Growth of CH3NH3PbI3 Perovskite on Stainless Steel Substrate Layered by ZnO Nanoparticles Using One-Step Spin Coating Route

NASA Astrophysics Data System (ADS)

Fuad, A.; Fibriyanti, A. A.; Mufti, N.; Taufiq, A.; Maryam, S.; Hidayat, N.

2018-04-01

In this work, we report the preparation of CH3NH3PbI3 perovskite using one-step spin coating route for solar cell application. CH3NH3I• PbI2•DMF•DMSO complexes were coated on stainless steel as a subtrate layered by ZnO nanoparticles as an electron transport layer. To obtain samples with a special performance, we annealed the samples at a temperature of 100, 120, and 140°C for 10 minutes. The samples were then characterized by means of XRD, SEM/EDX, and Spectroscopic Ellipsometry. The analysis of XRD data presented that the CH3NH3PbI3 perovskites were successfully prepared and crystallized in tetragonal structure confirming from crystalline planes (110) and (220). Meanwhile, the particle size of the samples prepared at a temperature of 100, 120, and 140°C presented 42.96, 54.73, and 55.19 nm, respectively with coincide with the SEM images. The results indicated that the increase in temperature during synthesis influenced the particle growth. Furthermore, the characterization using Spectroscopic Ellipsometry exhibited that the CH3NH3PbI3 successfully layered on the substrate sizing nano metric scale that open high opportunity to be applied to solar cells with high performance.

Fully relativistic pseudopotential formalism under an atomic orbital basis: spin-orbit splittings and magnetic anisotropies.

PubMed

Cuadrado, R; Cerdá, J I

2012-02-29

We present an efficient implementation of the spin-orbit coupling within the density functional theory based SIESTA code (2002 J. Phys.: Condens. Matter 14 2745) using the fully relativistic and totally separable pseudopotential formalism of Hemstreet et al (1993 Phys. Rev. B 47 4238). First, we obtain the spin-orbit splittings for several systems ranging from isolated atoms to bulk metals and semiconductors as well as the Au(111) surface state. Next, and after extensive tests on the accuracy of the formalism, we also demonstrate its capability to yield reliable values for the magnetic anisotropy energy in magnetic systems. In particular, we focus on the L1(0) binary alloys and on two large molecules: Mn(6)O(2)(H -sao)(6)(O(2)CH)(2)(CH(3)OH)(4) and Co(4)(hmp)(4)(CH(3)OH)(4)Cl(4). In all cases our calculated anisotropies are in good agreement with those obtained with full-potential methods, despite the latter being, in general, computationally more demanding.

Degradation of poly(2-hydroxyethyl methacrylate) by gamma irradiation

NASA Astrophysics Data System (ADS)

Hill, David J. T.; O'Donnell, James H.; Pomery, Peter J.; Saadat, Giti

1996-11-01

Electron Spin Resinance (ESR) spectroscopy has been utilised to examine the effect of high energy radiation on poly(2-hydroxyethyl methacrylate) PHEMA. Radiation chemical yields ( G-values) for radicals were 1.7 and 1.2 for γ-irradiation at 77 K and ambient temperature, respectively. The ESR spectra at 77 and 300 K were simulated. The ESR spectrum at 77 K is a combination of six types of radicals ·CH 3, ·CH 2CH 2OH, COOCHCH 2OH, ·COO-, -CH- and ·CHO. However, after room temperature irradiation, the spectrum is a combination of methacrylate main chain scission radical and -CH-. The high stability of this radical at room temperature indicates the system is very rigid as a result of hydrogen bonding from the inherent side chain structure and radiation induced crosslinking due to labile hydrogen atoms in the side chain.

Experimental observation of chiral magnetic bobbers in B20-type FeGe

NASA Astrophysics Data System (ADS)

Zheng, Fengshan; Rybakov, Filipp N.; Borisov, Aleksandr B.; Song, Dongsheng; Wang, Shasha; Li, Zi-An; Du, Haifeng; Kiselev, Nikolai S.; Caron, Jan; Kovács, András; Tian, Mingliang; Zhang, Yuheng; Blügel, Stefan; Dunin-Borkowski, Rafal E.

2018-06-01

Chiral magnetic skyrmions1,2 are nanoscale vortex-like spin textures that form in the presence of an applied magnetic field in ferromagnets that support the Dzyaloshinskii-Moriya interaction (DMI) because of strong spin-orbit coupling and broken inversion symmetry of the crystal3,4. In sharp contrast to other systems5,6 that allow for the formation of a variety of two-dimensional (2D) skyrmions, in chiral magnets the presence of the DMI commonly prevents the stability and coexistence of topological excitations of different types7. Recently, a new type of localized particle-like object—the chiral bobber (ChB)—was predicted theoretically in such materials8. However, its existence has not yet been verified experimentally. Here, we report the direct observation of ChBs in thin films of B20-type FeGe by means of quantitative off-axis electron holography (EH). We identify the part of the temperature-magnetic field phase diagram in which ChBs exist and distinguish two mechanisms for their nucleation. Furthermore, we show that ChBs are able to coexist with skyrmions over a wide range of parameters, which suggests their possible practical applications in novel magnetic solid-state memory devices, in which a stream of binary data bits can be encoded by a sequence of skyrmions and bobbers.

Proton spin-lattice relaxation in low-dimensional ferromagnetic copper halides (abstract)

NASA Astrophysics Data System (ADS)

Marzke, R. F.; Haines, D. N.; Raffaelle, D. P.; Chamberlin, R. V.; Ramakrishna, B. L.

1991-04-01

1H spin-lattice relaxation times have been measured as functions of temperature and frequency in powder samples of the two-dimensional ferromagnetic compound (CH3NH3)2CuCl4 and in single crystals of the one-dimensional ferromagnets (C6H11NH3)CuB3 (CHAB), (C6H11NH3)CuCl3 (CHAC), and (C4H12N)CuCl3 (TMCuC). Sample temperatures were varied between 4.2 and 298 K, and NMR frequencies ranging from 12.6 to 54.0 MHz were used. Widths and shapes of the lines, typically several hundred Gauss broad at low temperatures, were recorded. The dependence of T1 upon magnetic field orientation was measured for the one-dimensional (1D) single crystal samples. Each compound showed basically two temperature regimes of different spin-lattice relaxation behavior, separated by a narrow transition temperature region. From 4.2 K, T1 in the compounds decreased strongly as the temperature was raised, a behavior expected for second-order Raman processes [K. M. Kopinga, A. M. C. Tinus, W. J. M. de Jonge, and G. C. de Vries, Phys. Rev. B 36, 5398 (1987)]. At the transition temperature region the decrease of T1 ceased, and T1 began to increase weakly and quasilinearly to 300 K. In the three 1D compounds, the transition regions occurred well below temperatures corresponding to 1D exchange interaction strengths in CHAC (˜70 K), CHAB (˜55 K), and TMCuC (˜30 K), and also above the compounds' 3D ordering temperatures (˜1.5 K and below). We noted a correlation between the T1 transition temperatures and temperatures at which spin dimensionality ``crossovers'' are observed in magnetic susceptibilities, going from Heisenberg to non-Heisenberg behavior as the temperature is decreased. The latter occur at approximately 10 K in CHAC. TMCuC, which has the most isotropic J tensor of these compounds and also the lowest weak-strong T1 transition, does not show a spin dimensionality crossover in susceptibility down to 2 K, but based on our NMR results one would be expected at or below this temperature. Further theoretical work appears to be necessary in order to elucidate the role of magnons and solitons in the transition behavior of the temperature dependence of T1.

