerosol, ozone, carbon monoxide), Saharan mineral dust, stratospheric ozone, and other airborne species such as pollen. Our results provide evidence that {H2O, δD} observations are a valuable proxy for the transport of such tracers. To validate this finding, we consult a database of transport events (TNA and STI) covering 2013-2015 deduced by data filtering from in situ measurements at Zugspitze and lidar profiles at nearby Garmisch. Indeed, the FTIR data related to these verified TNA events (27 days) exhibit characteristic fingerprints in IWV (5.5 [4.9, 6.1] mm) and δDcol (-266 [-284, -247] ‰), which are significantly distinguishable from the rest of the time series (4.3 [4.1, 4.5] mm, -316 [-324, -308] ‰). This holds true for 136 STI days considering uncertainties of ±1 SE (4.2 [4.0, 4.3] mm, -322 [-327, -316] ‰) with respect to the remainder (4.6 [4.5, 4.8] mm, -302 [-307, -297] ‰). Furthermore, deep stratospheric intrusions to the Zugspitze summit (in situ humidity and beryllium-7 data filtering) show a significantly lower mean value (-334 [-337, -330] ‰) of lower-tropospheric δD (3-5 km a.s.l.) than the rest of the 2005-2015 time series (-284 [-286, -282] ‰) considering uncertainty of ±2 SE. Our results show that consistent {H2O, δD} observations at Zugspitze can serve as an operational indicator for long-range-transport events potentially affecting regional climate and air quality, as well as human health in central Europe.

Cross-validation of IASI/MetOp derived tropospheric δD with TES and ground-based FTIR observations

NASA Astrophysics Data System (ADS)

Lacour, J.-L.; Clarisse, L.; Worden, J.; Schneider, M.; Barthlott, S.; Hase, F.; Risi, C.; Clerbaux, C.; Hurtmans, D.; Coheur, P.-F.

2015-03-01

The Infrared Atmospheric Sounding Interferometer (IASI) flying onboard MetOpA and MetOpB is able to capture fine isotopic variations of the HDO to H2O ratio (δD) in the troposphere. Such observations at the high spatio-temporal resolution of the sounder are of great interest to improve our understanding of the mechanisms controlling humidity in the troposphere. In this study we aim to empirically assess the validity of our error estimation previously evaluated theoretically. To achieve this, we compare IASI δD retrieved profiles with other available profiles of δD, from the TES infrared sounder onboard AURA and from three ground-based FTIR stations produced within the MUSICA project: the NDACC (Network for the Detection of Atmospheric Composition Change) sites Kiruna and Izaña, and the TCCON site Karlsruhe, which in addition to near-infrared TCCON spectra also records mid-infrared spectra. We describe the achievable level of agreement between the different retrievals and show that these theoretical errors are in good agreement with empirical differences. The comparisons are made at different locations from tropical to Arctic latitudes, above sea and above land. Generally IASI and TES are similarly sensitive to δD in the free troposphere which allows one to compare their measurements directly. At tropical latitudes where IASI's sensitivity is lower than that of TES, we show that the agreement improves when taking into account the sensitivity of IASI in the TES retrieval. For the comparison IASI-FTIR only direct comparisons are performed because the sensitivity profiles of the two observing systems do not allow to take into account their differences of sensitivity. We identify a quasi negligible bias in the free troposphere (-3‰) between IASI retrieved δD with the TES, which are bias corrected, but important with the ground-based FTIR reaching -47‰. We also suggest that model-satellite observation comparisons could be optimized with IASI thanks to its high spatial and temporal sampling.

Transition Metal Phosphide Nanoparticles Supported on SBA-15 as Highly Selective Hydrodeoxygenation Catalysts for the Production of Advanced Biofuels.

PubMed

Yang, Yongxing; Ochoa-Hernández, Cristina; de la Peña O'Shea, Víctor A; Pizarro, Patricia; Coronado, Juan M; Serrano, David P

2015-09-01

A series of catalysts constituted by nanoparticles of transition metal (M = Fe, Co, Ni and Mo) phosphides (TMP) dispersed on SBA-15 were synthesized by reduction of the corresponding metal phosphate precursors previously impregnated on the mesostructured support. All the samples contained a metal-loading of 20 wt% and with an initial M/P mole ratio of 1, and they were characterized by X-ray diffraction (XRD), N2 sorption, H2-TPR and transmission electron microscopy (TEM). Metal phosphide nanocatalysts were tested in a high pressure continuous flow reactor for the hydrodeoxygenation (HDO) of a methyl ester blend containing methyl oleate (C17H33-COO-CH3) as main component (70%). This mixture constitutes a convenient surrogate of triglycerides present in vegetable oils, and following catalytic hydrotreating yields mainly n-alkanes. The results of the catalytic assays indicate that Ni2P/SBA-15 catalyst presents the highest ester conversion, whereas the transformation rate is about 20% lower for MoP/SBA-15. In contrast, catalysts based on Fe and Co phosphides show a rather limited activity. Hydrocarbon distribution in the liquid product suggests that both hydrodeoxygenation and decarboxylation/decarbonylation reactions occur simultaneously over the different catalysts, although MoP/SBA-15 possess a selectivity towards hydrodeoxygenation exceeding 90%. Accordingly, the catalyst based on MoP affords the highest yield of n-octadecane, which is the preferred product in terms of carbon atom economy. Subsequently, in order to conjugate the advantages of both Ni and Mo phosphides, a series of catalysts containing variable proportions of both metals were prepared. The obtained results reveal that the mixed phosphides catalysts present a catalytic behavior intermediate between those of the monometallic phosphides. Accordingly, only marginal enhancement of the yield of n-octadecane is obtained for the catalysts with a Mo/Ni ratio of 3. Nevertheless, owing to this high selectivity for hydrodeoxygenation MoP/SBA-15 appears as a very promising catalyst for the production of advanced biofuels.

Long open-path measurements of greenhouse gases in air using near-infrared Fourier transform spectroscopy

NASA Astrophysics Data System (ADS)

Griffith, David W. T.; Pöhler, Denis; Schmitt, Stefan; Hammer, Samuel; Vardag, Sanam N.; Platt, Ulrich

2018-03-01

In complex and urban environments, atmospheric trace gas composition is highly variable in time and space. Point measurement techniques for trace gases with in situ instruments are well established and accurate, but do not provide spatial averaging to compare against developing high-resolution atmospheric models of composition and meteorology with resolutions of the order of a kilometre. Open-path measurement techniques provide path average concentrations and spatial averaging which, if sufficiently accurate, may be better suited to assessment and interpretation with such models. Open-path Fourier transform spectroscopy (FTS) in the mid-infrared region, and differential optical absorption spectroscopy (DOAS) in the UV and visible, have been used for many years for open-path spectroscopic measurements of selected species in both clean air and in polluted environments. Near infrared instrumentation allows measurements over longer paths than mid-infrared FTS for species such as greenhouse gases which are not easily accessible to DOAS.In this pilot study we present the first open-path near-infrared (4000-10 000 cm-1, 1.0-2.5 µm) FTS measurements of CO2, CH4, O2, H2O and HDO over a 1.5 km path in urban Heidelberg, Germany. We describe the construction of the open-path FTS system, the analysis of the collected spectra, several measures of precision and accuracy of the measurements, and the results a four-month trial measurement period in July-November 2014. The open-path measurements are compared to calibrated in situ measurements made at one end of the open path. We observe significant differences of the order of a few ppm for CO2 and a few tens of ppb for CH4 between the open-path and point measurements which are 2 to 4 times the measurement repeatability, but we cannot unequivocally assign the differences to specific local sources or sinks. We conclude that open-path FTS may provide a valuable new tool for investigations of atmospheric trace gas composition in complex, small-scale environments such as cities.

Vibrational spectra of Mg2KH(XO4)2·15H2O (X = P, As) containing dimer units [H(XO4)2

NASA Astrophysics Data System (ADS)

Stefov, V.; Koleva, V.; Najdoski, M.; Abdija, Z.; Cahil, A.; Šoptrajanov, B.

2017-08-01

Infrared and Raman spectra of Mg2KH(PO4)2·15H2O and Mg2KH(AsO4)2·15H2O and a series of their partially deuterated analogues were recorded and analyzed. Compounds of the type Mg2KH(XO4)2·15H2O (X = P, As) are little-known and a rare case of phosphate and arsenate salts containing dimer units [H(XO4)2] in the crystal structure. The analysis of their IR spectra (recorded at room and liquid nitrogen temperature) and Raman spectra showed that the spectral characteristics of the XO4 groups connected in a dimer through a proton are not consistent with the presence of X-O-H covalent linkage and C1 crystallographic symmetry of the XO4 groups. The observation of a singlet Raman band for the ν1(XO4) mode as well as the absence of substantial splitting of the ν3(XO4) modes and IR activation of the ν1(XO4) mode suggest that the dimer units [H(XO4)2] are most probably symmetric rather than non-symmetric ones. It was found that, in the vibrational spectra of Mg2KH(AsO4)2·15H2O, both ν1(AsО4) and ν3(AsО4) modes have practically the same wavenumber around 830 cm- 1. It was also established that the ν4(PО4) modes in the deuterated hydrogendiphosphate compound are strongly coupled, most probably with HDO and/or D2O librations. As a whole, the spectral picture of Mg2KH(XO4)2·15H2O (X = P, As) very much resembles that observed for the struvite type compounds with the formula KMgXO4·6H2O (X = P, As) which do not contain X-OH groups. This means that vibrations of the dimers [H(XO4)2] play a relatively small part in the general spectral appearance.

The interaction of molecular hydrogen with α-radiolytic oxidants on a (U,Pu)O2 surface

NASA Astrophysics Data System (ADS)

Bauhn, Lovisa; Hansson, Niklas; Ekberg, Christian; Fors, Patrik; Delville, Rémi; Spahiu, Kastriot

2018-07-01

In order to assess the impact of α-radiolysis of water on the oxidative dissolution of spent fuel, an un-irradiated, annealed MOX fuel pellet with high content of Pu (∼24 wt%), and a specific α-activity of 4.96 GBq/gMOX, was leached in carbonate-containing solutions of low ionic strength. The high Pu content in the pellet stabilizes the (U,Pu)O2(s) matrix towards oxidative dissolution, whereas the α-decays emitted from the surface are expected to produce ∼3.6 × 10-7 mol H2O2/day, contributing to the oxidative dissolution of the pellet. Two sets of leaching tests were conducted under different redox conditions: Ar gas atmosphere and deuterium gas atmosphere. A relatively slow increase of the U and Pu concentrations was observed in the Ar case, with U concentrations increasing from 1·10-6 M after 1 h to ∼7 × 10-5 M after 58 days. Leaching under an atmosphere starting at 1 MPa deuterium gas was undertaken in order to evaluate any effect of dissolved hydrogen on the radiolytic dissolution of the pellet, as well as to investigate any potential recombination of the α-radiolytic products with dissolved deuterium. For the latter purpose, isotopic analysis of the D/H content was carried out on solution samples taken during the leaching. Despite the continuous production of radiolytic oxidants, the concentrations of U and Pu remained quite constant at the level of ∼3 × 10-8 M during the first 30 days, i.e. as long as the deuterium pressure remained higher than 0.8 MPa. These data rule out any oxidative dissolution of the pellet during the first month. The un-irradiated MOX fuel does not contain metallic ε-particles, hence it is mainly the interaction of radiolytic oxidants and dissolved deuterium with the surface of the mixed actinide oxide that causes the neutralization of the oxidants. This conclusion is supported by the steadily increasing levels of HDO measured in the leachate samples.

Intercomparison of open-path trace gas measurements with two dual-frequency-comb spectrometers

DOE PAGES

Waxman, Eleanor M.; Cossel, Kevin C.; Truong, Gar-Wing; ...

2017-09-11

We present the first quantitative intercomparison between two open-path dual-comb spectroscopy (DCS) instruments which were operated across adjacent 2 km open-air paths over a 2-week period. We used DCS to measure the atmospheric absorption spectrum in the near infrared from 6023 to 6376 cm −1 (1568 to 1660 nm), corresponding to a 355 cm −1 bandwidth, at 0.0067 cm −1 sample spacing. The measured absorption spectra agree with each other to within 5 × 10 −4 in absorbance without any external calibration of either instrument. The absorption spectra are fit to retrieve path-integrated concentrations for carbon dioxide (CO 2), methane (CH 4), water (H 2O), and deuteratedmore » water (HDO). The retrieved dry mole fractions agree to 0.14 % (0.57 ppm) for CO 2, 0.35 % (7 ppb) for CH 4, and 0.40 % (36 ppm) for H 2O at  ∼  30 s integration time over the 2-week measurement campaign, which included 24 °C outdoor temperature variations and periods of strong atmospheric turbulence. This agreement is at least an order of magnitude better than conventional active-source open-path instrument intercomparisons and is particularly relevant to future regional flux measurements as it allows accurate comparisons of open-path DCS data across locations and time. We additionally compare the open-path DCS retrievals to a World Meteorological Organization (WMO)-calibrated cavity ring-down point sensor located along the path with good agreement. Short-term and long-term differences between the open-path DCS and point sensor are attributed, respectively, to spatial sampling discrepancies and to inaccuracies in the current spectral database used to fit the DCS data. Finally, the 2-week measurement campaign yields diurnal cycles of CO 2 and CH 4 that are consistent with the presence of local sources of CO 2 and absence of local sources of CH 4.« less

Vibrational spectra of Mg2KH(XO4)2·15H2O (X=P, As) containing dimer units [H(XO4)2].

PubMed

Stefov, V; Koleva, V; Najdoski, M; Abdija, Z; Cahil, A; Šoptrajanov, B

2017-08-05

Infrared and Raman spectra of Mg 2 KH(PO 4 ) 2 ·15H 2 O and Mg 2 KH(AsO 4 ) 2 ·15H 2 O and a series of their partially deuterated analogues were recorded and analyzed. Compounds of the type Mg 2 KH(XO 4 ) 2 ·15H 2 O (X=P, As) are little-known and a rare case of phosphate and arsenate salts containing dimer units [H(XO 4 ) 2 ] in the crystal structure. The analysis of their IR spectra (recorded at room and liquid nitrogen temperature) and Raman spectra showed that the spectral characteristics of the XO 4 groups connected in a dimer through a proton are not consistent with the presence of X-O-H covalent linkage and C 1 crystallographic symmetry of the XO 4 groups. The observation of a singlet Raman band for the ν 1 (XO 4 ) mode as well as the absence of substantial splitting of the ν 3 (XO 4 ) modes and IR activation of the ν 1 (XO 4 ) mode suggest that the dimer units [H(XO 4 ) 2 ] are most probably symmetric rather than non-symmetric ones. It was found that, in the vibrational spectra of Mg 2 KH(AsO 4 ) 2 ·15H 2 O, both ν 1 (AsО 4 ) and ν 3 (AsО 4 ) modes have practically the same wavenumber around 830cm -1 . It was also established that the ν 4 (PО 4 ) modes in the deuterated hydrogendiphosphate compound are strongly coupled, most probably with HDO and/or D 2 O librations. As a whole, the spectral picture of Mg 2 KH(XO 4 ) 2 ·15H 2 O (X=P, As) very much resembles that observed for the struvite type compounds with the formula KMgXO 4 ·6H 2 O (X=P, As) which do not contain X-OH groups. This means that vibrations of the dimers [H(XO 4 ) 2 ] play a relatively small part in the general spectral appearance. Copyright © 2017 Elsevier B.V. All rights reserved.