C/2013 R1 (Lovejoy) at IR wavelengths and the variability of CO abundances among Oort Cloud comets

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

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

2014-08-20

We report production rates, rotational temperatures, and related parameters for gases in C/2013 R1 (Lovejoy) using the Near InfraRed SPECtrometer at the Keck Observatory, on six UT dates spanning heliocentric distances (R{sub h} ) that decreased from 1.35 AU to 1.16 AU (pre-perihelion). We quantified nine gaseous species (H{sub 2}O, OH*, CO, CH{sub 4}, HCN, C{sub 2}H{sub 6}, CH{sub 3}OH, NH{sub 3}, and NH{sub 2}) and obtained upper limits for two others (C{sub 2}H{sub 2} and H{sub 2}CO). Compared with organics-normal comets, our results reveal highly enriched CO, (at most) slightly enriched CH{sub 3}OH, C{sub 2}H{sub 6}, and HCN, andmore » CH{sub 4} consistent with {sup n}ormal{sup ,} yet depleted, NH{sub 3}, C{sub 2}H{sub 2}, and H{sub 2}CO. Rotational temperatures increased from ∼50 K to ∼70 K with decreasing R{sub h} , following a power law in R{sub h} of –2.0 ± 0.2, while the water production rate increased from 1.0 to 3.9 × 10{sup 28} molecules s{sup –1}, following a power law in R{sub h} of –4.7 ± 0.9. The ortho-para ratio for H{sub 2}O was 3.01 ± 0.49, corresponding to spin temperatures (T {sub spin}) ≥ 29 K (at the 1σ level). The observed spatial profiles for these emissions showed complex structures, possibly tied to nucleus rotation, although the cadence of our observations limits any definitive conclusions. The retrieved CO abundance in Lovejoy is more than twice the median value for comets in our IR survey, suggesting this comet is enriched in CO. We discuss the enriched value for CO in comet C/2013 R1 in terms of the variability of CO among Oort Cloud comets.« less

The Design of The Monitoring Tools Of Clean Air Condition And Dangerous Gas CO, CO2 CH4 In Chemical Laboratory By Using Fuzzy Logic Based On Microcontroller

NASA Astrophysics Data System (ADS)

Widodo, Slamet; Miftakul, Amin M.; Sutrisman, Adi

2018-02-01

There are many phenomena that human are exposed to toxins from certain types such as of CO2, CO2 and CH4 gases. The device used to detect large amounts of CO, CO2, and CH4 gas in air in enclosed spaces using MQ 135 gas sensors of different types based on the three sensitivity of the Gas. The results of testing the use of sensors MQ 135 on the gas content of CO, CO2 and CH4 received by the sensor is still in the form of ppm based on the maximum ppm detection range of each sensor. Active sensor detects CO 120 ppm gas, CO2 1600 ppm and CH4 1ppm "standby 1" air condition with intermediate rotary fan. Active sensor detects CO 30 ppm gas, CO2 490 ppm and CH4 7 ppm "Standby 2" with low rotating fan output. Fuzzy rulebase logic for motor speed when gas detection sensor CO, CO2, and CH4 output controls the motion speed of the fan blower. Active sensors detect CO 15 ppm, CO2 320 ppm and CH4 45 ppm "Danger" air condition with high fan spin fan. At the gas level of CO 15 ppm, CO2 390 ppm and CH4 3 ppm detect "normal" AC sensor with fan output stop spinning.

Dielectric properties and electrical conductivity of the hybrid organic-inorganic polyvanadates (H{sub 3}N(CH{sub 2}){sub 4}NH{sub 3})[V{sub 6}O{sub 14}

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

Nefzi, H.; Sediri, F., E-mail: faouzi.sediri@ipeit.rnu.tn; Faculte des Sciences de Tunis, Universite Tunis El Manar, 2092 El Manar, BP 94 CEDEX 1068, Cite Rommana Tunis

2012-06-15

Plate-like crystals of the polyvanadate (H{sub 3}N(CH{sub 2}){sub 4}NH{sub 3})[V{sub 6}O{sub 14}] have been synthesized via an hydrothermal treatment. X-ray powder diffraction, scanning electron microscope, Fourier transform infrared spectroscopy, electron spin resonance and complex impedance spectroscopy were used to analyze the hybrid material. The frequency dependence of AC conductivity at different temperatures indicates that the CBH model is the probable mechanism for the AC conduction behavior. The conductivity was measured by complex impedance spectroscopy which is equal to 31.10{sup -3} {Omega}{sup -1} m{sup -1} at 443 K. The Arrhenius diagram is not linear, it presents a rupture situated at 357more » K and the activation energies' average values are 0.22 eV and 0.14 eV, deduced from the Arrhenius relation. - Graphical abstract: At high temperature {epsilon} Double-Prime increases more rapidly which is due to the increasing conduction loss which rises with the increment in the DC conductivity. Highlights: Black-Right-Pointing-Pointer Rectangular plate-like crystals (H{sub 3}N(CH{sub 2}){sub 4}NH{sub 3})[V{sub 6}O{sub 14}] were synthesized. Black-Right-Pointing-Pointer frequency and temperature dependence of AC conductivity indicate CBH model. Black-Right-Pointing-Pointer The temperature dependence of DC conductivity exhibits two conduction mechanisms.« less

Thermotropic phase behavior of choline soaps.

PubMed

Klein, Regina; Dutton, Helen; Diat, Olivier; Tiddy, Gordon J T; Kunz, Werner

2011-04-14

Choline carboxylates (ChCm with m = 12-18) are simple biocompatible anionic surfactants with very low Krafft temperatures, possessing a rich aqueous phase behavior. In the present work, we have investigated the thermotropic mesomorphism of anhydrous ChCm salts for m = 12-18. Transition temperatures and enthalpies determined by differential scanning calorimetry reveal that all investigated compounds exhibit three different phases between -20 and 95 °C. The phases were further characterized by optical polarizing microscopy, NMR spin-spin relaxation, and X-ray scattering measurements. The nature of the phases was identified with increasing temperature as crystalline, semicrystalline, and liquid-crystalline lamellar. Even long-chain choline carboxylates (m = 18) were found to melt into a lamellar liquid-crystalline phase below 100 °C. Accordingly, with choline as counterion in simple fatty acid soaps, not only the water solubility is considerably enhanced but also the melting points are substantially reduced, hence facilitating thermotropic mesomorphism at temperatures between 35 and 95 °C. Thus, simple choline soaps with m = 12-18 may be classified as ionic liquids.

Structural features of a bituminous coal and their changes during low-temperature oxidation and loss of volatiles investigated by advanced solid-state NMR spectroscopy

USGS Publications Warehouse

Mao, J.-D.; Schimmelmann, A.; Mastalerz, Maria; Hatcher, P.G.; Li, Y.

2010-01-01

Quantitative and advanced 13C solid-state NMR techniques were employed to investigate (i) the chemical structure of a high volatile bituminous coal, as well as (ii) chemical structural changes of this coal after evacuation of adsorbed gases, (iii) during oxidative air exposure at room temperature, and (iv) after oxidative heating in air at 75 ??C. The solid-state NMR techniques employed in this study included quantitative direct polarization/magic angle spinning (DP/MAS) at a high spinning speed of 14 kHz, cross polarization/total sideband suppression (CP/TOSS), dipolar dephasing, CH, CH2, and CHn selection, 13C chemical shift anisotropy (CSA) filtering, two-dimensional (2D) 1H-13C heteronuclear correlation NMR (HETCOR), and 2D HETCOR with 1H spin diffusion. With spectral editing techniques, we identified methyl CCH 3, rigid and mobile methylene CCH2C, methine CCH, quaternary Cq, aromatic CH, aromatic carbons bonded to alkyls, small-sized condensed aromatic moieties, and aromatic C-O groups. With direct polarization combined with spectral-editing techniques, we quantified 11 different types of functional groups. 1H-13C 2D HETCOR NMR experiments indicated spatial proximity of aromatic and alkyl moieties in cross-linked structures. The proton spin diffusion experiments indicated that the magnetization was not equilibrated at a 1H spin diffusion time of 5 ms. Therefore, the heterogeneity in spatial distribution of different functional groups should be above 2 nm. Recoupled C-H long-range dipolar dephasing showed that the fraction of large charcoal-like clusters of polycondensed aromatic rings was relatively small. The exposure of this coal to atmospheric oxygen at room temperature for 6 months did not result in obvious chemical structural changes of the coal, whereas heating at 75 ??C in air for 10 days led to oxidation of coal and generated some COO groups. Evacuation removed most volatiles and caused a significant reduction in aliphatic signals in its DP/MAS spectrum. DP/MAS, but not CP/MAS, allowed us to detect the changes during low-temperature oxidation and loss of volatiles. These results demonstrate the applicability of advanced solid-state NMR techniques in chemical characterization of coal. ?? 2010 American Chemical Society.

Hydrogen-bonding effect on spin-center transfer of tetrathiafulvalene-linked 6-oxophenalenoxyl evaluated using temperature-dependent cyclic voltammetry and theoretical calculations.

PubMed

Nishida, Shinsuke; Fukui, Kozo; Morita, Yasushi

2014-02-01

The stable tetrathiafulvalene (TTF)-linked 6-oxophenalenoxyl neutral radical exhibits a spin-center transfer with a continuous color change in solution caused by an intramolecular electron transfer, which is dependent on solvent and temperature. Cyclic voltammetry measurements showed that addition of 2,2,2-trifluoroethanol (TFE) to a benzonitrile solution of the neutral radical induces a redox potential shift that is favorable for the spin-center transfer. Temperature-dependent cyclic voltammetry of the neutral radical using a novel low-temperature electrochemical cell demonstrated that the redox potentials change with decreasing temperature in a 199:1 CH2Cl2/TFE mixed solvent. Furthermore, theoretical calculation revealed that the energy levels of the frontier molecular orbitals involved in the spin-center transfer are lowered by the hydrogen-bonding interaction of TFE with the neutral radical. These results indicate that the hydrogen-bonding effect is a key factor for the occurrence of the spin-center transfer of TTF-linked 6-oxophenalenoxyl. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

THE VOLATILE COMPOSITION OF COMET C/2003 K4 (LINEAR) AT NEAR-IR WAVELENGTHS—COMPARISONS WITH RESULTS FROM THE NANÇAY RADIO TELESCOPE AND FROM THE ODIN, SPITZER, AND SOHO SPACE OBSERVATORIES

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

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

2015-07-20

We observed comet C/2003 K4 (LINEAR) using NIRSPEC at the Keck Observatory on UT 2004 November 28, when the comet was at 1.28 AU from the Sun (post-perihelion) and 1.38 AU from Earth. We detected six gaseous species (H{sub 2}O, OH*, C{sub 2}H{sub 6}, CH{sub 3}OH, CH{sub 4}, and HCN) and obtained upper limits for three others (H{sub 2}CO, C{sub 2}H{sub 2}, and NH{sub 3}). Our results indicate a water production rate of (1.72 ± 0.18) × 10{sup 29} molecules s{sup −1}, in reasonable agreement with production rates from SOHO (on the same day), Odin (one day earlier), and Nançaymore » (about two weeks earlier). We also report abundances (relative to water) for seven trace species: CH{sub 3}OH (∼1.8%), CH{sub 4} (∼0.9%), and C{sub 2}H{sub 6} (∼0.4%) that were consistent with mean values among Oort cloud (OC) comets, while NH{sub 3} (<0.55%), HCN (∼0.07%), H{sub 2}CO (<0.07%), and C{sub 2}H{sub 2} (<0.04%) were “lower” than the mean values in other OC comets. We extracted inner-coma rotational temperatures for four species (H{sub 2}O, C{sub 2}H{sub 6}, CH{sub 3}OH, and CH{sub 4}), all of which are consistent with 70 K (within 1σ). The extracted ortho-para ratio for water was 3.0 ± 0.15, corresponding to spin temperatures larger than 39 K (at the 1σ level) and agreeing with those obtained with the Spitzer Space Telescope at the 2σ level.« less

Synthesis of ZnO thin film by sol-gel spin coating technique for H2S gas sensing application

NASA Astrophysics Data System (ADS)

Nimbalkar, Amol R.; Patil, Maruti G.

2017-12-01

In this present work, zinc oxide (ZnO) thin film synthesized by a simple sol-gel spin coating technique. The structural, morphology, compositional, microstructural, optical, electrical and gas sensing properties of the film were studied by using XRD, FESEM, EDS, XPS, HRTEM, Raman, FTIR and UV-vis techniques. The ZnO thin film shows hexagonal wurtzite structure with a porous structured morphology. Gas sensing performance of synthesized ZnO thin film was tested initially for H2S gas at different operating temperatures as well as concentrations. The maximum gas response is achieved towards H2S gas at 300 °C operating temperature, at 100 ppm gas concentration as compared to other gases like CH3OH, Cl2, NH3, LPG, CH3COCH3, and C2H5OH with a good stability.

Magnetic Field Effects in Hybrid Perovskite Devices

NASA Astrophysics Data System (ADS)

Zhang, C.; Sun, D.; Sheng, C.-X.; Zhai, Y.; Mielczarek, K.; Zakhidov, A.; Vardeny, Z. V.

2015-03-01

Solar cells based on the organic-inorganic perovskites (CH3NH3PbX3, X =halogen) have reached a remarkable power conversion efficiency approaching 20%, which calls for research studies of the photophysics behind this high device performance. We measured significant magneto-photocurrent (MPC) response in CH3NH3PbI3-xClx photovoltaic cells, in the form of Lorentzian up to field B = 1T. We attribute the MPC(B) response to spin mixing of loosely-bound photogenerated e-h pairs having different g-factor (dubbed `` Δg mechanism''). We verified this mechanism by measuring Δg directly, using the field induced circularly polarized photoluminescence emission at low temperature, along with the photocarriers' lifetime measured by picosecond pump-probe spectroscopy. We conclude that MPC of spin 1/2 e-h pairs provides a promising method for investigating the spin-related properties of photoexcitations in the novel hybrid perovskites.

DISCOVERY OF METHYL ACETATE AND GAUCHE ETHYL FORMATE IN ORION

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

Tercero, B.; Cernicharo, J.; Lopez, A.

2013-06-10

We report on the discovery of methyl acetate, CH{sub 3}COOCH{sub 3}, through the detection of a large number of rotational lines from each one of the spin states of the molecule: AA species (A{sub 1} or A{sub 2}), EA species (E{sub 1}), AE species (E{sub 2}), and EE species (E{sub 3} or E{sub 4}). We also report, for the first time in space, the detection of the gauche conformer of ethyl formate, CH{sub 3}CH{sub 2}OCOH, in the same source. The trans conformer is also detected for the first time outside the Galactic center source SgrB2. From the derived velocity ofmore » the emission of methyl acetate, we conclude that it arises mainly from the compact ridge region with a total column density of (4.2 {+-} 0.5) Multiplication-Sign 10{sup 15} cm{sup -2}. The derived rotational temperature is 150 K. The column density for each conformer of ethyl formate, trans and gauche, is (4.5 {+-} 1.0) Multiplication-Sign 10{sup 14} cm{sup -2}. Their abundance ratio indicates a kinetic temperature of 135 K for the emitting gas and suggests that gas-phase reactions could participate efficiently in the formation of both conformers in addition to cold ice mantle reactions on the surface of dust grains.« less

Free radical generation by non-equilibrium atmospheric pressure plasma in alcohol-water mixtures: an EPR-spin trapping study

NASA Astrophysics Data System (ADS)

Uchiyama, Hidefumi; Ishikawa, Kenji; Zhao, Qing-Li; Andocs, Gabor; Nojima, Nobuyuki; Takeda, Keigo; Krishna, Murali C.; Ishijima, Tatsuo; Matsuya, Yuji; Hori, Masaru; Noguchi, Kyo; Kondo, Takashi

2018-03-01

Free radical species in aqueous solution—various alcohol-water reaction mixtures—by exposure to non-equilibrium cold atmospheric pressure Ar plasma (CAP), were monitored using electron paramagnetic resonance spin-trapping techniques with 3, 5-dibromo-4-nitrosobenzene sulfonate as a water soluble nitroso spin trap. The major radical species were formed by H-abstraction from alcohol molecules due to ·OH radicals. In the ethanol-water mixture ·CH2CH2OH produced by H abstraction from CH3 group of the ethanol and ·CH3 radicals were detected. The latter was due to the decomposition of unstable CH3·CHOH to form the ·CH3 radicals and the stable formaldehyde by C-C bond fission. These intermediates are similar to those observed by reaction with ·OH radicals generation in the H2O2-UV photolysis of the reaction mixtures. The evidence of ·CH3 radical formation in the pyrolytic decomposition of the reaction mixtures by exposure to ultrasound or in methane irradiated with microwave plasma have been reported previously. However, the pyrolytic ·CH3 radicals were not found in both plasma and H2O2-UV photolysis condition. These results suggests that free radicals produced by Ar-CAP are most likely due to the reaction between abundant ·OH radicals and alcohol molecules.

Temperature and Mechanisms of Methane Transport in Trees

NASA Astrophysics Data System (ADS)

Kutschera, E.; Khalil, A. K.; Rice, A. L.; Rosenstiel, T. N.; Butenhoff, C. L.

2012-12-01

The mechanisms of methane (CH4) transport through trees are still not well understood. Previous work has established that transport mechanisms likely differ from rice and emergent aquatic plants. Establishing the role of trees in overall plant CH4 emissions requires a thorough understanding of tree transport. Using stable isotope measurements of CH4 assists in elucidating these transport mechanisms. Although it has been shown that CH4 is transported through the stems of trees, emission from leaves by transpiration has not been ruled out. The effect of temperature on these mechanisms is important to the prediction of changes in CH4 emissions from the biosphere in altered global climates. The effect of temperature on methane (CH4) emitted from black cottonwood (Populus trichocarpa) trees has been measured. Trees were grown hydroponically under greenhouse conditions. After several months of growth, CH4 canopy flux was measured over three weeks. Temperatures were altered from 22oC the first week to 25oC the second week and to 18oC the final week. CH4 flux increased with temperature, where the difference in flux between the coolest and warmest week was statistically significant. A Q10 for CH4 flux from trees was calculated to be 2.7. Stable carbon isotope measurements of emitted CH4 were enriched at the warmest temperature compared to the coolest temperature, although all measurements were depleted with respect to the isotopic composition of root water CH4. This data not only gives insight into the temperature effects on CH4 flux from trees, but the mechanisms of CH4 flux themselves. This research was supported in part by the Office of Science (BER), U. S. Department of Energy, Grant No. DE-FG02-08ER64515, and through NASA / Oregon Space Grant Consortium, grants NNG05GJ85H and NNX10AK68H.