Ice Mapping Observations in Galactic Star-Forming Regions: the AKARI Legacy

NASA Astrophysics Data System (ADS)

Fraser, Helen Jane; Suutarinnen, Aleksi; Noble, Jennifer

2015-08-01

It is becoming increasingly clear that explaining the small-scale distribution of many gas-phase molecules relies on our interpretation of the complex inter-connectivity between gas- and solid-phase interstellar chemistries. Inputs to proto-stellar astrochemical models are required that exploit ice compositions reflecting the historical physical conditions in pre-stellar environments when the ices first formed. Such data are required to translate the near-universe picture of ice-composition to our understanding of the role of extra-galactic ices in star-formation at higher redshifts.Here we present the first attempts at multi-object ice detections, and the subsequent ice column density mapping. The AKARI space telescope was uniquely capable of observing all the ice features between 2 and 5 microns, thereby detecting H2O, CO and CO2 ices concurrently, through their stretching vibrational features. Our group has successfully extracted an unprecedented volume of ice spectra from AKARI, including sources with not more than 2 mJy flux at 3 microns, showing:(a) H2O CO and CO2 ices on 30 lines of sight towards pre-stellar and star-forming cores, which when combined with laboratory experiments indicate how the chemistries of these three ices are interlinked (Noble et al (2013)),(b) ice maps showing the spatial distribution of water ice across 12 pre-stellar cores, in different molecular clouds (Suutarinnen et al (2015)), and the distribution of ice components within these cores on 1000 AU scales (Noble et al (2015)),(c) over 200 new detections of water ice, mostly on lines of sight towards background sources (> 145), indicating that water ice column density has a minimum value as a function of Av, but on a cloud-by-cloud basis typically correlates with Av, and dust emissivity at 250 microns (Suutarinnen et al (2015)),(d) the first detections of HDO ice towards background stars (Fraser et al (2015)).We discuss whether these results support the picture of a generic chemical evolutionary scenario for interstellar ice chemistry, ranging from pre-stellar to extra-galactic scales.

A Portable FTIR Analyser for Field Measurements of Trace Gases and their Isotopologues: CO2, CH4, N2O, CO, del13C in CO2 and delD in water vapour

NASA Astrophysics Data System (ADS)

Griffith, D. W.; Bryant, G. R.; Deutscher, N. M.; Wilson, S. R.; Kettlewell, G.; Riggenbach, M.

2007-12-01

We describe a portable Fourier Transform InfraRed (FTIR) analyser capable of simultaneous high precision analysis of CO2, CH4, N2O and CO in air, as well as δ13C in CO2 and δD in water vapour. The instrument is based on a commercial 1 cm-1 resolution FTIR spectrometer fitted with a mid-IR globar source, 26 m multipass White cell and thermoelectrically-cooled MCT detector operating between 2000 and 7500 cm-1. Air is passed through the cell and analysed in real time without any pre-treatment except for (optional) drying. An inlet selection manifold allows automated sequential analysis of samples from one or more inlet lines, with typical measurement times of 1-10 minutes per sample. The spectrometer, inlet sampling sequence, real-time quantitative spectrum analysis, data logging and display are all under the control of a single program running on a laptop PC, and can be left unattended for continuous measurements over periods of weeks to months. Selected spectral regions of typically 100-200 cm-1 width are analysed by a least squares fitting technique to retrieve concentrations of trace gases, 13CO2 and HDO. Typical precision is better than 0.1% without the need for calibration gases. Accuracy is similar if measurements are referenced to calibration standard gases. δ13C precision is typically around 0.1‰, and for δD it is 1‰. Applications of the analyser include clean and polluted air monitoring, tower-based flux measurements such as flux gradient or integrated horizontal flux measurements, automated soil chambers, and field-based measurements of isotopic fractionation in soil-plant-atmosphere systems. The simultaneous multi-component advantages can be exploited in tracer-type emission measurements, for example of CH4 from livestock using a co-released tracer gas and downwind measurement. We have also developed an open path variant especially suited to tracer release studies and measurements of NH3 emissions from agricultural sources. An illustrative selection of applications will be presented.

Orbital Observatory for Planetary Science on Low Cost Autonomous Platform

NASA Astrophysics Data System (ADS)

Tavrov, Alexander; Bisikalo, Dmitry; Vedenkin, Nikolay; Korablev, Oleg; Markov, Alexander; Kiselev, Alexander; Kokorich, Mikhail

The Space Research Institute of Russian Academy of Science (IKI RAS) and Dauria Aerospace are currently developing the middle class space telescope project aiming to observe Solar system planets by a long term spectroscopy and polarimetry monitoring, as well aiming to extra solar planets (exoplanets) engineering and scientific goals. The spacecraft is scheduled to be launched in 2017. It is planned first to be delivered on board of the ISS by the Progress spacecraft, then it will be released to the desired orbit approx. 550 km by the Progress in the way to its final destination. The “Planetary monitoring” telescope has a 0.6 meter primary mirror diameter Telescope currently includes 5 science instruments: NIR: 1000..4000 nm high-resolution spectrometer with the spectral resolution of R>10000; Visible Field camera with filters wheel; UV-VIS field resolved Fourier spectrometer; UV-VIS spectropolarimeter; Stellar coronagraph linked with a low-resolution spectrometer. The scientific goals of the “Planetary monitoring” telescope are devoted to explore not yet well studied questions on Mars (methane, ozone, dust and clouds, isotope ratio of HDO/H2O), on Venus (UV absorber, night glow, atmosphere dynamics), icy and gaseous Solar system planets, Jovian moons, Lunar exosphere, comets, meteorites. This telescope aims also for engineering development of exoplanet study by stellar coronagraphy linked with a low-resolution spectrometry. This Orbital Observatory mission uses the first low cost small satellite platform developed by the Dauria Aerospace® - Russian private company and reuses the Progress to elevate the observatory orbit. The Progress launches four times per year to provide supplies and scientific instruments to the ISS. The Progress is capable of raising the height of the orbit for the piggyback scientific missions; therefore, the implementation of the Orbital Observatory mission is considered not just as a development of a successful science mission so it is most importantly developing an affordable and frequent flight opportunities for space sciences research in Russia and worldwide. The paper describes the scientific objectives and corresponding instruments, and introduces the low cost satellite platform and launch opportunities.

Intercomparison of open-path trace gas measurements with two dual-frequency-comb spectrometers

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

Waxman, Eleanor M.; Cossel, Kevin C.; Truong, Gar-Wing

We present the first quantitative intercomparison between two open-path dual-comb spectroscopy (DCS) instruments which were operated across adjacent 2 km open-air paths over a 2-week period. We used DCS to measure the atmospheric absorption spectrum in the near infrared from 6023 to 6376 cm −1 (1568 to 1660 nm), corresponding to a 355 cm −1 bandwidth, at 0.0067 cm −1 sample spacing. The measured absorption spectra agree with each other to within 5 × 10 −4 in absorbance without any external calibration of either instrument. The absorption spectra are fit to retrieve path-integrated concentrations for carbon dioxide (CO 2), methane (CH 4), water (H 2O), and deuteratedmore » water (HDO). The retrieved dry mole fractions agree to 0.14 % (0.57 ppm) for CO 2, 0.35 % (7 ppb) for CH 4, and 0.40 % (36 ppm) for H 2O at  ∼  30 s integration time over the 2-week measurement campaign, which included 24 °C outdoor temperature variations and periods of strong atmospheric turbulence. This agreement is at least an order of magnitude better than conventional active-source open-path instrument intercomparisons and is particularly relevant to future regional flux measurements as it allows accurate comparisons of open-path DCS data across locations and time. We additionally compare the open-path DCS retrievals to a World Meteorological Organization (WMO)-calibrated cavity ring-down point sensor located along the path with good agreement. Short-term and long-term differences between the open-path DCS and point sensor are attributed, respectively, to spatial sampling discrepancies and to inaccuracies in the current spectral database used to fit the DCS data. Finally, the 2-week measurement campaign yields diurnal cycles of CO 2 and CH 4 that are consistent with the presence of local sources of CO 2 and absence of local sources of CH 4.« less

Detecting Isotopic Signatures and Measuring Isotopic Ratios on Solid Icy Surfaces:Implications for Origin and Evolution

NASA Astrophysics Data System (ADS)

Clark, R. N.; Brown, R. H.; Swayze, G. A.; Cruikshank, D. P.

2017-12-01

Infrared spectroscopy has long been used to detect isotopes in planetaryatmospheres and in the galaxy. Given sufficient spectral resolution,or large enough changes in mass, isotopes are also detectable in solids.Gas absorption lines can be quite narrow, but in some solids, e.g. H2Oice, absorptions are very broad with little to no fine structure. H2O icehas broad absorptions due to its orientationally disordered structure butmany ices, minerals, and other compounds display sufficiently narrowabsorptions to enable detection of isotopes with small mass changes atmoderate spectral resolution.D2O ice and HDO ice also show orientationally-disordered spectra withvery broad absorption bands. But as deuterium decreases to low levelsdeuterium apparently goes into ordered sites in the H2O ice structure,producing narrow absorptions and shifting to longer wavelengths.Trace D2O condensed on basalt at 80 Kelvin shows an O-D stretch at 4.0microns, but at D/H 0.1 or less in H2O ice, the D-O stretch occursnear 4.13 microns with a width in reflectance decreasing to 0.027 micronas D/H decreases. The narrow D-O stretch absorption shows an absorptioncoefficient of 80,000 cm^-1 enabling detection below Vienna Standard MeanOcean Water (VSMOW) with achievable S/N in the lab and from spacecraft.Isotopes of carbon have been detected in CO2 on Saturn's satelliteswith 16 nm FWHM using the VIMS instrument on the Cassini spacecraft.Deuterium has been detected at close to terrestrial levels in Saturn'srings and on Rhea, and an apparent enhancement on Phoebe using VIMSdata. The ocean world Enceladus is currently being analyzed. We alsodetect an enhancement in 13C on Phoebe, but not on Iapetus or Rhea,consistent with the suggestion from previous studies that suggest Phoebe'sorigin might be external to the Saturn system. The MISE instrumenton the Europa Clipper mission has the capability to detect deuteriumand carbon isotopes in the Jupiter system. The higher temperaturesin the Jupiter system may result in more fractionation, depending upona given isotope and the physical processes involved, potentially withimplications for origin and evolution.

Greenhouse Observations of the Stratosphere and Troposphere (GHOST): a novel shortwave infrared spectrometer developed for the Global Hawk unmanned aerial vehicle

NASA Astrophysics Data System (ADS)

Humpage, Neil; Boesch, Hartmut; Palmer, Paul; Parr-Burman, Phil; Vick, Andy; Bezawada, Naidu; Black, Martin; Born, Andy; Pearson, David; Strachan, Jonathan; Wells, Martyn

2014-05-01

The tropospheric distribution of greenhouse gases (GHGs) is dependent on surface flux variations, atmospheric chemistry and transport processes over a wide range of spatial and temporal scales. Errors in assumed atmospheric transport can adversely affect surface flux estimates inferred from surface, aircraft or satellite observations of greenhouse gas concentrations using inverse models. We present a novel, compact shortwave infrared spectrometer (GHOST) for installation on the NASA Global Hawk unmanned aerial vehicle to provide tropospheric column observations of CO2, CO, CH4, H2O and HDO over the ocean to address the need for large-scale, simultaneous, finely resolved measurements of key GHGs. These species cover a range of lifetimes and source processes, and measurements of their tropospheric columns will reflect the vertically integrated signal of their vertical and horizontal transport within the troposphere. The primary science objectives of GHOST are to: 1) provide observations which can be used to test atmospheric transport models; 2) validate satellite observations of GHG column observations over oceans, thus filling a critical gap in current validation capabilities; and 3) complement in-situ tropopause transition layer tracer observations from other instrumentation on board the Global Hawk to provide a link between upper and lower troposphere concentration measurements. The GHOST spectrometer system comprises a target acquisition module (TAM), a fibre slicer and feed system, and a multiple order spectrograph. The TAM design utilises a gimbal behind an optical dome, which is programmed to direct solar radiation reflected by the ocean surface into a fibre optic bundle. The fibre slicer and feed system then splits the light into the four spectral bands using order sorting filters. The fibres corresponding to each band are arranged with a small sideways offset to correctly centre each spectrum on the detector array. The spectrograph design is unique in that a single grating and detector is used for all four spectral bands. The whole instrument is housed within a liquid nitrogen cooled cryostat to ensure thermal stability. We summarise the GHOST project and its objectives, and will provide a detailed overview of the instrument concept, development, and proposed deployment on board the Global Hawk.

Studying the Mars atmosphere using a SOIR Instrument

NASA Astrophysics Data System (ADS)

Drummond, R.; Vandaele, A.; Daerden, F.; Neefs, E.; Mahieux, A.; Wilquet, V.; Montmessin, F.; Bertaux, J.; McConnell, J. C.; Kaminski, J. W.