Optogalvanic spectroscopy of the C"5Pi ui-A' 5Sigma+g electronic system of N2.

PubMed

Pirali, O; Tokaryk, D W

2006-11-28

We have recorded spectra involving the 3-1, 4-2, 2-0, and 2-2 bands of the C" 5Pi(ui)-A' (5)Sigma+(g) electronic system of N(2) using optogalvanic detection in a discharge through a supersonic jet expansion of argon mixed with a trace of nitrogen gas. The spectra have an effective rotational temperature of about 45 K. They involve all five spin-orbit components of the C" 5Pi(ui) state, which has allowed for precise determination of the spin-orbit coupling in this state. Analysis of the C" 5Pi(ui) state Lambda-doubling shows that it is caused primarily by a first-order spin-spin effect rather than by interaction with Sigma(u) (+/-) states. Our results allow us to assign lines in the 4-2 and 2-0 bands observed in a fluorescence depletion experiment conducted over ten years ago [Ch. Ottinger and A. F. Vilesov, J. Chem. Phys. 103, 9929 (1995)], and to comment on the suggestion that perturbations to the C (3)Pi(u) v=1 level of N(2) arise from interactions with the C" 5Pi(ui) state.

Spin-crossover phenomena of the mononuclear Mn(III) complex tuned by metal dithiolene counteranions.

PubMed

Chen, Ying; Cao, Fan; Wei, Rong-Min; Zhang, Yang; Zhang, Yi-Quan; Song, You

2014-03-07

Three ion-pair complexes based on spin-crossover [Mn(5-Br-sal-N-1,5,8,12)]ClO4 with TBA2[Ni(mnt)2], TBA2[Pt(mnt)2] (mnt = maleonitriledithiolate) and TBA[Ni(dmit)2] respectively (dmit = 2-thioxo-1,3-dithiole-4,5-dithiolato) have been synthesized and structurally characterized. Complexes [Mn(5-Br-sal-N-1,5,8,12)]2[Ni(mnt)2] and [Mn(5-Br-sal-N-1,5,8,12)]2[Pt(mnt)2] are isomorphic and show the axial compression of the octahedral coordination environment of Mn(III) ions. With the temperature increasing the equatorial metal-ligand bond lengths show significant elongation, but the axial bond lengths remain unchanged. Complex [Mn(5-Br-sal-N-1,5,8,12)][Ni(dmit)2]·CH3CN contains π-π, p-π and H-bonds weak interactions. Magnetic investigation shows the spin-crossover phenomena for and , and T1/2 has been increased by 230 K comparing with the reactant complex. However, no spin-crossover was observed in complex , and theoretical calculations show that there are weak antiferromagnetic couplings mediated through π-π interactions.

Survey for Ortho-to-Para Abundance Ratios (OPRs) of NH2 in Comets: Revisit to the Meaning of OPRs of Cometary Volatiles

NASA Astrophysics Data System (ADS)

Kawakita, Hideyo; Shinnaka, Yoshiharu; Jehin, Emmanuel; Decock, Alice; Hutsemekers, Damien; Manfroid, Jean

2016-10-01

Since molecules having identical protons can be classified into nuclear-spin isomers (e.g., ortho-H2O and para-H2O for water) and their inter-conversions by radiative and non-destructive collisional processes are believed to be very slow, the ortho-to-para abundance ratios (OPRs) of cometary volatiles such as H2O, NH3 and CH4 in coma have been considered as primordial characters of cometary molecules [1]. Those ratios are usually interpreted as nuclear-spin temperatures although the real meaning of OPRs is in strong debate. Recent progress in laboratory studies about nuclear-spin conversion in gas- and solid-phases [2,3] revealed short-time nuclear-spin conversions for water, and we have to reconsider the interpretation for observed OPRs of cometary volatiles. We have already performed the survey for OPRs of NH2 in more than 20 comets by large aperture telescopes with high-resolution spectrographs (UVES/VLT, HDS/Subaru, etc.) in the optical wavelength region [4]. The observed OPRs of ammonia estimated from OPRs of NH2, cluster around ~1.1 (cf. 1.0 as a high-temperature limit), indicative of ~30 K as nuclear-spin temperatures. We present our latest results for OPRs of cometary NH2 and discuss about the real meaning of OPRs of cometary ammonia, in relation to OPRs of water in cometary coma. Chemical processes in the inner coma may play an important role to achieve un-equilibrated OPRs of cometary volatiles in coma.This work was financially supported by MEXT Supported Program for the Strategic Research Foundation at Private Universities, 2014-2018 (No. S1411028) (HK) and by Graint-in-Aid for JSPS Fellows, 15J10864 (YS).References:[1] Mumma & Charnley, 2011, Annu. Rev. Astro. Astrophys. 49, 471.[2] Hama & Watanabe, 2013, Chem. Rev. 113, 8783.[3] Hama et al., 2008, Science 351, 6268.[4] Shinnaka et al., 2011, ApJ 729, 81.

Cr[(H3N-(CH2)2-PO3)(Cl)(H2O)]: X-ray single-crystal structure and magnetism of a polar organic-inorganic hybrid chromium(II) organophosphonate.

PubMed

Bauer, Elvira M; Bellitto, Carlo; Colapietro, Marcello; Portalone, Gustavo; Righini, Guido

2003-10-06

Cr[(H(3)N-(CH(2))(2)-PO(3))(Cl)(H(2)O)], a rare example of a polar organic-inorganic hybrid material containing Cr(2+), was prepared from CrCl(2), 2-aminoethylphosphonic acid, and urea in water and isolated as light-blue crystals. It crystallizes in the noncentrosymmetric monoclinic space group P2(1), with a = 5.249(1) A, b = 14.133(3) A, c = 5.275(1) A, and beta = 105.55(2) degrees. The inorganic layer of the hybrid network is formed by Cr(II) five-coordinated by three oxygen atoms from the phosphonates and one from the water molecule in a square pyramidal unit, whose apical position is occupied by the Cl(-) ion. Hydrogen bonds are established between the coordinating water molecule and the oxygen atoms of adjacent phosphonate ligands. The inorganic network is interspersed by ethylammonium groups, and the terminal ammonium moiety is linked to the apical Cl(-) ions through hydrogen bonds. Electrostatic interactions as well as hydrogen bonds and the coordinated chlorine atoms ensure the cohesion of the 3D structure. The lattice is polar (lack of inversion center), and this fact determines the magnetic behavior of the compound at low temperatures. The magnetic susceptibility data in the temperature range from 300 to 50 K show Curie-Weiss behavior, with C = 2.716 cm(3) K mol(-1) and the Weiss constant theta = -2.2 K. The corresponding effective magnetic moment of 4.7 mu(B) compares well with the expected value for Cr(2+) in d(4) high-spin configuration. A slight decrease of the chiT product versus T observed at temperatures below 50 K indicates nearest-neighbor antiferromagnetic exchange interactions. On cooling below T = 6 K, the magnetic susceptibility increases sharply up to a maximum at ca. 5 K and then decreases again. Below T = 6 K, hysteresis loops taken at different temperatures show that Cr[(H(3)N-(CH(2))(2)-PO(3))(Cl)(H(2)O)] behaves as a weak ferromagnet with the critical temperature T(N) at 5.5 K. The spin canting is responsible of the long-range magnetic ordering. The values of the coercive field, H(c), and of remnant magnetization, M(r), obtained from the hysteresis loop at T = 4.5 K (the lowest measured temperature) are 30 Oe and 0.08 mu(B), respectively.

Searching for trans ethyl methyl ether in Orion KL★,★★

PubMed Central

Tercero, B.; Cernicharo, J.; López, A.; Brouillet, N.; Kolesniková, L.; Motiyenko, R. A.; Margulès, L.; Alonso, J. L.; Guillemin, J.-C.

2015-01-01

We report on the tentative detection of trans ethyl methyl ether (tEME), t-CH3CH2OCH3, through the identification of a large number of rotational lines from each one of the spin states of the molecule towards Orion KL. We also search for gauche-trans-n-propanol, Gt-n-CH3CH2CH2OH, an isomer of tEME in the same source. We have identified lines of both species in the IRAM 30 m line survey and in the ALMA Science Verification data. We have obtained ALMA maps to establish the spatial distribution of these species. Whereas tEME mainly arises from the compact ridge component of Orion, Gt-n-propanol appears at the emission peak of ethanol (south hot core). The derived column densities of these species at the location of their emission peaks are ≤(4.0 ± 0.8) × 1015 cm−2 and ≤(1.0 ± 0.2)× 1015 cm−2 for tEME and Gt-n-propanol, respectively. The rotational temperature is ~100 K for both molecules. We also provide maps of CH3OCOH, CH3CH2OCOH, CH3OCH3, CH3OH, and CH3CH2OH to compare the distribution of these organic saturated O-bearing species containing methyl and ethyl groups in this region. Abundance ratios of related species and upper limits to the abundances of non-detected ethers are provided. We derive an abundance ratio N(CH3OCH3)/N(tEME) ≥ 150 in the compact ridge of Orion. PMID:26869726

Searching for trans ethyl methyl ether in Orion KL.

PubMed

Tercero, B; Cernicharo, J; López, A; Brouillet, N; Kolesniková, L; Motiyenko, R A; Margulès, L; Alonso, J L; Guillemin, J-C

2015-10-01

We report on the tentative detection of trans ethyl methyl ether (tEME), t-CH 3 CH 2 OCH 3 , through the identification of a large number of rotational lines from each one of the spin states of the molecule towards Orion KL. We also search for gauche-trans-n-propanol, Gt-n-CH 3 CH 2 CH 2 OH, an isomer of tEME in the same source. We have identified lines of both species in the IRAM 30 m line survey and in the ALMA Science Verification data. We have obtained ALMA maps to establish the spatial distribution of these species. Whereas tEME mainly arises from the compact ridge component of Orion, Gt-n-propanol appears at the emission peak of ethanol (south hot core). The derived column densities of these species at the location of their emission peaks are ≤(4.0 ± 0.8) × 10 15 cm -2 and ≤(1.0 ± 0.2)× 10 15 cm -2 for tEME and Gt-n-propanol, respectively. The rotational temperature is ~100 K for both molecules. We also provide maps of CH 3 OCOH, CH 3 CH 2 OCOH, CH 3 OCH 3 , CH 3 OH, and CH 3 CH 2 OH to compare the distribution of these organic saturated O-bearing species containing methyl and ethyl groups in this region. Abundance ratios of related species and upper limits to the abundances of non-detected ethers are provided. We derive an abundance ratio N (CH 3 OCH 3 )/ N (tEME) ≥ 150 in the compact ridge of Orion.

Highly Depleted Ethane and Slightly Depleted Methanol in Comet 21P/Giacobini-Zinner: Application of Empirical g-Factors for CH3OH Near 50K

NASA Technical Reports Server (NTRS)

DiSanti, Michael A.; Bonev, Boncho P.; Mumma, Michael J.; Villanueva, Geronimo L.

2010-01-01

We report high resolution (lambda/delta lambda approximately 24,000) observations of Comet 21 P/Giacobini-Zinner (21P) between approximately 2.85 -- 3.54 micrometers, obtained with NIRSPEC at Keck 2 on UT 2005 June 03 (R(sub h) = 1.12 AU, delta = 1.45 AU). These simultaneously sampled multiple emissions from the v7 band of C2H6 and the v2 and v3 bands of CH3OH, together with several hot bands of H2O, permitting a direct measure of parent volatile abundances in 21P. Our spectra reveal highly depleted C2H6 (0.13-0.14 percent relative to H2O) and CH3OH/C2H6 approximately 10, consistent with previously published abundances from observations in the IR [1,2] and millimeter sub-mm (reporting CH3OH/H2O [3]) during its previous apparition in 1998. We observed similarly high CH3OH/C2H6, and also similar rotational temperature to that measured for 21 P, in Comet 8P/Tuttle [4,5]. We used our (higher signal-to-noise) NIRSPEC observations of 8P to produce effective (empirical) CH3OH g-factors for several lines in the v2 band. These will be presented together with interpretation of our results, including constraints on the spin temperature of water. We acknowledge support from the NASA Planetary Atmospheres, Planetary Astronomy, and Astrobiology Programs and from the NSF Astronomy and Astrophysics Research Grants Program.

Magnetic resonances in perovskite-type layer structures

NASA Astrophysics Data System (ADS)

Strobel, K.; Geick, R.

1981-08-01

We have studied the q=0 magnetic excitations of the perovskite-type layer structures A 2MnCl 4 with A=Rb, C nH 2n+1NH 3 (n=1,2,3), and NH 3(CH 2) mNH 3MnCl 4 (m=2,4,5) in the antiferromagnetic and in the spin flop regime by means of magnetic resonance in the mm-wave range (30-130GHz) and microwave range (9.2GHz). The length of the organic molecules determines the separation of the MnCl 6 octahedra. With increasing separation the Néel temperature and the antiferromagnetic resonance frequency decrease, which mainly originates from a decrease of the anisotropy field.

Local structural order and relaxation effects in metal-chalcogenide glasses

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

Saleh, Z.M.

1990-01-01

Nuclear quadrupole resonance (NQR) and nuclear magnetic resonance (NMR) have been employed to study the local structural order and the relaxation mechanisms in metal-arsenic-chalcogenide glasses for metal concentrations within the glass forming region. The glass forming region in the Cu-As-S and Cu-As-se glassy systems extends approximately to 6 and 25 at. % copper, respectively. In the composition Cu[sub x](As[sub 2/5]Ch[sub 3/5])[sub 1[minus]x], where Ch = S or Se, there is evidence of dramatic changes in the local structure as copper is added to the system. One important change is the formation of As-As bonds which are absent in As[sub 2]Ch[submore » 3]. The [sup 75]As NQR measurements indicate that the density of these bonds increases with copper concentration x. These results are consistent with the predictions of a model proposed recently to explain the local structural order in glassy metal chalcogenides. While NQR data show that arsenic atoms are threefold coordinated, EXAFs measurements have shown that copper is fourfold coordinated within the glass forming ranges in both systems. The NMR measurements confirm this result and quantitatively determine the local environment around the copper nuclei. For the naturally occurring mineral luzonite (Cu[sub 3]AsS[sub 4]) copper is fourfold coordinated. The known structure of this mineral has been used as a guide to understanding the local structure in the glasses. Copper and arsenic nuclear relaxation measurements were used to study the dynamics of these systems. The temperature and frequency dependence of the spin-lattice and spin-spin relaxation times have been carefully measured to determine the relaxation mechanisms.« less

Climate change impact of livestock CH4 emission in India: Global temperature change potential (GTP) and surface temperature response.

PubMed

Kumari, Shilpi; Hiloidhari, Moonmoon; Kumari, Nisha; Naik, S N; Dahiya, R P

2018-01-01

Two climate metrics, Global surface Temperature Change Potential (GTP) and the Absolute GTP (AGTP) are used for studying the global surface temperature impact of CH 4 emission from livestock in India. The impact on global surface temperature is estimated for 20 and 100 year time frames due to CH 4 emission. The results show that the CH 4 emission from livestock, worked out to 15.3 Tg in 2012. In terms of climate metrics GTP of livestock-related CH 4 emission in India in 2012 were 1030 Tg CO 2 e (GTP 20 ) and 62 Tg CO 2 e (GTP 100 ) at the 20 and 100 year time horizon, respectively. The study also illustrates that livestock-related CH 4 emissions in India can cause a surface temperature increase of up to 0.7mK and 0.036mK over the 20 and 100 year time periods, respectively. The surface temperature response to a year of Indian livestock emission peaks at 0.9mK in the year 2021 (9 years after the time of emission). The AGTP gives important information in terms of temperature change due to annual CH 4 emissions, which is useful when comparing policies that address multiple gases. Copyright © 2017 Elsevier Inc. All rights reserved.

BariumCopperChFluorine (Ch = Sulfur, Selenium, Tellurium) p-type transparent conductors

NASA Astrophysics Data System (ADS)

Zakutayev, Andriy

BaCuChF (Ch = S, Se, Te) materials are chalcogen-based transparent conductors with wide optical band gaps (2.9 -- 3.5 eV) and a high concentration of free holes (1018 -- 1020 cm-3 ) caused by the presence of copper vacancies. Chalcogen vacancies compensate copper vacancies in these materials, setting the Fermi level close to the valence band maximum. BaCuChF thin film solid solutions prepared by pulsed laser deposition (PLD) have tunable properties, such as lattice constants, conductivity and optical band gaps. BaCuSF and BaCuSeF materials also feature room-temperature stable 3D excitons with spin-orbit-split levels. BaCuTeF has forbidden lowest-energy optical transitions which extends its transparency range. BaCuChF surfaces oxidize when exposed to air, but can be protected using Ch capping layers. Polycrystalline BaCuSeF thin films have a 4.85 eV work function, a 0.11 eV hole injection barrier into ZnPc, and 0.00 eV valence band offset with ZnTe. BaCuSeF should have s similar band offset and similar interfacial properties with CdTe and Cu(InGa)Se2, and BaCuSF should have no valence band offset with Cu2ZnSnS4, according to the transitivity rule. Therefore, BaCuSeF is suitable for applications as a p-layer in organic light-emitting diodes, p-i-n double-heterojunction and tandem chalcogenide solar cells.