2009-05-01

SOIR (Solar Occultation InfraRed spectrometer) is currently part of the SPICAV/SOIR instrument on board the Venus Express orbiter (VEX). SOIR, an Echelle infrared spectrometer using an acousto-optic tunable filter (AOTF) for the order selection, is probing the atmosphere by solar occultation, operating between 2.2 and 4.3 μm, with a resolution of 0.15 cm-1. This spectral range is suitable for the detection of several key components of planetary atmospheres, including H2O and its isotopologue HDO, CH4 and other trace species. The SOIR instrument was designed to have a minimum of moving parts, to be light and compact in order to fit on top of the SPICAV instrument. The AOTF allows a narrow range of wavelengths to pass, according to the radio frequency applied to the TeO2 crystal; this selects the order. The advantage of the AOTF is that different orders can be observed quickly and easily during one occultation. To obtain a compact optical scheme, a Littrow configuration was implemented in which the usual collimating and imaging lenses are merged into a single off-axis parabolic mirror. The light is diffracted on the echelle grating, where orders overlap and addition occurs, and finally is recorded by the detector. The detector is 320x256 pixels and is cooled to 88K during an occultation measurement, to maximise the signal to noise ratio. SOIR on VEX has been in orbit around Venus since April 2006, allowing us to characterise the instrument and study its performance. These data have allowed the engineering team to devise several instrumental improvements. The next step in further improving the readiness for Martian atmospheric studies comes in close collaboration with the Mars Atmospheric Modelling group at BIRA-IASB. A General Circulation Model is used to simulate the Martian atmosphere. Currently work is underway with SPICAM data to verify the GCM inputs and outputs. Later the GCM output will be used as feedback for instrumental design of both an improved version of SOIR and the UVIS instrument for the ExoMars mission. We will show Mars data as could be observed by a SOIR instrument to demonstrate what SOIR would be capable of in Mars orbit.

Expanding the scope and applicability of laser-based spectroscopy to studies of ecohydrology by removing organic contaminants in natural water

NASA Astrophysics Data System (ADS)

Dennis, K. J.; Rees-Owen, R. L.; Brooks, P. D.; Carter, J.; Dawson, T. E.

2014-12-01

The ability to measure the stable isotopic composition of plant and soil waters, surface waters and ambient atmospheric vapor is essential to understanding an ecosystem's water budget, including how water cycles between the air, plants and the subsurface. With the advent of laser-based spectroscopy, e.g., Cavity Ring-Down Spectroscopy (CRDS), the isotopic analysis of waters has become increasingly cost-effective and prevalent, with comparable precision to conventional isotope ratio mass spectrometry methods. However, early work [1,2] demonstrated that the accuracy of isotopic analysis by laser-absorption techniques could be compromised by the spectral interference from organic compounds, in particular methanol and ethanol [1], which are prevalent in ecologically-derived waters. Here we present results from the Picarro Micro-Combustion Module (MCM), which acts to destructively remove these interfering organic species from the analyzed water vapor stream by oxidizing them to CO2 and H2O. Analyzed samples include simulated plant water solutions, waters doped with varying concentrations of potentially problematic organic compounds, and actual plant water extracts. We find that the median offset between IRMS and a Picarro L2130-i outfitted with a MCM is less than 0.5 ‰ for δ18O and less than 1 ‰ for δD. In parallel to the destruction of organic contaminants, a software tool can also be used to assess the probability of spectral interference. This software performs a statistical analysis of spectral fit parameters, e.g., the shift in the spectral baseline, and compares unknown samples to clean standard waters. In general, the most common primary metabolites present in plant materials include the light organic acids, e.g., benzoic and formic acid. At low concentrations (0.1 and 1%) formic acid does not appear to interfere with the resolved absorption spectra for H2O, HDO and H218O. Similar tests will be conducted for benzoic acid. Conversely, although methanol and ethanol are only present in trace amounts in plants, these alcohols can cause large interferences even at the low concentrations (1% and 0.025% for ethanol and methanol, respectively). Using these results, we will propose when CRDS for ecologically-derived waters functions best. [1] Brand et al. (2009), RCM, 23 [2] West et al. (2010), RCM, 24

Origins Space Telescope: HEterodyne Receiver for OST (HERO)

NASA Astrophysics Data System (ADS)

Bergin, Edwin; Wiedner, Martina; Laurens, Andre; Gerin, Maryvonne; HERO team, Origins Space Telescope Science and Technology Definition Team

2018-01-01

The Origins Space Telescope (OST) is a mission concept for the Far-Infrared Surveyor, one of the four science and technology definition studies selected by NASA HQ for the 2020 Astronomy and Astrophysics Decadal survey. The OST study will encompass two mission concepts (poster by A. Cooray). Concept 1 is an extremely versatile observatory with 5 science instruments, of which the HEterodyne Receivers for OST (HERO) is one.HERO’s main targets are high spectral resolution observations (Dl/l up to 107 or Dv = 0.03km/s) of water to follow its trail from cores to YSOs as well as H2O and HDO observations on comets to explore the origins of water. HERO will probe all neutral ISM phases using cooling lines ([CII], [OI]) and hydrides as probes of CO-dark H2 (CH, HF). HERO will reveal how molecular clouds and filaments form in the local ISM up to nearby galaxies. HERO will enable detailed understanding of feedback mechanisms : shocks, cosmic rays, UV induced feedback and will provide a map of the cosmic ray ionization rate in the Galaxy and nearby galaxies using molecular ions (ArH+, OH+, H3O+).In order to achieve these observational goals, HERO will cover an extremely wide frequency range from 468 to 2700 GHz (641 to 111microns) and a window around the OI line at 4563 to 4752GHz (66 to 63 microns). It will consist of very large focal plane arrays of 128 pixels between 900 - 2700 GHz and at 4.7 THz, and 32 pixels for the 468 to 900 GHz range. The instrument is exploiting Herschel/HIFI heritage, but will go well beyond HIFIs capacities. HERO’s large arrays require low dissipation and low power components. The HERO concept makes use of the latest cryogenic SiGe amplifier technology, as well as CMOS technology for the backends with 2 orders of magnitude lower power. Advances in Local Oscillator technology have also been taken into account and ambitious, but realistic assumptions have been made for future amplifier multiplier chains going up to 4.7 THz.Origins will enable flagship-quality general observing programs led by the astronomical community in the 2030s. We welcome you to contact the Science and Technology Definition Team (STDT) with your science needs and ideas by emailing us at ost_info@lists.ipac.caltech.edu

Aluminum and Other Coatings for the Passivation of Tritium Storage Vessels

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

Spencer, W.; Korinko, P.

Using a highly sensitive residual gas analyzer, the off-gassing of hydrogen, water, and hydrocarbons from surface-treated storage vessels containing deuterium was measured. The experimental storage vessels were compared to a low-off-gassing, electro-polished 304L canister. Alternative vessels were made out of aluminum, or were coatings on 304L steel. Coatings included powder pack aluminide, electro-plated aluminum, powder pack chromide, dense electro-plated chromium, copper plated, and copper plated with 25 and 50 percent nano-diamond. Vessels were loaded with low pressure deuterium to observe exchange with protium or hydrogen as observed with formation of HD and HDO. Off gas of D 2O or possiblemore » CD 4 was observed at mass 20. The main off-gas in all of the studies was H 2. The studies indicated that coatings required significant post-coating treatment to reduce off-gas and enhance the permeation barrier from gases likely added during the coating process. Dense packed aluminum coatings needed heating to drive off water. Electro-plated aluminum, chromium and copper coatings appeared to trap hydrogen from the plating process. Nano-diamond appeared to enhance the exchange rate with hydrogen off gas, and its coating process trapped significant amounts of hydrogen. Aluminum caused more protium exchange than chromium-treated surfaces. Aluminum coatings released more water, but pure aluminum vessels released small amounts of hydrogen, little water, and generally performed well. Chromium coating had residual hydrogen that was difficult to totally outgas but otherwise gave low residuals for water and hydrocarbons. Our studies indicated that simple coating of as received 304L metal will not adequately block hydrogen. The base vessel needs to be carefully out-gassed before applying a coating, and the coating process will likely add additional hydrogen that must be removed. Initial simple bake-out and leak checks up to 350° C for a few hours was found to be inadequate. All of the studies indicated that vessels needed several days of vacuum baking at 350-450° C to fully outgas the residual gases, which were mostly hydrogen. The current standard practice of out-gassing from ultra-clean, electro-polished 304L vessels with both vacuum bake-out and followed by an oxidative bake out to enhance the chromium surface performed the best in these studies.« less

The dependence of entrainment and drizzle in marine stratiform clouds on biomass burning aerosols derived from stable isotope and thermodynamic profiles

NASA Astrophysics Data System (ADS)

Henze, D.; Noone, D.

2017-12-01

A third of the world's biomass burning aerosol (BBA) particles are generated in southern Africa, and these particles are swept into the midlevel troposphere over the southeast Atlantic Ocean. The presence of these aerosols over the marine environment of the south east Atlantic offers a unique natural laboratory for studying aerosol effects on climate, and specifically a modification to the hydrologic cycle and microphysical characteristics of clouds. Different rates of condensation with high aerosol numbers change the precipitation rates in drizzling stratiform clouds, while the mixing of aerosols into the cloud layer is synonymous with entrainment from above cloud top near the top of the subtropical inversion. To better understanding the magnitude of the aerosol influence on southeast Atlantic boundary layer clouds we analyze the cloud-top entrainment and drizzle as a function of aerosol loading to determine the impact of BBA. Entrainment was determined from mixing line analysis based on profile measurements of moist static energy, total water, and the two most common heavy isotopes of water - HDO and H218O. Data was collected on the P-3 Orion aircraft during the NASA 2017 ORACLES campaign. Using these measurements, a box model was constructed using the combined conservation laws associated with all four of these quantities to estimate the entrainment and rainout of cloud liquid. The population of profiles sampled by the aircraft over the course of the 30 day mission spans varying concentrations of BBA. Initial plots of the water isotope mixing lines show where and to what degree the BBA air mass has mixed into the boundary layer air mass from above. This is demonstrated by the fact that the mixing end-members are the same for the different areas sampled, but the rate at which the various mixing lines are traversed as a function of altitude varies. Further, the mixing lines as a function of height traverse back and forth between end members multiple times over one profile. This suggests that air masses are mixing by `layering' into each other, and helps us to better represent entrainment in our box model. Meanwhile, isotope ratios measured below vs above the cloud layer show that the air above the clouds is depleted of heavy water isotopes in comparison to below - the degree of depletion could correspond to drizzle amount.

Challenges in preparing, preserving and detecting para-water in bulk: overcoming proton exchange and other hurdles.

PubMed

Mammoli, Daniele; Salvi, Nicola; Milani, Jonas; Buratto, Roberto; Bornet, Aurélien; Sehgal, Akansha Ashvani; Canet, Estel; Pelupessy, Philippe; Carnevale, Diego; Jannin, Sami; Bodenhausen, Geoffrey

2015-10-28

Para-water is an analogue of para-hydrogen, where the two proton spins are in a quantum state that is antisymmetric under permutation, also known as singlet state. The populations of the nuclear spin states in para-water are believed to have long lifetimes just like other Long-Lived States (LLSs). This hypothesis can be verified by measuring the relaxation of an excess or a deficiency of para-water, also known as a "Triplet-Singlet Imbalance" (TSI), i.e., a difference between the average population of the three triplet states T (that are symmetric under permutation) and the population of the singlet state S. In analogy with our recent findings on ethanol and fumarate, we propose to adapt the procedure for Dissolution Dynamic Nuclear Polarization (D-DNP) to prepare such a TSI in frozen water at very low temperatures in the vicinity of 1.2 K. After rapid heating and dissolution using an aprotic solvent, the TSI should be largely preserved. To assess this hypothesis, we studied the lifetime of water as a molecular entity when diluted in various solvents. In neat liquid H2O, proton exchange rates have been characterized by spin-echo experiments on oxygen-17 in natural abundance, with and without proton decoupling. One-dimensional exchange spectroscopy (EXSY) has been used to study proton exchange rates in H2O, HDO and D2O mixtures diluted in various aprotic solvents. In the case of 50 mM H2O in dioxane-d8, the proton exchange lifetime is about 20 s. After dissolving, one can observe this TSI by monitoring intensities in oxygen-17 spectra of H2O (if necessary using isotopically enriched samples) where the AX2 system comprising a "spy" oxygen A and two protons X2 gives rise to binomial multiplets only if the TSI vanishes. Alternatively, fast chemical addition to a suitable substrate (such as an activated aldehyde or ketone) can provide AX2 systems where a carbon-13 acts as a spy nucleus. Proton signals that relax to equilibrium with two distinct time constants can be considered as a hallmark of a TSI. We optimized several experimental procedures designed to preserve and reveal dilute para-water in bulk.

Atmospheric influences on infrared-laser signals used for occultation measurements between Low Earth Orbit satellites

NASA Astrophysics Data System (ADS)

Schweitzer, S.; Kirchengast, G.; Proschek, V.

2011-10-01

LEO-LEO infrared-laser occultation (LIO) is a new occultation technique between Low Earth Orbit (LEO) satellites, which applies signals in the short wave infrared spectral range (SWIR) within 2 μm to 2.5 μm. It is part of the LEO-LEO microwave and infrared-laser occultation (LMIO) method that enables to retrieve thermodynamic profiles (pressure, temperature, humidity) and altitude levels from microwave signals and profiles of greenhouse gases and further variables such as line-of-sight wind speed from simultaneously measured LIO signals. Due to the novelty of the LMIO method, detailed knowledge of atmospheric influences on LIO signals and of their suitability for accurate trace species retrieval did not yet exist. Here we discuss these influences, assessing effects from refraction, trace species absorption, aerosol extinction and Rayleigh scattering in detail, and addressing clouds, turbulence, wind, scattered solar radiation and terrestrial thermal radiation as well. We show that the influence of refractive defocusing, foreign species absorption, aerosols and turbulence is observable, but can be rendered small to negligible by use of the differential transmission principle with a close frequency spacing of LIO absorption and reference signals within 0.5%. The influences of Rayleigh scattering and terrestrial thermal radiation are found negligible. Cloud-scattered solar radiation can be observable under bright-day conditions, but this influence can be made negligible by a close time spacing (within 5 ms) of interleaved laser-pulse and background signals. Cloud extinction loss generally blocks SWIR signals, except very thin or sub-visible cirrus clouds, which can be addressed by retrieving a cloud layering profile and exploiting it in the trace species retrieval. Wind can have a small influence on the trace species absorption, which can be made negligible by using a simultaneously retrieved or a moderately accurate background wind speed profile. We conclude that the set of SWIR channels proposed for implementing the LMIO method (Kirchengast and Schweitzer, 2011) provides adequate sensitivity to accurately retrieve eight trace species of key importance to climate and atmospheric chemistry (H2O, CO2, 13CO2, C18OO, CH4, N2O, O3, CO) in the upper troposphere/lower stratosphere region outside clouds under all atmospheric conditions. Two further species (HDO, H218O) can be retrieved in the upper troposphere.