Theoretical Study of the Jahn-Teller effect in CH3CN+ (X2E) and CD3CN+ (X2E): multimode spin-vibronic energy level calculations.

PubMed

Zhang, Shiyang; Mo, Yuxiang

2009-10-15

The spin-vibronic energy levels for CH(3)CN(+)(X(2)E) and CD(3)CN(+)(X(2)E) have been calculated using a diabatic model including multimode vibronic couplings and spin-orbit interaction without adjusting any parameter. The diabatic potential energy surfaces are represented by the Taylor expansions including linear, quadratic and bilinear vibronic coupling terms. The normal coordinates used in the Taylor expansion were expressed by the mass-weighted Cartesian coordinates. The adiabatic potential energy surfaces for CH(3)CN(+) and CD(3)CN(+) were calculated at the level of CASPT2/cc-pvtz, and the spin-orbit coupling constant was calculated at the level of MRCI/CAS/cc-pvtz. The spin-orbit energy splittings for the ground vibrational states of CH(3)CN(+)(X(2)E) and CD(3)CN(+)(X(2)E) are 20 and 16 cm(-1), respectively, which are resulted from the quenching of the spin-orbit coupling strength of 51 cm(-1). The calculated spin-vibronic levels are in good agreement with the experimental data. The calculation results show that the Jahn-Teller effects in CH(3)CN(+)(X(2)E) and CD(3)CN(+)(X(2)E) are essential to understand their spin-vibronic energy structure.

A two-state computational investigation of methane C--H and ethane C--C oxidative addition to [CpM(PH3)]n+ (M = Co, Rh, Ir; n = 0, 1).

PubMed

Petit, Alban; Richard, Philippe; Cacelli, Ivo; Poli, Rinaldo

2006-01-11

Reductive elimination of methane from methyl hydride half-sandwich phosphane complexes of the Group 9 metals has been investigated by DFT calculations on the model system [CpM(PH(3))(CH(3))(H)] (M = Co, Rh, Ir). For each metal, the unsaturated product has a triplet ground state; thus, spin crossover occurs during the reaction. All relevant stationary points on the two potential energy surfaces (PES) and the minimum energy crossing point (MECP) were optimized. Spin crossover occurs very near the sigma-CH(4) complex local minimum for the Co system, whereas the heavier Rh and Ir systems remain in the singlet state until the CH(4) molecule is almost completely expelled from the metal coordination sphere. No local sigma-CH(4) minimum was found for the Ir system. The energetic profiles agree with the nonexistence of the Co(III) methyl hydride complex and with the greater thermal stability of the Ir complex relative to the Rh complex. Reductive elimination of methane from the related oxidized complexes [CpM(PH(3))(CH(3))(H)](+) (M = Rh, Ir) proceeds entirely on the spin doublet PES, because the 15-electron [CpM(PH(3))](+) products have a doublet ground state. This process is thermodynamically favored by about 25 kcal mol(-1) relative to the corresponding neutral system. It is essentially barrierless for the Rh system and has a relatively small barrier (ca. 7.5 kcal mol(-1)) for the Ir system. In both cases, the reaction involves a sigma-CH(4) intermediate. Reductive elimination of ethane from [CpM(PH(3))(CH(3))(2)](+) (M = Rh, Ir) shows a similar thermodynamic profile, but is kinetically quite different from methane elimination from [CpM(PH(3))(CH(3))(H)](+): the reductive elimination barrier is much greater and does not involve a sigma-complex intermediate. The large difference in the calculated activation barriers (ca. 12.0 and ca. 30.5 kcal mol(-1) for the Rh and Ir systems, respectively) agrees with the experimental observation, for related systems, of oxidatively induced ethane elimination when M = Rh, whereas the related Ir systems prefer to decompose by alternative pathways.

Reaction of the Mo3S4 cluster with dimethylacetylenedicarboxylate: an ESR-active cluster and an organometallic cluster formed by alpha,beta-conjugate addition.

PubMed

Ide, Yasuhiro; Shibahara, Takashi

2007-01-22

A seven-electron cluster [Mo3(mu3-S){mu3-SC(CO(2)CH(3))=C(CO(2)CH(3))S}{mu-SC(CO(2)CH(3))=CH(CO(2)CH(3))}(dtp)3(mu-OAc)] [2, S2P(OC(2)H(5))2-; dtp = diethyldithiophosphate] and an organometallic cluster [Mo3(mu3-S){mu3-SC(CO(2)CH(3))=C(CO(2)CH(3))S}{mu-SC(CO(2)CH(3))CH(OCH(3))(CO2)}(dtp)2(CH(3)OH)(mu-OAc)](Mo-C) (3) were obtained by reaction in methanol of the sulfur-bridged trinuclear complex [Mo3(mu3-S)(mu-S)3(dtp)3(CH(3)CN)(mu-OAc)] (1) with dimethylacetylenedicarboxylate (DMAD). The X-ray structures of 2 and 3 revealed the adduct formation of two DMAD molecules to the respective Mo(3)S(4) cores. 2 is paramagnetic and obeys the Curie-Weiss law: the mu(eff) value at 300 K is 1.90 muB. The electron spin resonance signal was observed at 173 K. The density functional theory calculation of 2 demonstrated that the main components of the singly occupied molecular orbitals of alpha and beta spins are Mo d electrons and the main components of lowest unoccupied molecular orbitals are of Mo and the olefin moiety with one C-S bond. A one-electron reversible oxidation process of 2 was observed at E1/2 = -0.11 V vs Fc/Fc+. The electronic spectrum of 2 has a peak at 468 nm (epsilon = 2170 M(-1) cm(-1)) and shoulders at 640 (918) and 797 (605) nm, and 3 has shoulders at 441 (1740) and 578 (625) nm and a distinct peak at 840 (467) nm. An intermediate [Mo3(mu3-S){mu3-SC(CO(2)CH(3))=C(CO(2)CH(3))S}{mu-SC(CO(2)CH(3))=CH(CO(2)CH(3))}(dtp)3(mu-OAc)]+ (4) is tentatively suggested: a one-electron reduction of 4 gives 2, and a nucleophilic conjugate addition of CH(3)O- to the alpha,beta-unsaturated carbonyl group of 4 gives 3.

Collisional excitation of CH2 rotational/fine-structure levels by helium

NASA Astrophysics Data System (ADS)

Dagdigian, P. J.; Lique, F.

2018-02-01

Accurate determination of the abundance of CH2 in interstellar media relies on both radiative and collisional rate coefficients. We investigate here the rotational/fine-structure excitation of CH2 induced by collisions with He. We employ a recoupling technique to generate fine-structure-resolved cross-sections and rate coefficients from close coupling spin-free scattering calculations. The calculations are based on a recent, high-accuracy CH2-He potential energy surface computed at the coupled clusters level of theory. The collisional cross-section calculations are performed for all fine-structure transitions among the first 22 and 24 energy levels of ortho- and para-CH2, respectively, and for temperatures up to 300 K. As a first application, we simulate the excitation of CH2 in typical molecular clouds. The excitation temperatures of the CH2 lines are found to be small at typical densities of molecular clouds, showing that the non-local thermodynamic equilibrium approach has to be used to analyse interstellar spectra. We also found that the fine-structure lines connected with the 404 - 313 and 505 - 414 rotational transitions show possible maser emissions so that they can be easily seen in emission. These calculations show that CH2 may have to be detected mainly through absorption spectra.

Methane fluxes show consistent temperature dependence across microbial to ecosystem scales.

PubMed

Yvon-Durocher, Gabriel; Allen, Andrew P; Bastviken, David; Conrad, Ralf; Gudasz, Cristian; St-Pierre, Annick; Thanh-Duc, Nguyen; del Giorgio, Paul A

2014-03-27

Methane (CH4) is an important greenhouse gas because it has 25 times the global warming potential of carbon dioxide (CO2) by mass over a century. Recent calculations suggest that atmospheric CH4 emissions have been responsible for approximately 20% of Earth's warming since pre-industrial times. Understanding how CH4 emissions from ecosystems will respond to expected increases in global temperature is therefore fundamental to predicting whether the carbon cycle will mitigate or accelerate climate change. Methanogenesis is the terminal step in the remineralization of organic matter and is carried out by strictly anaerobic Archaea. Like most other forms of metabolism, methanogenesis is temperature-dependent. However, it is not yet known how this physiological response combines with other biotic processes (for example, methanotrophy, substrate supply, microbial community composition) and abiotic processes (for example, water-table depth) to determine the temperature dependence of ecosystem-level CH4 emissions. It is also not known whether CH4 emissions at the ecosystem level have a fundamentally different temperature dependence than other key fluxes in the carbon cycle, such as photosynthesis and respiration. Here we use meta-analyses to show that seasonal variations in CH4 emissions from a wide range of ecosystems exhibit an average temperature dependence similar to that of CH4 production derived from pure cultures of methanogens and anaerobic microbial communities. This average temperature dependence (0.96 electron volts (eV)), which corresponds to a 57-fold increase between 0 and 30°C, is considerably higher than previously observed for respiration (approximately 0.65 eV) and photosynthesis (approximately 0.3 eV). As a result, we show that both the emission of CH4 and the ratio of CH4 to CO2 emissions increase markedly with seasonal increases in temperature. Our findings suggest that global warming may have a large impact on the relative contributions of CO2 and CH4 to total greenhouse gas emissions from aquatic ecosystems, terrestrial wetlands and rice paddies.

Atmospheric CH4 oxidation by Arctic permafrost and mineral cryosols as a function of water saturation and temperature.

PubMed

Stackhouse, B; Lau, M C Y; Vishnivetskaya, T; Burton, N; Wang, R; Southworth, A; Whyte, L; Onstott, T C

2017-01-01

The response of methanotrophic bacteria capable of oxidizing atmospheric CH 4 to climate warming is poorly understood, especially for those present in Arctic mineral cryosols. The atmospheric CH 4 oxidation rates were measured in microcosms incubated at 4 °C and 10 °C along a 1-m depth profile and over a range of water saturation conditions for mineral cryosols containing type I and type II methanotrophs from Axel Heiberg Island (AHI), Nunavut, Canada. The cryosols exhibited net consumption of ~2 ppmv CH 4 under all conditions, including during anaerobic incubations. Methane oxidation rates increased with temperature and decreased with increasing water saturation and depth, exhibiting the highest rates at 10 °C and 33% saturation at 5 cm depth (260 ± 60 pmol CH 4 gdw -1 d -1 ). Extrapolation of the CH 4 oxidation rates to the field yields net CH 4 uptake fluxes ranging from 11 to 73 μmol CH 4  m -2 d -1 , which are comparable to field measurements. Stable isotope mass balance indicates ~50% of the oxidized CH 4 is incorporated into the biomass regardless of temperature or saturation. Future atmospheric CH 4 uptake rates at AHI with increasing temperatures will be determined by the interplay of increasing CH 4 oxidation rates vs. water saturation and the depth to the water table during summer thaw. © 2016 John Wiley & Sons Ltd.

Formation of doubly and triply bonded unsaturated compounds HCN, HNC, and CH2NH via N + CH4 low-temperature solid state reaction: from molecular clouds to solar system objects

NASA Astrophysics Data System (ADS)

Mencos, Alejandro; Krim, Lahouari

2018-06-01

We show in the current study carried out in solid phase at cryogenic temperatures that methane (CH4) ice exposed to nitrogen atoms is a source of two acids HCN, HNC, and their corresponding hydrogenated unsaturated species CH2NH, in addition to CH3, C2H6, CN-, and three nitrogen hydrides NH, NH2, and NH3. The solid state N + CH4 reaction taken in the ground state seems to be strongly temperature dependent. While at temperatures lower than 10 K only CH3, NH, NH2, and NH3 species formation is promoted due to CH bond dissociation and NH bond formation, stable compounds with CN bonds are formed at temperatures ranged between 10 and 40 K. Many of these reaction products, resulting from CH4 + N reaction, have already been observed in N2-rich regions such as the atmospheres of Titan, Kuiper belt objects, and molecular clouds of the interstellar medium. Our results show the power of the solid state N-atom chemistry in the transformation of simple astrochemical relevant species, such as CH4 molecules and N atoms into complex organic molecules which are also potentially prebiotic species.

Investigating temperature effects on methane production and oxidation in the rice ecosystem using stable carbon and hydrogen isotope ratios

NASA Astrophysics Data System (ADS)

Rice, A. L.; Sithole, A.; Shearer, M. J.; Hanson, E.; Fisher, A.; Khalil, A. K.

2010-12-01

Irrigated rice is a major agricultural source of methane emissions that contributes about 15% of global atmospheric methane (CH4). Our work investigates the relationships between temperature and CH4 production, oxidation, and flux in the rice ecosystem. This is central to understanding the response of the global CH4 emissions from rice under a changing climate. Temperatures were regulated in sixteen rice plots grown in a research greenhouse using four waterbath-temperature control systems held at 20°C, 24°C, 28°C, and 32°C over the course of a growing season. Belowground porewater samples were collected from each treatment weekly and CH4 was extracted into headspace N2 after vigorous shaking. Weekly flux samples were collected using acrylic static flux chambers placed over the rice plots. CH4 concentrations below and aboveground were measured using gas chromatography-flame ionization detection. The carbon (δ13C) and hydrogen (δD) isotopic composition of CH4 was measured using continuous-flow gas chromatography isotope ratio mass spectrometry. Results show that CH4 flux ranged from near zero to 30-60 mg/m2/hr in mid-season corresponding to a rise in porewater CH4 to 8-12 mg/L. Early season CH4 fluxes were larger in elevated temperature treatments but this difference was smaller, or even reversed in some cases, in the late season. Similar trends were observed in CH4 porewater concentration profiles. Results from isotopic measurements show mean belowground δ13C values between -44‰ and -52‰ relative to VPDB and δD values between -290‰ and -320‰ relative to VSMOW. Emitted CH4 had mean δ13C values which ranged from -50‰ to -60‰ VPDB. We integrate these results and interpret them using an empirically-driven concentration and isotope model to understand CH4 dynamics and to examine the effect of temperature on mechanisms that control CH4 emissions.

Dielectric Study of the Phase Transitions in [P(CH3)4]2CuY4 (Y = Cl, Br)

NASA Astrophysics Data System (ADS)

Gesi, Kazuo

2002-05-01

Phase transitions in [P(CH3)4]2CuY4 (Y = Cl, Br) have been studied by dielectric measurements. In [P(CH3)4]2CuCl4, a slight break and a discontinuous jump on the dielectric constant vs. temperature curve are seen at the normal-incommensurate and the incommensurate-commensurate phase transitions, respectively. A small peak of dielectric constant along the b-direction exists just above the incommensurate-to-commensurate transition temperature. The anisotropic dielectric anomalies of [P(CH3)4]2CuBr4 at phase transitions were measured along the three crystallographic axes. The pressure-temperature phase diagram of [P(CH3)4]2CuCl4 was determined. The initial pressure coefficients of the normal-to-incommensurate and the incommensurate-to-commensurate transition temperatures are 0.19 K/MPa and 0.27 K/MPa, respectively. The incommensurate phase in [P(CH3)4]2CuCl4 disappears at a triple point which exists at 335 MPa and 443 K. The stability and the pressure effects of the incommensurate phases are much different among the four [Z(CH3)4]2CuY4 crystals (Z = N, P; Y = Cl, Br).

Effects of shifting growth stage and regulating temperature on seasonal variation of CH4 emission from rice

NASA Astrophysics Data System (ADS)

Watanabe, Akira; Yamada, Hiromi; Kimura, Makoto

2001-09-01

Seasonal variations in CH4 emission rates from rice paddies have been reported to have one or more maxima during the middle and late periods of rice growth. The factor affecting an appearance of CH4 emission maxima was examined in three types of pot experiments. In the experiment 1, four rice cultivars with difference in length of the period from transplanting to heading were transplanted on the same days. For the experiment 2, a cultivar was transplanted 4 times with interval of two weeks. In these experiments, the heading differed about a month between the earliest and latest treatments, respectively. However, shifting growth stage of rice plants did not shift the CH4 emission maxima, and the CH4 emission maxima often matched the maxima of daily mean air temperature. The effect of variation in temperature on CH4 emission rate was further investigated in the experiment 3 by placing the rice-planted pots under regulated temperature. Besides the first emission peak of CH4 attributable to rice straw (RS) carbon, three emission peaks corresponding to the peaks of air temperature were detected for the RS-applied pots placed outdoors. These three peaks were not observed or much less conspicuous for the RS-applied pots in a phytotron at 30°C. Temporal decreases in CH4 emission were detected both for the pots placed in the phytotron and outdoors just after the topdressing of (NH4)2SO4, which was considered to be a major cause of irregular disagreement between the variations in CH4 emission rates and in air temperature during the middle period of rice growth.