ACCURATE: Influence of Cloud Layers and Aerosol on Infrared Laser Occultation Signals for Sensing of Greenhouse Gases

NASA Astrophysics Data System (ADS)

Proschek, V.; Schweitzer, S.; Emde, C.; Ladstädter, F.; Fritzer, J.; Kirchengast, G.

2009-04-01

ACCURATE (Atmospheric Climate and Chemistry in the UTLS Region And climate Trends Explorer), a new climate satellite concept, enables simultaneous measurement of profiles of greenhouse gases, isotopes, wind and thermodynamic variables from Low Earth Orbit (LEO) satellites. The measurement principle applied is a combination of the novel LEO-LEO infrared laser occultation (LIO) technique and the well-studied but not yet flown LEO-LEO microwave occultation (LMO) technique. As intrinsic to the space-borne occultation technique, the measurements are evenly distributed around the world, have high vertical resolution and high accuracy and are stable over long time periods. The LIO uses near-monochromatic signals in the short-wave infrared range (~2-2.5 m in the case of ACCURATE) which are absorbed by various trace species in the Earth's atmosphere. From signal transmission measurements, profiles of the concentration of the absorbing species can be derived given that temperature and pressure are accurately known from LMO. The current ACCURATE mission design is arranged for the measurement of six greenhouse gases (H2O, CO2, CH4, N2O, O3, CO) and four isotopes (13CO2, C18OO, HDO, H218O) with focus on the upper troposphere/lower stratosphere region (UTLS, 5-35 km). Wind speed in line-of-sight can be derived from a line-symmetric transmission difference which is caused by wind-induced Doppler shift. By-products are information on cloud layering, aerosol extinction and scintillation strength. This contribution presents an overview on the ACCURATE mission design and the expected accuracy of retrieved atmospheric variables and further focuses on the influence of clouds and aerosols on propagating LIO signals. Special emphasis will be given to sub-visible cirrus clouds which are semi-transparent to infrared signals. A simple frequency dependent cloud extinction parametrization was included into the occultation propagation software EGOPS and evaluated against results of the advanced radiative transfer model libRadtran. Use of this parametrization also allows to separate the disturbance by clouds from other atmospheric influences on signal transmission. The influence of aerosols was investigated by means of an extinction model developed on the basis of SAGE (Stratospheric Aerosol and Gas Experiment) measurements. The effects of different cases from background to volcanic aerosol levels are presented.

Synthesis and characterization of catalysts for the selective transformation of biomass-derived materials

NASA Astrophysics Data System (ADS)

Ghampson, Isaac Tyrone

The experimental work in this thesis focuses on generating catalysts for two intermediate processes related to the thermal conversion of lignocellulosic biomass: the synthesis and characterization of mesoporous silica supported cobalt catalysts for the Fischer-Tropsch reaction, and an exploration of the reactivity of bulk and supported molybdenum-based nitride catalysts for the hydrodeoxygenation (HDO) of guaiacol, a lignin model compound. The first section of the work details the synthesis of a series of silica-supported cobalt Fischer-Tropsch catalysts with pore diameters ranging from 2-23 nm. Detailed X-ray diffraction measurements were used to determine the composition and particle diameters of the metal fraction, analyzed as a three-phase system containing Cofcc, Cohcp and CoO particles. Catalyst properties were determined at three stages in catalyst history: (1) after the initial calcination step to thermally decompose the catalyst precursor into Co3O4, (2) after the hydrogen reduction step to activate the catalyst to Co and (3) after the FT reaction. From the study, it was observed that larger pore diameters supported higher turnover frequency; smaller pore diameters yielded larger mole fraction of CoO; XRD on post-reduction and post-FTS catalyst samples indicated significant changes in dispersivity after reduction. In the next section, the catalytic behaviors of unsupported, activated carbon-, alumina-, and SBA-15 mesoporous silica-supported molybdenum nitride catalysts were evaluated for the hydrodeoxygenation of guaiacol (2-methoxy phenol) at 300°C and 5 MPa. The nitride catalysts were prepared by thermal decomposition of bulk and supported ammonium heptamolybdate to form MoO 3 followed by nitridation in either flowing ammonia or a nitrogen/hydrogen mixture. The catalytic properties were strongly affected by the nitriding and purging treatment as well as the physical and chemical properties of support. The overall reaction was influenced by the crystalline phase present in the catalyst, dispersion of molybdenum nitride/oxynitride, and the porosity of the support. The hydrodeoxygenation of guaiacol followed two proposed reaction pathways: demethylation (DME) of guaiacol to form catechol, followed by dehydroxylation to form phenol; or a direct demethoxylation (DMO) to form phenol. The selectivity of the reaction was expressed in terms of the phenol/catechol ratio. Phenol was the predominant product for all the catalysts studied, except for the alumina-supported catalysts (an effect of the alumina support). The results from this thesis are encouraging for the application of Mo nitride based catalysts for hydrodeoxygenation of whole pyrolysis oil.

Blood pressure in Warmblood horses before and during a euglycemic-hyperinsulinemic clamp.

PubMed

Nostell, Katarina E A; Lindåse, Sanna S; Bröjer, Johan T

2016-10-20

Insulin resistance (IR) in humans is related to hypertension and impaired vasodilation. Insulin administration has been shown to lower blood pressure both in insulin resistant as well as in insulin sensitive individuals. The aim of the study was to investigate the association between insulin sensitivity and alterations in blood pressure in healthy horses before and after a euglycemic-hyperinsulinemic clamp (EHC). A 3-h EHC was performed in 13 healthy horses (11 mares, 2 geldings). Blood samples for measurement of plasma glucose and insulin were collected before the start of the EHC, every 10 min during the EHC and immediately after the EHC. Mean, systolic- and diastolic blood pressure was measured before and during the final 10 min of the EHC using an indirect high-definition oscillometric monitor (HDO, horse model) applied to the middle of the coccygeal artery. Five consecutive measurements were made in each horse and on each occasion. Insulin and glucose data from the EHC were used to calculate the mean rate of glucose disposal per unit of insulin during steady state (M/I ratio). Insulin resistance was defined as a M/I ratio <5 mg/kg/min/mUL (Lindåse et al. in Am J Vet Res 77:300-309, 2016). Insulin administration decreased systolic, diastolic and mean arterial pressure in all horses. The M/I ratio for all horses was negatively correlated with the decrease in systolic blood pressure (r 2  = 0.55, P = 0.004) and mean arterial pressure (r 2  = 0.31, P = 0.048) but not diastolic blood pressure (r 2  = 0.12, P = 0.26). Eight horses were defined as insulin resistant (IR) and five horses had normal insulin sensitivity. The five horses with normal insulin sensitivity showed a greater decrease in systolic blood pressure (-17.0 ± 7.4 vs. -3.4 ± 4.6 mmHg, P = 0.001) and MAP (19.2 ± 14.7 vs. 6.9 ± 8.7 mmHg, P = 0.04) than IR horses. There was no difference in the decrease in diastolic blood pressure between groups (16 ± 12.8 vs. 8.9 ± 12.1 mmHg, P = 0.17). This study indicates that there is a relationship between insulin sensitivity and systolic and MAP in horses. However, studies on a larger number of horses are needed to confirm this association.

Performance of greenhouse gas profiling by infrared-laser and microwave occultation in cloudy air

NASA Astrophysics Data System (ADS)

Proschek, V.; Kirchengast, G.; Emde, C.; Schweitzer, S.

2012-12-01

ACCURATE is a proposed future satellite mission enabling simultaneous measurements of greenhouse gases (GHGs), wind and thermodynamic variables from Low Earth Orbit (LEO). The measurement principle is a combination of LEO-LEO infrared-laser occultation (LIO) and microwave occultation (LMO), the LMIO method, where the LIO signals are very sensitive to clouds. The GHG retrieval will therefore be strongly influenced by clouds in parts of the troposphere. The IR-laser signals, at wavelengths within 2--2.5μ m, are chosen to measure six GHGs (H2O, CO2, CH4, N2O, O3, CO; incl.~key isotopes 13CO2, C18OO, HDO). The LMO signals enable to co-measure the thermodynamic variables. In this presentation we introduce the algorithm to retrieve GHG profiles under cloudy-air conditions by using quasi-realistic forward simulations, including also influence of Rayleigh scattering, scintillations and aerosols. Data from CALIPSO--Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations--with highest vertical resolution of about 60 m and horizontal resolution of about 330 m were used for simulation of clouds. The IR-laser signals consist for each GHG of a GHG-sensitive and a close-by reference signal. The key process, ``differencing'' of these two signals, removes the atmospheric ``broadband'' effects, resulting in a pure GHG transmission profile. Very thin ice clouds, like sub-visible cirrus, are fairly transparent to the IR-laser signals, thicker and liquid water clouds block the signals. The reference signal is used to produce a cloud layering profile from zero to blocking clouds and is smoothed in a preprocess to suppress scintillations. Sufficiently small gaps, of width <2 km in the cloud layering profile, are found to enable a decent retrieval of entire GHG profiles over the UTLS under broken cloudiness and are therefore bridged by interpolation. Otherwise in case of essentially continuous cloudiness the profiles are found to terminate at cloud top level. The accuracy of retrieved GHG profiles is found better than 1% to 4% for single profiles in the UTLS region outside clouds and through broken cloudiness, and the profiles are essentially unbiased. Cloud gap-interpolation increases the tropospheric penetration of GHG profiles for scientific applications. The associated cloud layering profile provides quality-control information on cloud gap-interpolations, if they occured, and on cloud-top altitude for cloud blocking cases. The LMIO technique shows promising prospects for GHG monitoring even under cloudy-air conditions.

High-Power Single-Mode 2.65-micron InGaAsSb/AlInGaAsSb Diode Lasers

NASA Technical Reports Server (NTRS)

Frez, Clifford F.; Briggs, Ryan M.; Forouhar, Siamak; Borgentun, Carl E.; Gupta, James

2013-01-01

Central to the advancement of both satellite and in-situ science are improvements in continuous-wave and pulsed infrared laser systems coupled with integrated miniaturized optics and electronics, allowing for the use of powerful, single-mode light sources aboard both satellite and unmanned aerial vehicle platforms. There is a technological gap in supplying adequate laser sources to address the mid-infrared spectral window for spectroscopic characterization of important atmospheric gases. For high-power applications between 2 to 3 micron, commercial laser technologies are unsuitable because of limitations in output power. For instance, existing InP-based laser systems developed for fiber-based telecommunications cannot be extended to wavelengths longer than 2 micron. For emission wavelengths shorter than 3 micron, intersubband devices, such as infrared quantum cascade lasers, become inefficient due to band-offset limitations. To date, successfully demonstrated singlemode GaSb-based laser diodes emitting between 2 and 3 micron have employed lossy metal Bragg gratings for distributed- feedback coupling, which limits output power due to optical absorption. By optimizing both the quantum well design and the grating fabrication process, index-coupled distributed-feedback 2.65-micron lasers capable of emitting in excess of 25 mW at room temperature have been demonstrated. Specifically, lasers at 3,777/cm (2.65 micron) have been realized to interact with strong absorption lines of HDO and other isotopologues of H2O. With minor modifications of the optical cavity and quantum well designs, lasers can be fabricated at any wavelength within the 2-to-3-micron spectral window with similar performance. At the time of this reporting, lasers with this output power and wavelength accuracy are not commercially available. Monolithic ridge-waveguide GaSb lasers were fabricated that utilize secondorder lateral Bragg gratings to generate single-mode emission from InGaAsSb/ AlInGaAsSb multi-quantum well structures. The device fabrication utilizes etched index-coupled gratings in the top AlGaAsSb cladding of the laser chip along the ridge waveguide, whereas commercial lasers that emit close to this wavelength include loss-coupled metal gratings that limit the output power of the laser. Semiconductor-laser-based spectrometers can be used to replace gas sensors currently used in industry and government. With the availability of high-power laser sources at mid-infrared wavelengths, sensors can target strong fundamental gas absorption lines to maximize instrument sensitivity.

A spectral line survey of Orion KL in the bands 486-492 and 541-577 GHz with the Odin satellite. I. The observational data

NASA Astrophysics Data System (ADS)

Olofsson, A. O. H.; Persson, C. M.; Koning, N.; Bergman, P.; Bernath, P. F.; Black, J. H.; Frisk, U.; Geppert, W.; Hasegawa, T. I.; Hjalmarson, Å.; Kwok, S.; Larsson, B.; Lecacheux, A.; Nummelin, A.; Olberg, M.; Sandqvist, Aa.; Wirström, E. S.

2007-12-01

Aims:Spectral line surveys are useful since they allow identification of new molecules and new lines in uniformly calibrated data sets. The subsequent multi-transition analysis will provide improved knowledge of molecular abundances, cloud temperatures and densities, and may also reveal previously unsuspected blends of molecular lines, which otherwise may lead to erroneous conclusions. Nonetheless, large portions of the sub-millimetre spectral regime remain unexplored due to severe absorptions by H{2}O and O{2} in the terrestrial atmosphere. The purpose of the measurements presented here is to cover wavelength regions at and around 0.55 mm - regions largely unobservable from the ground. Methods: Using the Odin astronomy/aeronomy satellite, we performed the first spectral survey of the Orion KL molecular cloud core in the bands 486-492 and 541-576 GHz with rather uniform sensitivity (22-25 mK baseline noise). Odin's 1.1 m size telescope, equipped with four cryo-cooled tuneable mixers connected to broad band spectrometers, was used in a satellite position-switching mode. Two mixers simultaneously observed different 1.1 GHz bands using frequency steps of 0.5 GHz (25 h each). An on-source integration time of 20 h was achieved for most bands. The entire campaign consumed 1100 orbits, each containing one hour of serviceable astro-observation. Results: We identified 280 spectral lines from 38 known interstellar molecules (including isotopologues) having intensities in the range 80 to 0.05 K. An additional 64 weak lines remain unidentified. Apart from the ground state rotational 1{1,0}-1{0,1} transitions of ortho-H{2}O, H{2}18O and H{2}17O, the high energy 6{2,4}-7{1,7} line of para-H{2}O (Eu=867 K) and the HDO(2{0,2}-1{1,1}) line have been observed, as well as the 1{0}-0{1} lines from NH{3} and its rare isotopologue 15NH{3}. We suggest assignments for some unidentified features, notably the new interstellar molecules ND and SH-. Severe blends have been detected in the line wings of the H{2}18O, H{2}17O and 13CO lines changing the true linewidths of the outflow emission. Odin is a Swedish-led satellite project funded jointly by the Swedish National Space Board (SNSB), the Canadian Space Agency (CSA), the National Technology Agency of Finland (Tekes), and the Centre National d'Études Spatiales (CNES, France). The Swedish Space Corporation (SSC) was the industrial prime contractor and is also responsible for the satellite operation. Appendix B is only available at electronic form at http://www.aanda.org

The Rovibrational Intensities of the (40 deg 1) and (00 deg 0) Pentad Absorption Bands of 12C16O2 Between 7284 and 7921 cm(exp-1)

NASA Technical Reports Server (NTRS)

Giver, L. P.; Chackerian, C., Jr.; Spencer, N.; Brown, L. R.; Wattson, R. B.; Gore, Warren J. (Technical Monitor)

1995-01-01

Carbon dioxide is the major constituent of the atmospheres of both Mars and Venus. Correct interpretations of spectra of these atmospheres require accurate knowledge of a substantial number of absorption bands of this gas. This is especially true for Venus; many weak CO2 bands that are insignificant in the earth's atmosphere are prominent absorbers in Venus' hot, dense lower atmosphere. Yet, recent near-infrared spectra of Venus' nightside have discovered emission windows, which occur between CO2 absorption bands, at 4040-4550 cm(exp-1), 5700-5900 cm(exp-1), and several smaller ones between 7500 and 9400 cm(exp-1). This radiation is due to thermal emission from Venus' lower atmosphere, diminished by scattering and absorption within the sulfuric acid clouds on its way to space. Simulations of these data with radiative transfer models can provide improved information on the abundances of a number of constituents of the lower atmosphere (e.g. H2O, CO, HDO, HCl, HF, and OCS) and the optical properties of the clouds, whose spatial variation modulates the brightness of the emissions. However, the accuracy of these retrievals has been limited by insufficient knowledge of the opacity of some of the gas species, including CO2, at the large pathlengths and high temperatures and pressures that exist on Venus. In particular, modeling the emission spectrum did not produce a good fit for the emission window centered at 7830 cm(exp-1). In an ongoing effort to assist analyses of these Venus spectra, we have been making laboratory intensity measurements of several weak bands of CO2 which are significant absorbers in these Venus emission windows. The CO2 bands that are prominent in the 7830 cm(exp-1) region belong to the vibrational sequence 4v1+v3 and associated hot bands. Only 2 of the 5 bands of this sequence have been previously measured. Modeling Venus' emission spectrum in the 7830 cm(exp-1) region had to rely on calculated intensity values for the weak ground state band at 7921 cm-1 and the associated hot bands. Since the calculated intensities of ground state bands are known to have significant uncertainties, we decided to measure this (40 deg 1)I (left arrow) (00 deg 0) band with the Ames 25 meter multiple reflection absorption cell and Fourier transform spectrometer. We also measured the (40 deg 1) (sub IV) (left arrow) (00 deg 0) band at 7460 cm(exp-1), which also had not been previously measured. These measurements are reported in this article, and we also give our reanalysis of the prior measurements of the (40 deg 1) (sub III) (left arrow) (00 deg 0) bands. These measurements provide the basis for improving calculated intensities for related hot bands as well as simulations of Venus' spectrum.

D/H fractionation in the H2-H2O system at supercritical water conditions: Compositional and hydrogen bonding effects

NASA Astrophysics Data System (ADS)

Foustoukos, Dionysis I.; Mysen, Bjorn O.

2012-06-01

A series of experiments has been conducted in the H2-D2-D2O-H2O-Ti-TiO2 system at temperatures ranging from 300 to 800 °C and pressures between ∼0.3 and 1.3 GPa in a hydrothermal diamond anvil cell, utilizing Raman spectroscopy as a quantitative tool to explore the relative distribution of hydrogen and deuterium isotopologues of the H2 and H2O in supercritical fluids. In detail, H2O-D2O solutions (1:1) were reacted with Ti metal (3-9 h) in the diamond cell, leading to formation of H2, D2, HD, and HDO species through Ti oxidation and H-D isotope exchange reactions. Experimental results obtained in situ and at ambient conditions on quenched samples indicate significant differences from the theoretical estimates of the equilibrium thermodynamic properties of the H-D exchange reactions. In fact, the estimated enthalpy for the H2(aq)-D2(aq) disproportionation reaction (ΔHrxn) is about -3.4 kcal/mol, which differs greatly from the +0.16 kcal/mol predicted for the exchange reaction in the gas phase by statistical mechanics models. The exothermic behavior of the exchange reaction implies enhanced stability of H2 and D2 relative to HD. Accordingly, the significant energy difference of the internal H2(aq)-D2(aq)-HD(aq) equilibrium translates to strong differences of the fractionation effects between the H2O-H2 and D2O-D2 isotope exchange relationships. The D/H fractionation factors between H2O-H2(aq) and D2O-D2(aq) differ by 365‰ in the 600-800 °C temperature range, and are indicative of the greater effect of D2O contribution to the δD isotopic composition of supercritical fluids. The negative ΔHrxn values for the H2(aq)-D2(aq)-HD(aq) equilibrium and the apparent decrease of the equilibrium constant with increasing temperature might be because of differences of the Henry’s law constant between the H- and D-bearing species dissolved in supercritical aqueous solutions. Such effects may be attributed to the stronger hydrogen bonding in the O-H⋯O relative to the O-D⋯O environment. This difference allows enhanced gas solubility in the denser and more polar H2O clusters, and thus, affects the D/H exchange between the H2-D2 volatiles and the coexisting H2O-D2O mixtures. The proposed role of temperature in promoting differences in the density and polarity of hydrogen-bonded OHO and ODO molecules may be explained with isotope-specific molar volume effects similar to those suggested to account for the hydrogen isotope fractionation between H2O and hydroxide mineral phases (e.g. brucite) across large pressure intervals.

Anisotropic diffusion at the field scale in a 4-year multi-tracer diffusion and retention experiment - I: Insights from the experimental data

NASA Astrophysics Data System (ADS)

Gimmi, Thomas; Leupin, Olivier X.; Eikenberg, Jost; Glaus, Martin A.; Van Loon, Luc R.; Waber, H. Niklaus; Wersin, Paul; Wang, Hao A. O.; Grolimund, Daniel; Borca, Camelia N.; Dewonck, Sarah; Wittebroodt, Charles

2014-01-01

Claystones are considered worldwide as barrier materials for nuclear waste repositories. In the Mont Terri underground research laboratory (URL), a nearly 4-year diffusion and retention (DR) experiment has been performed in Opalinus Clay. It aimed at (1) obtaining data at larger space and time scales than in laboratory experiments and (2) under relevant in situ conditions with respect to pore water chemistry and mechanical stress, (3) quantifying the anisotropy of in situ diffusion, and (4) exploring possible effects of a borehole-disturbed zone. The experiment included two tracer injection intervals in a borehole perpendicular to bedding, through which traced artificial pore water (APW) was circulated, and a pressure monitoring interval. The APW was spiked with neutral tracers (HTO, HDO, H2O-18), anions (Br, I, SeO4), and cations (Na-22, Ba-133, Sr-85, Cs-137, Co-60, Eu-152, stable Cs, and stable Eu). Most tracers were added at the beginning, some were added at a later stage. The hydraulic pressure in the injection intervals was adjusted according to the measured value in the pressure monitoring interval to ensure transport by diffusion only. Concentration time-series in the APW within the borehole intervals were obtained, as well as 2D concentration distributions in the rock at the end of the experiment after overcoring and subsampling which resulted in ∼250 samples and ∼1300 analyses. As expected, HTO diffused the furthest into the rock, followed by the anions (Br, I, SeO4) and by the cationic sorbing tracers (Na-22, Ba-133, Cs, Cs-137, Co-60, Eu-152). The diffusion of SeO4 was slower than that of Br or I, approximately proportional to the ratio of their diffusion coefficients in water. Ba-133 diffused only into ∼0.1 m during the ∼4 a. Stable Cs, added at a higher concentration than Cs-137, diffused further into the rock than Cs-137, consistent with a non-linear sorption behavior. The rock properties (e.g., water contents) were rather homogeneous at the centimeter scale, with no evidence of a borehole-disturbed zone. In situ anisotropy ratios for diffusion, derived for the first time directly from field data, are larger for HTO and Na-22 (∼5) than for anions (∼3-4 for Br and I). The lower ionic strength of the pore water at this location (∼0.22 M) as compared to locations of earlier experiments in the Mont Terri URL (∼0.39 M) had no notable effect on the anion accessible pore fraction for Cl, Br, and I: the value of 0.55 is within the range of earlier data. Detailed transport simulations involving different codes will be presented in a companion paper.

Isotopes in the Arctic atmospheric water cycle

NASA Astrophysics Data System (ADS)

Bonne, Jean-Louis; Werner, Martin; Meyer, Hanno; Kipfstuhl, Sepp; Rabe, Benjamin; Behrens, Melanie; Schönicke, Lutz; Steen Larsen, Hans Christian; Masson-Delmotte, Valérie

2016-04-01

The ISO-ARC project aims at documenting the Arctic atmospheric hydrological cycle, by assessing the imprint of the marine boundary conditions (e.g. temperature variations, circulation changes, or meltwater input) to the isotopic composition of the atmospheric water cycle (H218O and HDO) with a focus on North Atlantic and Arctic oceans. For this purpose, two continuous monitoring water vapour stable isotopes cavity ring-down spectrometers have been installed in July 2015: on-board the Polarstern research vessel and in the Siberian Lena delta Samoylov research station (N 72° 22', E 126° 29'). The Polarstern measurements cover the summer 2015 Arctic campaign from July to mid-October, including six weeks in the Fram Strait region in July- August, followed by a campaign reaching the North Pole and a transect from the Norwegian Sea to the North Sea. These vapour observations are completed by water isotopic measurements in samples from the surface ocean water for Polarstern and from precipitation in Samoylov and Tiksi (120 km south-east of the station). A custom-made designed automatic calibration system has been implemented in a comparable manner for both vapour instruments, based on the injection of different liquid water standards, which are completely vaporised in dry air at high temperature. Subsequent humidity level can be adjusted from 2000 to at least 30000 ppm. For a better resilience, an independent calibration system has been added on the Samoylov instrument, allowing measurements of one standard at humidity levels ranging from 2000 to 15000 ppm: dry air is introduced in a tank containing a large amount of liquid water standard, undergoing evaporation under a controlled environment. The measurement protocol includes an automatic calibration every 25 hours. First instrument characterisation experiments depict a significant isotope-humidity effect at low humidity, dependant on the isotopic composition of the standard. For ambient air, our first isotope measurements highlighted significant synoptic variations in summer in both sites. In Samoylov, the premises of a seasonal cycle have been observed during the summer-fall transition, with a fast humidity level and isotopic decrease. The latitudinal gradient is also highly visible on the Polarstern record. Complementing simulations of the water vapour isotopic composition by the ECHAM5-wiso model reproduce the Polarstern synoptic variability and spatial patterns with a good accuracy. In the near future, our records will be combined with simultaneous water isotope measurements in Iceland (by Hans Christian Steen-Larsen, CIC), Svalbard (by Valérie-Masson Delmotte, LSCE) and paired with complementing climate simulations enhanced by water isotope diagnostics. These data sets, covering an approx. 6,000 km transect of Northern Eurasia will allow for a quantitative assessment of the isotopic variations of the Arctic water cycle. The results of these analyses will also be of relevance for the interpretation of isotope signals found in ice cores and on terrestrial Arctic sites in terms of past climate change.

METHANE AND WATER ON MARS: MAPS OF ACTIVE REGIONS AND THEIR SEASONAL VARIABILITY

NASA Astrophysics Data System (ADS)

Villanueva, G. L.; Mumma, M. J.; Novak, R. E.

2009-12-01

We have detected methane on Mars, and measured it simultaneously with water using powerful ground-based telescopes [1, 2]. Its presence in such a strongly oxidized atmosphere (CO2: 95.3%) requires recent release; the ultimate origin of this methane is uncertain, but it could either be abiotic or biotic. On Earth, methane is produced primarily by biology, with a small fraction produced by abiotic means. The sources and sinks of hydrogen-bearing species (e.g., H2O and CH4) on Mars are still poorly known. In particular, the roles of the regolith and the sub-surface hydrogen reservoirs in the Martian water cycle have been broadly studied, but have not been conclusively quantified. If water is being released from the sub-surface or shares a common source with other H-bearing species, we might see correlations among them. Previous searches for such correlations have been precluded because of the lack of simultaneity of the measurements and the intrinsic variability of water on Mars, which is a condensable whose total local abundance is partitioned among several competing phases controlled largely by temperature (ensuring its variability on a variety of time scales, from diurnal to seasonal to epochal). We sampled multiple spectral lines of methane and water vapor on Mars in a campaign spanning seven years (three Mars years; 1999-2006) and sampling three seasons on Mars. Data were ac-quired using long-slit infrared spectrometers: CSHELL (Cryogenic Echelle Spectrograph) at NASA-IRTF (Infrared Telescope Facility) and NIRSPEC (Near Infrared Spectrograph) at Keck 2. These instruments offer spatially-resolved spectra with the high spectral resolving power (λ/δλ ~ 40,000) needed to reduce confusion among telluric, Martian, and Fraunhofer lines (in reflected solar radiation). Since 2005, we greatly improved our data processing algorithms and increased the sensitivity of our measurements by an order of magnitude. Using these new techniques, we detected multiple lines of methane on Mars [1] and discovered two new band sys-tems of isotopic CO2 (at 3.3 and 3.7 μm) that can interfere with signatures of CH4 and HDO [3, 4]. The spectral signatures of these isotopic CO2 transitions may affect searches based on low spectral resolution methods, but they do not affect the searches reported herein. We present the spatial distributions of methane and water-vapor on Mars extracted from our seven-year spectral database, and we compare these with geological parameters. Both gases are depleted at vernal equinox but are enhanced in warm seasons (spring/summer), though often with dissimilar spatial distributions. In Northern Summer we observe a polar outburst of water but no methane, while in Southern Spring we observe release of abundant methane but little water. Regions of methane release appear mainly over ancient terrain (Noachian/Hesperian, older than 3 billion years) known to have a rich hydration history. [1] Mumma et al. (2009) Science 323:1041-1045. [2] Villanueva et al. (2009), submitted. [3] Villanueva et al. (2008) Icarus 195(1):34-44. [4] Villanueva et al. (2008) JQSRT 109(6):883-894.

Infrared Measurements of Atmospheric Gases Above Mauna Loa, Hawaii, in February 1987

NASA Technical Reports Server (NTRS)

Rinsland, C. P.; Goldman, A.; Murcray, F. J.; Murcray, F. H.; Blatherwick, R. D.; Murcray, D. G.

1988-01-01

Infrared solar absorption spectra recorded at 0.02/ cm resolution from the National Oceanic and Atmospheric Administration (NOAA) Geophysical Monitoring for Climate Change (GMCC) program station at Mauna Loa, Hawaii (latitude 19.5 deg N, longitude 155.6 deg W, elevation 3.40 km), in February 1997 have been analyzed to determine simultaneous total vertical column amounts for 13 atmospheric gases. Average tropospheric concentrations of CO2, N2O, CH4, and CHCIF2 and the daytime diurnal variations or the total columns of NO and NO2 have also been inferred. The retrieved total columns (in molecules /sq cm) of the nondiurnally varying gases are 1.6 +/- 0.2 x 10(exp 15) for HCl, 5.9 +/- 1.2 x 10(exp 15) for HNO3, 2.0 +/- 0.2 x 10(exp 21) for H2O16, 4.4 +/- 0.7 x 10(exp 18) for H2O18, 2.7 +/- 0.1 x 10(exp 17) for HDO, 2.3 +/- 0.2 x 10(exp 19) for CH4, 5.0 +/- 0.5 x 10(exp 21) for CO2, 6.7 +/- 0.8 x 10(exp 18) for O3, 4.3 +/- 0.4 x 10(exp 18) for N2O, 1.0 +/- 0.2 x 10(exp 16) for C2H6, and 9.7 +/- 2.5 x 10(exp 14) for CHClF2. We compare the total column measurements of HCl and HNO3 with previously reported ground-based, aircraft, and satellite measurements. The results for HCl are or particular interest because of the expected temporal increase in the concentration of this gas in the stratosphere. However, systematic differences among stratospheric HCl total column measurements from 1978 to 1980 and the absence of observations of free tropospheric HCl above Mauna Loa make it impossible to obtain a reliable estimate of the trend in the total burden of HCl. The measured HNO3 total column is consistent with aircraft measurements from approx. 12 km altitude. The O3 total column deduced from the IR spectra agrees with correlative Mauna Loa Umkehr measurements within the estimated error limits. The column-averaged D/H ratio of water vapor is (68 +/- 9) x- 10(exp -6), which is 0.44 +/- 0.06 times the reference value of 155.76 x 10(exp -6) for standard mean ocean water (SMOW). This large depletion in the D content of water vapor is similar to published measurements of the upper troposphere and lower stratosphere. Average tropospheric concentrations deduced for CO2, N2O, and CH4 are in good agreement with correlative NOAA GMCC surface data, indicating consistency between the measurement techniques for determining tropospheric volume mixing ratios. Results of the present study indicate that Mauna Loa is a favorable site for infrared monitoring of atmospheric gases. The site is particularly favorable for monitoring the tropospheric volume mixing ratios of long-lived gases, since the high altitude of the tropopause reduces corrections required to account for the decrease in volume mixing ratio in the stratosphere.

The study of the martian atmosphere from top to bottom with SPICAM light on mars express

NASA Astrophysics Data System (ADS)

Bertaux, Jean-Loup; Fonteyn, D.; Korablev, O.; Chassefière, E.; Dimarellis, E.; Dubois, J. P.; Hauchecorne, A.; Cabane, M.; Rannou, P.; Levasseur-Regourd, A. C.; Cernogora, G.; Quemerais, E.; Hermans, C.; Kockarts, G.; Lippens, C.; de Maziere, M.; Moreau, D.; Muller, C.; Neefs, B.; Simon, P. C.; Forget, F.; Hourdin, F.; Talagrand, O.; Moroz, V. I.; Rodin, A.; Sandel, B.; Stern, A.

2000-10-01

SPICAM Light is a small UV-IR instrument selected for Mars Express to recover most of the science that was lost with the demise of Mars 96, where the SPICAM set of sensors was dedicated to the study of the atmosphere of Mars (Spectroscopy for the investigation of the characteristics of the atmosphere of mars). The new configuration of SPICAM Light includes optical sensors and an electronics block. A UV spectrometer (118-320 nm, resolution 0.8 nm) is dedicated to Nadir viewing, limb viewing and vertical profiling by stellar occultation (3.8 kg). It addresses key issues about ozone, its coupling with H 2O, aerosols, atmospheric vertical temperature structure and ionospheric studies. An IR spectrometer (1.2- 4.8 μm, resolution 0.4-1 nm) is dedicated to vertical profiling during solar occultation of H 2O, CO 2, CO, aerosols and exploration of carbon compounds (3.5 kg). A nadir looking sensor for H 2O abundances (1.0- 1.7 μm, resolution 0.8 nm) is recently included in the package (0.8 kg). A simple data processing unit (DPU, 0.9 kg) provides the interface of these sensors with the spacecraft. In nadir orientation, SPICAM UV is essentially an ozone detector, measuring the strongest O 3 absorption band at 250 nm in the spectrum of the solar light scattered back from the ground. In the stellar occultation mode the UV Sensor will measure the vertical profiles of CO 2, temperature, O 3, clouds and aerosols. The density/temperature profiles obtained with SPICAM Light will constrain and aid in the development of the meteorological and dynamical atmospheric models, from the surface to 160 km in the atmosphere. This is essential for future missions that will rely on aerocapture and aerobraking. UV observations of the upper atmosphere will allow study of the ionosphere through the emissions of CO, CO +, and CO 2+, and its direct interaction with the solar wind. Also, it will allow a better understanding of escape mechanisms and estimates of their magnitude, crucial for insight into the long-term evolution of the atmosphere. The SPICAM Light IR sensor is inherited from the IR solar part of the SPICAM solar occultation instrument of Mars 96. Its main scientific objective is the global mapping of the vertical structure of H 2O, CO 2, CO, HDO, aerosols, atmospheric density, and temperature by the solar occultation. The wide spectral range of the IR spectrometer and its high spectral resolution allow an exploratory investigation addressing fundamental question of the possible presence of carbon compounds in the Martian atmosphere. Because of severe mass constraints this channel is still optional. An additional nadir near IR channel that employs a pioneering technology acousto-optical tuneable filter (AOTF) is dedicated to the measurement of water vapour column abundance in the IR simultaneously with ozone measured in the UV. It will be done at much lower telemetry budget compared to the other instrument of the mission, planetary fourier spectrometer (PFS).

The Atmospheric Chemistry Experiment (ACE): Mission Overview

NASA Astrophysics Data System (ADS)

Bernath, P. F.; Boone, C.; Walker, K.; McLeod, S.; Nassar, R.

2003-12-01

The ACE mission goals are: (1) to measure and to understand the chemical and dynamical processes that control the distribution of ozone in the upper troposphere and stratosphere, with a particular emphasis on the Arctic region; (2) to explore the relationship between atmospheric chemistry and climate change; (3) to study the effects of biomass burning in the free troposphere; (4) to measure aerosol number density, size distribution and composition in order to reduce the uncertainties in their effects on the global energy balance. ACE will make a comprehensive set of simultaneous measurements of trace gases, thin clouds, aerosols, and temperature by solar occultation from a satellite in low earth orbit. A high inclination (74 degrees) low earth orbit (650 km) gives ACE coverage of tropical, mid-latitudes and polar regions. The solar occultation advantages are high sensitivity and self-calibration. A high-resolution (0.02 cm-1) infrared Fourier Transform Spectrometer (FTS) operating from 2 to 13 microns (750-4100 cm-1) will measure the vertical distribution of trace gases, and the meteorological variables of temperature and pressure. The ACE concept is derived from the now-retired ATMOS FTS instrument, which flew on the Space Shuttle in 1985, 1992, 1993, 1994. Climate-chemistry coupling may lead to the formation of an Arctic ozone hole. ACE will provide high quality data to confront these model predictions and will monitor polar chemistry as chlorine levels decline. The ACE-FTS can measure water vapor and HDO in the tropical tropopause region to study dehydration and strat-trop exchange. The molecular signatures of massive forest fires will evident in the ACE infrared spectra. The CO2 in our spectra can be used to either retrieve atmospheric pressure or (if the instrument pointing knowledge proves to be satisfactory) for an independent retrieval of a CO2 profile for carbon cycle science. Aerosols and clouds will be monitored using the extinction of solar radiation at 0.525 and 1.02 microns as measured by two filtered imagers as well as by their infrared spectra. A dual spectrograph called MAESTRO has been added to the mission to extend the wavelength coverage to the 280-1000 nm spectral region. The broad-band atmospheric extinction measured with high signal-to-noise ratio by MAESTRO is particularly useful for the derivation of aerosol and cloud physical properties. The PI for the MAESTRO instrument is T. McElroy from the Meteorological Service of Canada (MSC). ACE is unique in that MAESTRO, the ACE-FTS and the imagers all share the same suntracker and make simultaneous measurements of the same scene. The FTS and imagers have been built by ABB-Bomem in Quebec City, while the satellite bus has been made by Bristol Aerospace in Winnipeg. ACE was selected in the Canadian Space Agency's SCISAT-1 program, and was successfully launched by NASA on August 12, 2003 for a 2 year mission. The main international partners for ACE are NASA, for the launch and algorithm work at NASA-Langley, and Belgium/ESA, for the CMOS imaging arrays and scientific support.

The Atmospheric Chemistry Experiment (ACE): Mission Overview

NASA Astrophysics Data System (ADS)

Bernath, P.

2003-04-01

The ACE mission goals are: (1) to measure and to understand the chemical and dynamical processes that control the distribution of ozone in the upper troposphere and stratosphere, with a particular emphasis on the Arctic region; (2) to explore the relationship between atmospheric chemistry and climate change; (3) to study the effects of biomass burning in the free troposphere; (4) to measure aerosol number density, size distribution and composition in order to reduce the uncertainties in their effects on the global energy balance. ACE will make a comprehensive set of simultaneous measurements of trace gases, thin clouds, aerosols, and temperature by solar occultation from a satellite in low earth orbit. A high inclination (74 degrees) low earth orbit (650 km) will give ACE coverage of tropical, mid-latitudes and polar regions. The solar occultation advantages are high sensitivity and self-calibration. A high-resolution (0.02 cm-1) infrared Fourier Transform Spectrometer (FTS) operating from 2 to 13 microns (750-4100 cm-1) will measure the vertical distribution of trace gases, and the meteorological variables of temperature and pressure. The ACE concept is derived from the now-retired ATMOS FTS instrument, which flew on the Space Shuttle in 1985, 1992, 1993, 1994. Climate-chemistry coupling may lead to the formation of an Arctic ozone hole. ACE will provide high quality data to confront these model predictions and will monitor polar chemistry as chlorine levels decline. The ACE-FTS can measure water vapor and HDO in the tropical tropopause region to study dehydration and strat-trop exchange. The molecular signatures of massive forest fires will evident in the ACE infrared spectra. The CO_2 in our spectra can be used to either retrieve atmospheric pressure or (if the instrument pointing knowledge proves to be satisfactory) for an independent retrieval of a CO_2 profile for carbon cycle science. Aerosols and clouds will be monitored using the extinction of solar radiation at 0.525 and 1.02 microns as measured by two filtered imagers as well as by their infrared spectra. A dual spectrograph called MAESTRO has been added to the mission to extend the wavelength coverage to the 280-1000 nm spectral region. The broad-band atmospheric extinction measured with high signal-to-noise ratio by MAESTRO is particularly useful for the derivation of aerosol and cloud physical properties. The PI for the MAESTRO instrument is T. McElroy from the Meteorological Service of Canada. ACE is unique in that MAESTRO, the ACE-FTS and the imagers all share the same suntracker and make simultaneous measurements of the same scene. The FTS and imagers have been built by ABB-Bomem in Quebec City, while the satellite bus has been made by Bristol Aerospace in Winnipeg. ACE has been selected in the Canadian Space Agency's SCISAT-1 program for a planned launch by NASA in May 2003 for a 2 year mission. The main international partners for ACE are NASA, for the launch and algorithm work at NASA-Langley, and Belgium/ESA, for the CMOS imaging arrays and scientific support.

Lattice Boltzmann Simulation of Kinetic Isotope Effect During Snow Crystal Formation

NASA Astrophysics Data System (ADS)

Lu, G.; Depaolo, D. J.; Kang, Q.; Zhang, D.

2007-12-01

The isotopic composition of precipitation, especially that of snow, plays a special role in the global hydrological cycle and in reconstruction of past climates using polar ice cores. The fractionation of the major water isotope species (HHO, HDO, HHO-18) during ice crystal formation is critical to understanding the global distribution of isotopes in precipitation. Ice crystal growth in clouds is traditionally treated with a spherically-symmetric steady state diffusion model, with semi-empirical modifications added to account for ventilation and for complex crystal morphology. Although it is known that crystal growth rate, which depends largely on the degree of vapor over- saturation, determines crystal morphology, there are no quantitative models that relate morphology to the vapor saturation factor. Since kinetic (vapor phase diffusion-controlled) isotopic fractionation also depends on growth rate, there should be direct relationships between vapor saturation, crystal morphology, and crystal isotopic composition. We use a 2D lattice Boltzmann model to simulate diffusion-controlled ice crystal growth from vapor- oversaturated air. In the model, crystals grow solely according to the diffusive fluxes just above the crystal surfaces, and hence crystal morphology arises from the initial and boundary conditions in the model and does not need to be specified a priori. Crystal growth patterns can be varied between random growth and deterministic growth (along the maximum concentration gradient for example). The input parameters needed are the isotope- dependent vapor deposition rate constant (k) and the water vapor diffusivity in air (D). The values of both k and D can be computed from kinetic theory, and there are also experimentally determined values of D. The deduced values of k are uncertain to the extent that the condensation coefficient for ice is uncertain. The ratio D/k is a length (order 1 micron) that determines the minimum scale of dendritic growth features and allows us to scale the numerical calculations to atmospheric conditions. Our calculations confirm that the crystal/vapor isotopic fractionation approaches the equilibrium value, and the crystals are compact (circular in 2D) as the saturation factor approaches unity (S= 1.0). However, few natural crystals form under such conditions. At higher oversaturation (e.g. S = 1.2), dendritic crystals of millimeter size develop on timescales appropriate to cloud processes, and kinetic effects control isotopic fractionation. Fractionation factors for dendritic crystals are similar to those predicted by the spherical diffusion model, but the model also gives estimates of crystal heterogeneity. Dendritic crystals are constrained to be relatively large, with dimension much greater than about 20D/k. The most difficult aspect of the modeling is to account for the large density difference between air and ice, which requires us to use a fictitious higher density for the vapor-oversaturated air and scale the crystal growth time accordingly. An approach using a larger scale simulation and the domain decomposition method can provide a vapor flux for a nested smaller scale calculation. The results clarify the controls on crystal growth, and the relationships between saturation state, growth rate, crystal morphology and isotopic fractionation.

Lattice Boltzmann Simulation of Water Isotope Fractionation During Growth of Ice Crystals in Clouds

NASA Astrophysics Data System (ADS)

Lu, G.; Depaolo, D.; Kang, Q.; Zhang, D.

2006-12-01

The isotopic composition of precipitation, especially that of snow, plays a special role in the global hydrological cycle and in reconstruction of past climates using polar ice cores. The fractionation of the major water isotope species (HHO, HDO, HHO-18) during ice crystal formation is critical to understanding the global distribution of isotopes in precipitation. Ice crystal growth in clouds is traditionally treated with a spherically- symmetric steady state diffusion model, with semi-empirical modifications added to account for ventilation and for complex crystal morphology. Although it is known that crystal growth rate, which depends largely on the degree of vapor over-saturation, determines crystal morphology, there are no existing quantitative models that directly relate morphology to the vapor saturation factor. Since kinetic (vapor phase diffusion-controlled) isotopic fractionation also depends on growth rate, there should be a direct relationship between vapor saturation, crystal morphology, and crystal isotopic composition. We use a 2D Lattice-Boltzmann model to simulate diffusion-controlled ice crystal growth from vapor- oversaturated air. In the model, crystals grow solely according to the diffusive fluxes just above the crystal surfaces, and hence crystal morphology arises from the initial and boundary conditions in the model and does not need to be specified a priori. The input parameters needed are the isotope-dependent vapor deposition rate constant (k) and the water vapor diffusivity in air (D). The values of both k and D can be computed from kinetic theory, and there are also experimentally determined values of D. The deduced values of k are uncertain to the extent that the sticking coefficient (or accommodation coefficient) for ice is uncertain. The ratio D/k is a length that determines the minimum scale of dendritic growth features and allows us to scale the numerical calculations to atmospheric conditions using a dimensionless Damkohler number: Da = kh/D, where h is the width of the 2D calculation domain. Varying the nondimensional Da in the model is equivalent to varying the scale (h) in the model. Our calculations confirm that the crystal/vapor isotopic fractionation approaches the equilibrium value, and the crystals are compact (circular in 2D) as the saturation factor approaches unity (S= 1.0). At higher oversaturation (e.g. S = 1.2), dendritic crystals of millimeter size develop on timescales appropriate to cloud processes, the isotopic fractionations are dominated by kinetic effects, and similar to those predicted by the spherical diffusion model. Dendritic crystals are constrained to be relatively large, with dimension much greater than D/k. The most difficult aspect of the modeling is to account for the large density difference between air and ice, which requires us to use a fictitious higher density for the vapor-oversaturated air and scale the crystal growth time accordingly. A different approach, using a larger scale simulation to derive boundary conditions for a nested smaller scale calculation is in progress. The results to date clarify the controls on dendritic crystal growth, the relationships between saturation state, growth rate, crystal morphology and isotopic fractionation, and provide limits on the value of the accommodation coefficient.

ACCURATE: Greenhouse Gas Profiles Retrieval from Combined IR-Laser and Microwave Occultation Measurements

NASA Astrophysics Data System (ADS)

Proschek, Veronika; Kirchengast, Gottfried; Schweitzer, Susanne; Fritzer, Johannes

2010-05-01

The new climate satellite concept ACCURATE (Atmospheric Climate and Chemistry in the UTLS Region And climate Trends Explorer) enables simultaneous measurement of profiles of greenhouse gases, isotopes, wind and thermodynamic variables from Low Earth Orbit (LEO) satellites. The measurement principle applied is a combination of the novel LEO-LEO infrared laser occultation (LIO) technique and the already better studied LEO-LEO microwave occultation (LMO) technique. Resulting occultation events are evenly distributed around the world, have high vertical resolution and accuracy and are stable over long time periods. The LIO uses near-monochromatic signals in the short-wave infrared range (~2-2.5 μm for ACCURATE). These signals are absorbed by various trace species in the Earth's atmosphere. Profiles of the concentration of the absorbing species can be derived from signal transmission measurements. Accurately known temperature, pressure and humidity profiles derived from simultaneously measured LMO signals are essential pre-information for the retrieval of the trace species profiles. These LMO signals lie in the microwave band region from 17-23 GHz and, optionally, 178-195 GHz. The current ACCURATE mission design is arranged for the measurement of six greenhouse gases (GHG) (H2O, CO2, CH4, N2O, O3, CO) and four isotopes (13CO2, C18OO, HDO, H218O), with focus on the upper troposphere/lower stratosphere region (UTLS, 5-35 km). Wind speed in line-of-sight can be derived from a line-symmetric transmission difference which is caused by wind-induced Doppler shift. By-products are information on cloud layering, aerosol extinction, and scintillation strength. We introduce the methodology to retrieve GHG profiles from quasi-realistic forward-simulated intensities of LIO signals and thermodynamic profiles retrieved in a preceding step from LMO signals. Key of the retrieval methodology is the differencing of two LIO transmission signals, one being GHG sensitive on a target absorption line and one being a close-by reference outside of any absorption lines. The reference signal is used to remove atmospheric broadband" effects by this differential absorption" approach. Refractivity and impact parameter of the LIO signals, needed for the retrieval, can be computed from the LMO-derived thermodynamic profiles. An Abel Transform converts the differential LIO log-transmission profile to the absorption coefficient. Based on the absorption coefficient and the absorption cross section of the GHG under investigation, that can as well be computed from the LMO-derived profiles, the number density profile or volume mixing ratio of the desired GHG can be finally derived. When using several LIO signals, best sensitive to the same GHG at different heights, a joint optimal GHG profile can be constructed by combining the individual profiles in an inverse-variance-weighted manner (practically used for H2O, obtained from 3-4 signals, and for CO2, obtained from 2 isotope signals). The thermodynamic parameters (temperature, pressure and humidity) derived from LMO as basis for the LIO retrieval are found to be accurate to better than 0.5 K for temperature, 0.2% for pressure, and 10% for humidity. The accuracy of retrieved trace species profiles is found better than 1% to 4% for single profiles in the UTLS region (outside clouds which block infrared) and the profiles are essentially unbiased (biases

Joint profiling of greenhouse gases, isotopes, thermodynamic variables, and wind from space by combined microwave and IR laser occultation: the ACCURATE concept

NASA Astrophysics Data System (ADS)

Kirchengast, G.; Schweitzer, S.

2008-12-01

The ACCURATE (Atmospheric Climate and Chemistry in the UTLS Region And climate Trends Explorer) mission was conceived at the Wegener Center in late 2004 and subsequently proposed in 2005 by an international team of more than 20 scientific partners from more than 12 countries to an ESA selection process for next Earth Explorer Missions. While the mission was not selected for formal pre-phase A study, it received very positive evaluation and was recommended for further development and demonstration. ACCURATE employs the occultation measurement principle, known for its unique combination of high vertical resolution, accuracy and long-term stability, in a novel way. It systematically combines use of highly stable signals in the MW 17-23/178-196 GHz bands (LEO-LEO MW crosslink occultation) with laser signals in the SWIR 2-2.5 μm band (LEO-LEO IR laser crosslink occultation) for exploring and monitoring climate and chemistry in the atmosphere with focus on the UTLS region (upper troposphere/lower stratosphere, 5-35 km). The MW occultation is an advanced and at the same time compact version of the LEO-LEO MW occultation concept, studied in 2002-2004 for the ACE+ mission project of ESA for frequencies including the 17-23 GHz band, complemented by U.S. study heritage for frequencies including the 178-196 GHz bands (R. Kursinski et al., Univ. of Arizona, Tucson). The core of ACCURATE is tight synergy of the IR laser crosslinks with the MW crosslinks. The observed parameters, obtained simultaneously and in a self-calibrated manner based on Doppler shift and differential log-transmission profiles, comprise the fundamental thermodynamic variables of the atmosphere (temperature, pressure/geopotential height, humidity) retrieved from the MW bands, complemented by line-of-sight wind, six greenhouse gases (GHGs) and key species of UTLS chemistry (H2O, CO2, CH4, N2O, O3, CO) and four CO2 and H2O isotopes (HDO, H218O, 13CO2, C18OO) from the SWIR band. Furthermore, profiles of aerosol extinction, cloud layering, and turbulence are obtained. All profiles come with accurate height knowledge (< 10 m uncertainty), since measuring height as a function of time is intrinsic to the MW occultation part of ACCURATE. The presentation will introduce ACCURATE along the lines above, with emphasis on the climate science value and the new IR laser occultation capability. The focus will then be on retrieval performance analysis results obtained so far, in particular regarding the profiles of GHGs, isotopes, and wind. The results provide evidence that the GHG and isotope profiles can generally be retrieved within 5-35 km outside clouds with < 1% to 5% rms accuracy at 1-2 km vertical resolution, and wind with < 2 m/s accuracy. Monthly mean climatological profiles, assuming ~40 profiles per climatologic grid box per month, are found unbiased (free of time-varying biases) and at < 0.2% to 0.5% rms accuracy. These encouraging results are discussed in light of the potential of the ACCURATE technique to provide benchmark data for future monitoring of climate, GHGs, and chemistry variability and change. European science and demonstration activities are outlined, including international participation opportunities.

Water stable isotope measurements of Antarctic samples by means of IRMS and WS-CRDS techniques

NASA Astrophysics Data System (ADS)

Michelini, Marzia; Bonazza, Mattia; Braida, Martina; Flora, Onelio; Dreossi, Giuliano; Stenni, Barbara

2010-05-01

In the last years in the scientific community there has been an increasing interest for the application of stable isotope techniques to several environmental problems such as drinking water safeguarding, groundwater management, climate change, soils and paleoclimate studies etc. For example, the water stable isotopes, being natural tracers of the hydrological cycle, have been extensively used as tools to characterize regional aquifers and to reconstruct past temperature changes from polar ice cores. Here the need for improvements in analytical techniques: the high request for information calls for technologies that can offer a great quantity of analyses in short times and with low costs. Furthermore, sometimes it is difficult to obtain big amount of samples (as is the case for Antarctic ice cores or interstitial water) preventing the possibility to replicate the analyses. Here, we present oxygen and hydrogen measurements performed on water samples covering a big range of isotopic values (from very negative antarctic precipitation to mid-latitude precipitation values) carried out with both the conventional Isotope Ratio Mass Spectrometry (IRMS) technique and with a new method based on laser absorption techniques, the Wavelenght Scanned Cavity Ringdown Spectroscopy (WS-CRDS). This study is focusing on improving the precision of the measurements carried out with WS-CRDS in order to extensively apply this method to Antarctic ice core paleoclimate studies. The WS-CRDS is a variation of the CRDS developed in 1988 by O'Keef and Deacon. In CRDS a pulse of light goes through a box with high reflective inner surfaces; when there is no sample in the box the light beam doesn't find any obstacle in its path, but the reflectivity of the walls is not perfect so eventually there will be an absorption of the light beam; when the sample is injected in the box there is absorption and the difference between the time of absorption without and with sample is proportional to the quantity of the sample in the box. In the WS-CRDS the path of laser is longer, producing higher-sensitivity measurements. The instrument is paired with an autosampler and can be used without it and the vaporizer to analyze directly the isotopic composition of the water vapour in the atmosphere. In addition, the instrument can be moved from the laboratory and also used for outdoor measurements. The more important improvements over traditional IRMS techniques are that WS-CRDS needs less sample in order to perform the analysis (<2 ul vs. 3/5 ml); that it doesn't need manipulation of the sample (like the gas/water equilibration techniques) and the analyses are faster. Coversely, memory effects may affect the measurements so there is the need to increase the number of injection to have a high precision measurement. The laboratory of Isotope Geochemistry of the Department of Geosciences has recently acquired a WS-CRDS system from PICARRO. The isotopic data obtained with this new method have been compared with the ones obtained by means of IRMS methods. An HDO device coupled with a Thermo Finnigan Delta Plus Advantage mass spectrometer has been used, using the well know CO2 and H2/water equilibration technique. At the moment of the writing of the abstract the mean difference between the values obtained using PICARRO and using the traditional IRMS method is of the order of 0.1 per mil for the ratio 18O/16O and 1.00 per mil for the ratio D/H, but further measurements are currently underway. O'Keef A., Deacon D.A.G., 1988. Cavity ring-down optical spectrometer for absorption measurements using pulsed laser sources, Rev. Sci. Instrum., 59, 2544.

Loss of Water to Space from Mars: Processes and Implications

NASA Astrophysics Data System (ADS)

Kass, D. M.

2001-12-01

One of the major sinks for water on Mars is the loss to space. This occurs via a complex series of processes that transport the individual atoms to the upper atmosphere, where several escape mechanisms remove them. Hydrogen and deuterium are lost primarily by Jeans escape. Non-thermal processes also remove H and D, but are only important in determining D loss at solar minimum under modern conditions. The present H loss rate is equivalent to the loss of 10-3~pr-\\micron~yr-1 of water. The loss of oxygen is more complicated. The three main processes are indirect (or ionospheric) sputtering, solar wind pickup of O+, and O2+ dissociative recombination. Their relative importance has varied over the history of Mars. The combined effect of the O loss processes is to remove a ~ 50~m global layer of water over the last 3.5 Gyr. Based on photochemical modeling, the loss of oxygen and hydrogen are balanced (over geological timescales) by a feedback process. During the early history of Mars, impact erosion and hydrodynamic blow-off may have removed significant water. But, it is difficult to estimate their quantitative effects. The transport of individual H, D and O atoms to the exosphere where they can escape is not completely understood. It occurs primarily via intermediate species, H2, HD, O2 and CO2. The H2 and HD are formed by photolysis of water and the odd hydrogen photochemistry. One open issue is the mechanism regulating the partitioning of D between HDO and HD (which controls the supply of D available for escape from the exosphere). The various loss processes isotopically enrich Martian water since the exospheric escape source region is depleted. Jeans escape and the transport from the lower atmosphere further fractionate hydrogen, the most useful isotopic system. Based on recent observations, the D/H fractionation factor, F ~ 0.02. Measurements of atmospheric water vapor indicate it is enriched in deuterium, with a D/H ratio ~ 5 times the terrestrial value. Since most of the water on Mars is likely to be in the form of ice, it is presumably further fractionated by ~ 0.8 due to ice/water vapor interactions. This yields an effective D/H enrichment of ~ 7 for reservoirs in equilibrium with the atmosphere. From a loss to space point of view, Martian water can be divided into three reservoirs. The first is the thin, 10 pr-\\micron, atmospheric water. The second is a global exchangeable reservoir in long term isotopic equilibrium with the atmosphere. This probably encompasses the polar caps, ice in polar layered deposits and any other near surface ice or adsorbed water. The third, more speculative, reservoir is a non-exchanging reservoir (a deep sub-surface cryosphere). In addition, due to the small size of the atmospheric reservoir, difficulty in isotopically equilibrating it with the entire exchangeable reservoir, and the relatively rapid H2 loss rate, there is also an intermediate exchangeable reservoir of ~ 4~mm. This is probably either a surface layer on the polar caps or near surface ice deposits. By assuming an initial terrestrial D/H ratio for Martian water (based on condritic meteorites) and a loss to space of ~ 50~m (based on the total O loss), the size of the exchangeable reservoir can be estimated. Two conceptual models are possible, depending on whether or not the non-exchangeable reservoir replenishes the exchangeable one. Quantitatively, the two models yield almost identical reservoir sizes, ~ 9~m (about the size of the northern polar cap). If, due to slow rate of isotopic diffusion in ice, the exchangeable reservoir actually has the same isotopic enrichment as the atmosphere, it would contain ~ 12~m of water.

Techno-Economic Analysis of Camelina-Derived Hydroprocessed Renewable Jet Fuel and its Implications on the Aviation Industry

NASA Astrophysics Data System (ADS)

Shila, Jacob Joshua Howard

Although the aviation industry contributes toward global economic growth via transportation of passengers and cargo, the increasing demand for air transportation causes concern due to the corresponding increase in aircraft engine exhaust emissions. Use of alternative fuels is one pathway that has been explored for reducing emissions in the aviation industry. Hydroprocessed renewable jet (HRJ) (also known as Hydroprocessed Esters and Fatty Acids - HEFA) fuels have been approved for blending with traditional jet fuel up to 50% by volume to be used as drop-in fuels. However, limited information exists on the economic viability of these fuels. While techno-economic studies have been conducted on the HRJ production process using soybean oil, different vegetable oils possess different hydrocarbon structures that affect the yield of HRJ fuels. This study involves the techno-economic analysis of producing Camelina-derived HRJ fuel using the option of hydro-deoxygenation (HDO). The hydrodeoxygenation option requires extra hydrogen and hence affects the overall cost of HRJ fuel production. Similar studies have been conducted on the production of Camelina-derived HRJ fuels using the same path of hydrodeoxygenation with minor contributions from both decarbonylation and decarboxylation reactions. This study, however, employs the UOP Honeywell procedure using the hydrodeoxygenation chemical reaction to estimate the breakeven price of Camelina-derived HRJ fuel. In addition, the study treats the cultivation of Camelina oilseeds, extraction of oilseeds, and the conversion of HRJ fuel as separate entities. The production of Camelina oilseed, Camelina oil, and finally Camelina-derived HRJ fuel is modeled in order to estimate the breakeven price of the fuel. In addition, the information obtained from the techno-economic analysis is used to assess the breakeven carbon price. All costs are analyzed based on 2016 US dollars. The breakeven price of Camelina oilseeds is found to be 228.71 per MT assuming a yield of 2.3 MT/hectare and oilseed oil content of 35%. The nameplate capacities of the extraction and HRJ process facilities are 3000 MT/day and 378 MML per year respectively. Based on these assumptions, the breakeven price of Camelina oil for a centralized extraction facility is found to be 0.35 per liter for a 20-year operating plant, and 0.34/liter for a 30-year operating plant. The option of producing Jet A and diesel are each explored for plants operating for 20 years or 30 years. An additional scenario of investing in a hydrogen plant on site is explored. The deterministic breakeven price of HRJ fuel produced from plants that operate for 20 years is found to be 0.87 per liter for facilities using commercial hydrogen, and 1.01 per liter for facilities using self-produced hydrogen. If the plant operates for 30 years, the breakeven price of HRJ is found to be 0.85 per liter for a facility that uses utility hydrogen, and 0.99 per liter for a facility that uses self-produced hydrogen. Sensitivity analysis indicates that if the HRJ facility invests in hydrogen plant, the final breakeven price will range from 0.87 to 1.44 per liter while for the facility that uses commercial hydrogen, the breakeven price of HRJ fuel will be between 0.75 and 1.26 per liter. Investors have to pay at least additional 0.02 of capital investment cost per liter of HRJ fuel if they want to maximize the production of HRJ fuel instead of Hydroprocessed Renewable Diesel (HRD) fuel. The penalty for investing in a hydrogen plant on site ranges between 0.13 and 0.15 of capital cost per liter of fuel produced depending on the main fuel being produced and the duration of operation of the plant. Finally, the breakeven price of carbon is calculated by taking into account the difference between the calculated breakeven price of HRJ fuels and the five-year average of Jet A fuel. The range of breakeven carbon price is found to be between 109.63 and 177.53 per MT of CO2e. The results of this study serve as a preliminary assessment for investors who are interested in pursuing production of this fuel type. While the breakeven prices of the fuels may provide information to the potential investors, the breakeven carbon prices are also useful for exploring other policies regarding the establishment of aviation biofuels.

Hydrodesulfurization on Transition Metal Catalysts: Elementary Steps of C-S Bond Activation and Consequences of Bifunctional Synergies

NASA Astrophysics Data System (ADS)

Yik, Edwin Shyn-Lo

The presence of heteroatoms (e.g. S, N) in crude oil poses formidable challenges in petroleum refining processes as a result of their irreversible binding on catalytically active sites at industrially relevant conditions. With increasing pressures from legislation that continues to lower the permissible levels of sulfur content in fuels, hydrodesulfurization (HDS), the aptly named reaction for removing heteroatoms from organosulfur compounds, has become an essential feedstock pretreatment step to remove deleterious species from affecting downstream processing. Extensive research in the area has identified the paradigm catalysts for desulfurization; MoSx or WSx, promoted with Co or Ni metal; however, despite the vast library of both empirical and fundamental studies, a clear understanding of site requirements, the elementary steps of C-S hydrogenolysis, and the properties that govern HDS reactivity and selectivity have been elusive. While such a lack of rigorous assessments has not prevented technological advancements in the field of HDS catalysis, fundamental interpretations can inform rational catalyst and process design, particularly in light of new requirements for "deep" desulfurization and in the absence of significant hydrotreatment catalyst developments in recent decades. We report HDS rates of thiophene, which belongs to a class of compounds that are most resistant to sulfur removal (i.e. substituted alkyldibenzothiophenes), over a range of industrially relevant temperatures and pressures, measured at differential conditions and therefore revealing their true kinetic origins. These rates, normalized by the number of exposed metal atoms, on various SiO 2-supported, monometallic transition metals (Re, Ru, Pt), range several orders of magnitude. Under relevant HDS conditions, Pt and Ru catalysts form a layer of chemisorbed sulfur on surfaces of a metallic bulk, challenging reports that assume the latter exists as its pyrite sulfide phase during reaction. While convergence to a single phase is expected and predictable from thermodynamics at a given temperature and sulfur chemical potential, metastability of two phases can exist. We demonstrate, through extensive characterization and kinetic evidence, such behaviors exist in Re, where structural disparities between its phases lead to kinetic hurdles that prevent interconversions between layered ReSx nanostructures and sulfur-covered Re metal clusters. Such features allowed, for the first time, direct comparisons of reaction rates at identical conditions on two disparate phases of the same transition metal identity. Rigorous assessments of kinetic and selectivity data indicated that more universal mechanistic features persist across all catalysts studied, suggesting that differences in their catalytic activity were the result of different densities of HDS sites, which appeared to correlate with their respective metal-sulfur bond energies. Kinetic responses and product distributions indicated that the consumption of thiophene proceeds by the formation of a partially-hydrogenated surface intermediate, which subsequently produces tetrahydrothiophene (THT) and butene/butane (C4) via primary routes on similar types of sites. These sites are formed from desorption of weakly-bound sulfur adatoms on sulfur-covered metal surfaces, which can occur when the heat of sulfur adsorption is sufficiently low at high sulfur coverage as a result of increased sulfur-sulfur repulsive interactions. Relative stabilities and differences in the molecularity of the respective transition states that form THT and C4 dictate product distributions. THT desulfurization to form C4 occurs via readsorption and subsequent dehydrogenation, evidenced by secondary rates that exhibited negative H2 dependences. These behaviors suggest that C-S bond activation occurs on a partially (un)saturated intermediate, analogous to behaviors observed in C-C bond scission reactions of linear and cycloalkanes on hydrogen-covered metal surfaces. Our interpretations place HDS in a specific class of more general C-X hydrogenolysis reactions, including hydrodeoxygenation (HDO) that has gained popular appeal in recent biomass conversion processes. These hydrodearomatization routes, hydrogenolysis and hydrogenation, act as probes for studying hydrogen spillover, a frequently observed phenomenon in bifunctional systems. Indeed, we observe enhancements solely in the rates of thiophene hydrogenation when monofunctional catalysts, which generate equilibrated concentrations of surface H-species, are mixed with materials (e.g. Al 2O3) that cannot dissociate H2. Conventional mechanisms that suggest gas phase or surface diffusion of atomic H-species (or H +-e- pairs) are implausible across distances along insulating surfaces (i.e. SiO2, Al2O3). We propose, with kinetic-transport models that are consistent with all observed behaviors, that mobility of active H-species occurs through gas phase diffusion of thiophene-derived molecular H-carriers, whose formation rate on HDS sites can control maximum spillover enhancements. This synergy is disrupted when the ability of thiophene to form these H-carriers is suppressed, leading to an absence of spillover-mediated rates and further challenging any diffusive roles of atomic H-species. Such implications help guide optimal designs of bifunctional cascades to permit the uninhibited access and egress of larger molecules within both catalytic functions. (Abstract shortened by UMI.).

Obituary: William Merz Sinton, 1925-2004

NASA Astrophysics Data System (ADS)

Spencer, John Robert

2004-12-01

Bill Sinton, one of the pioneers of infrared planetary astronomy, died at his home in Flagstaff, Arizona, on March 16th 2004, at the age of 78. Bill was born in Baltimore on April 11, 1925. He developed lifelong interests in railroads and radios while still a child, and by age 15 he had already built a shortwave radio receiver and won his ham radio license. His abiding interest in electronic and mechanical devices would serve him well in his professional career. He fought with the 26th Infantry Division in the Second World War and was wounded in France in October 1944. After the war he obtained his bachelor's degree in physics at Johns Hopkins (1949). His doctoral work at the same institution, with John Strong, gave him his first taste of infrared astronomy, including the first measurements of the moon at 1-millimeter wavelength. He obtained his PhD, on the infrared spectrum and temperature of Venus, in 1953. During a 1-year postdoc at Johns Hopkins he probed the lunar subsurface by observing the cooling of the moon during eclipse at millimeter wavelengths, and observed the diurnal variation in Martian surface temperatures in the 10-micron window. He joined Harvard College Observatory as a research associate and lecturer in 1954, and became interested in the question of life on Mars and the then-plausible possibility that Mars's dark markings were due to vegetation. In 1956, using a monochromator that he built himself, he detected absorptions near 3.4 microns in the Martian spectrum which he attributed to a C-H stretch transition in Martian vegetation. These "Sinton bands," as they came to be known, sparked great interest at the time, and though at least some of the spectral structure was later found to be due to terrestrial HDO, and the presence of abundant organic molecules on the Martian surface was finally ruled out by the Viking landers, some of the spectral features that he detected appear to be intrinsic to Mars and are still not well understood. In 1957, Bill moved to Lowell Observatory, and spent the next nine years there. He considered these to be the most productive years of his career. In his time at Lowell, he continued his studies of the Moon's thermal emission, and built an infrared Michelson interferometer spectrometer that he put to use in identifying the 3.1-micron water of hydration band on Mars. He also met and married his wife Marge in 1960, and their three sons, Bob, David, and Alan were born during the Flagstaff years. In 1965, Bill was invited by John Jefferies to join the faculty of the University of Hawaii, and to help in the development of the fledgling Mauna Kea Observatory. His work on the design the 88-inch telescope on Mauna Kea, the cornerstone of the observatory, included designing its telescope control system, making it one of the first computer-controlled optical telescopes. His scientific work at the Institute for Astronomy included continued studies of Mars, with his PhD student Terry Martin, as well as the infrared spectrum of Uranus and Neptune. He sometimes translated his pseudocolored maps of the thermal emission from the planets, pixel by pixel, into the unique medium of stained glass. In 1979, following the discovery of Io's volcanoes by Voyager, he obtained some of the first ground-based observations of the infrared thermal emission from the volcanoes. He devoted the last decade of his career to the ground-based study of Io's volcanoes, working to characterize their time variability and developing techniques to identify their locations on Io. He was one of the founding members of the International Jupiter Watch in 1987, and was the first leader of its Satellite Discipline. When he retired from the University of Hawaii in 1990, he and Marge returned to Flagstaff, and he renewed his association with Lowell Observatory as an adjunct astronomer. He built a miniature steam-powered railroad around his house, to the delight of the neighborhood children who would get to ride on it on special occasions. In 1993 he was diagnosed with ALS (Lou Gehrig's disease), and was confined to a wheelchair shortly afterwards, but he continued to attend scientific meetings, and to contribute to Lowell Observatory as a member of its Advisory Board, till shortly before his death. In 2002 he published an autobiography, I Choose to Live, which described his life and his battle with ALS. Because he could no longer use a keyboard he wrote the entire book using voice-recognition software- a testament to his determination to keep as active and productive as possible despite the encroachments of the disease.We remember Bill as a warm, gentle, and enthusiastic man with an encyclopedic knowledge of all things infrared. He had a love of mechanical gadgets of all types, whether he was designing plumbing for a He3 cooled germanium bolometer or for a model steam engine. He is greatly missed by his family, friends, and former colleagues. Within two weeks of Bill's death came the announcement that CH4 gas had been discovered on Mars by the Mars Express spacecraft, confirming similar results from ground-based telescopes. The methane, touted as possible evidence for extant Martian life, was discovered via its 3.3-micron C-H stretch band. This is essentially the same vibrational transition, potentially carrying the same hints of living Martian organisms, which Bill thought he had seen on Mars 45 years earlier. So while Bill's initial conclusion that Mars is covered with extensive vegetation turned out to be wrong, his insight that the 3-micron region, with its telltale signature of carbon-hydrogen bonds, was the best place to search for evidence of life on our sister world, may have been right all along.