Electron spin resonance of (CO 2 H)CH 2 CH 2 CH(CO 2 H) in irradiated glutaric acid

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

Horsfield, A.; Morton, J. R.; Whiffen, D. H.

It is concluded from electron spin resonance spectra that the radical (CO 2 H)CH 2 CH 2 CH(CO 2 H) remains trapped in a glutaric acid crystal after gamma -irradiation. This radical is found in two different conformations. Approximate hyperfine coupling constants are given for each, although exact interpretation is hindered by the overlapping of spectra. Reasons for the formation of the two forms of the radical are discussed.

A comparative DFT study of interactions of Au and small gold clusters Aun (n = 2-4) with CH3S and CH2 radicals

NASA Astrophysics Data System (ADS)

Blaško, Martin; Rajský, Tomáš; Urban, Miroslav

2017-03-01

We compare DFT binding energies (BEs) of Au and small gold clusters interacting with CH3S and CH2 ligands (Aun-L complexes, n = 1-4). The spin state and the binding mechanism in Aun-L varies with the participation of singly occupied non-bonding orbitals or doubly occupied lone-pair orbitals of a ligand and on the number of atoms (even or odd) of Aun. The highest BE, 354 kJ/mol, exhibits the Au3-CH2 complex with the covalent bond in which participate two singly occupied orbitals of the triplet state of CH2. With CH3S the highest BE (277 kJ/mol) is calculated for Au3-SCH3 with the single Au-S bond.

NMR spin-rotation relaxation and diffusion of methane

NASA Astrophysics Data System (ADS)

Singer, P. M.; Asthagiri, D.; Chapman, W. G.; Hirasaki, G. J.

2018-05-01

The translational diffusion-coefficient and the spin-rotation contribution to the 1H NMR relaxation rate for methane (CH4) are investigated using MD (molecular dynamics) simulations, over a wide range of densities and temperatures, spanning the liquid, supercritical, and gas phases. The simulated diffusion-coefficients agree well with measurements, without any adjustable parameters in the interpretation of the simulations. A minimization technique is developed to compute the angular velocity for non-rigid spherical molecules, which is used to simulate the autocorrelation function for spin-rotation interactions. With increasing diffusivity, the autocorrelation function shows increasing deviations from the single-exponential decay predicted by the Langevin theory for rigid spheres, and the deviations are quantified using inverse Laplace transforms. The 1H spin-rotation relaxation rate derived from the autocorrelation function using the "kinetic model" agrees well with measurements in the supercritical/gas phase, while the relaxation rate derived using the "diffusion model" agrees well with measurements in the liquid phase. 1H spin-rotation relaxation is shown to dominate over the MD-simulated 1H-1H dipole-dipole relaxation at high diffusivity, while the opposite is found at low diffusivity. At high diffusivity, the simulated spin-rotation correlation time agrees with the kinetic collision time for gases, which is used to derive a new expression for 1H spin-rotation relaxation, without any adjustable parameters.

The addition of iodine to tetramethylammonium iodide

USGS Publications Warehouse

Foote, H.W.; Fleischer, M.

1953-01-01

The system tetramethylammonium iodide-iodine-toluene has been studied by the solubility method at 6 and at 25??. The compounds (CH3)4NI3, (CH3)4NI5 and (CH3)4NI11 were found to be stable phases at both temperatures. In addition, the compound (CH3)4NI10 was found at 6?? and the compound (CH3)4NI9 at 25??. The dissociation pressures of the compounds at these temperatures were calculated from the solubility data.

The temperature response of methane emission in Arctic wet sedge tundra

NASA Astrophysics Data System (ADS)

Lim, Edward; Zona, Donatella

2015-04-01

Since the last glacial maximum Arctic tundra soils have acted as an important carbon sink, having accumulated carbon under cold, anaerobic conditions (Zona et al. 2009). Several studies indicate that recent climate warming has altered this balance, with the Arctic tundra now posited to be a significant annual source of atmospheric methane (CH4) (McGuire et al. 2012). Nonetheless, the response of Arctic tundra CH4 fluxes to continued climate warming remains uncertain. Laboratory and field studies indicate that CH4 fluxes are temperature sensitive, thus accurate calculation of the temperature sensitivity is vital for the prediction of future CH4 emission. For this, the increase in reaction rate over a 10°C range (Q10) is frequently used, with single fixed Q10 values (between 2 and 4) commonly incorporated into climate-carbon cycle models. However, the temperature sensitivity of CH4 emission can vary considerably depending on factors such as vegetation composition, water table and season. This promotes the use of spatially and seasonally variable Q10 values for accurate CH4 flux estimation under different future climate change scenarios. This study investigates the temperature sensitivity (Q10) of Arctic tundra methane fluxes, using an extensive number of soil cores (48) extracted from wet sedge polygonal tundra (Barrow Experimental Observatory, Alaska). 'Wet' and 'dry' cores were taken from the centre and raised perimeter of ice-wedge polygons, where the water tables are 0cm and -15cm respectively. Cores were incubated in two controlled environment chambers (University of Sheffield, UK) for 12 weeks under different thaw depth treatments (control and control + 6.8cm), water tables (surface and -15cm), and CO2 concentrations (400ppm and 850ppm) in a multifactorial manner. Chamber temperature was gradually increased from -5°C to 20°C, then gradually decreased to -5°C, with each temperature stage lasting one week. Average CH4 fluxes from 'dry' cores were consistently low and did not change significantly with temperature, indicating that CH4 emission from drier Arctic tundra soils is not particularly temperature sensitive. Average CH4 emission from 'wet' cores increased with increasing temperature between -5°C and 20°C. Interestingly, continued increases in average CH4 emission as chamber temperature decreased (20°C to 0°C) were observed. Importantly, when chamber temperature was increased (-5°C to 20°C), average CH4 emission in the 'wet' cores was consistently lower at the end of each week-long temperature stage compared to at the start. This suggests that the response of CH4 emission to climate warming might acclimate. Overall, this study is critical for refining the temperature sensitivity of Arctic tundra CH4 emission, and thus improving model predictions of the response of CH4 fluxes to climate change. References McGuire, AD; Christensen, TR; Hayes, D. et al. (2012). An assessment of the carbon balance of Arctic tundra: comparisons among observations, process models, and atmospheric inversions. Biogeosciences. Vol.9, p.3185-3204, doi:10.5194/bg-9-3185-2012. Zona, D; Oechel, WC; Kochendorfer, J. et al. (2009). Methane fluxes during the initiation of a large-scale water table manipulation experiment in the Alaskan Arctic tundra. Global Biogeochemical Cycles. Vol.23, GB2013, doi:10.1029/2009GB003487.

High Temperature Superconducting Compounds

DTIC Science & Technology

1992-11-30

broadened interest in superconductivity in both the engineering and scientific communities. Superconducting materials may be offered as a solution to a...YBa2Cu307- has been made. For yttrium, the tris( isopropoxide ) was used exclusively, while the use of both Ba(O-i-Pr)2 and Ba(OCH2Ch2OEt)2 (prepared in... solutions of Cu(acac)2, Ba(OCH2CH 2OEt)2 , and Y(O-i-Pr)3 were spin coated on SrTiO 3 (100) and fired under oxygen to give oriented (b axis normal to the

Abiotic methane formation during experimental serpentinization of olivine

PubMed Central

2016-01-01

Fluids circulating through actively serpentinizing systems are often highly enriched in methane (CH4). In many cases, the CH4 in these fluids is thought to derive from abiotic reduction of inorganic carbon, but the conditions under which this process can occur in natural systems remain unclear. In recent years, several studies have reported abiotic formation of CH4 during experimental serpentinization of olivine at temperatures at or below 200 °C. However, these results seem to contradict studies conducted at higher temperatures (300 °C to 400 °C), where substantial kinetic barriers to CH4 synthesis have been observed. Here, the potential for abiotic formation of CH4 from dissolved inorganic carbon during olivine serpentinization is reevaluated in a series of laboratory experiments conducted at 200 °C to 320 °C. A 13C-labeled inorganic carbon source was used to unambiguously determine the origin of CH4 generated in the experiments. Consistent with previous high-temperature studies, the results indicate that abiotic formation of CH4 from reduction of dissolved inorganic carbon during the experiments is extremely limited, with nearly all of the observed CH4 derived from background sources. The results indicate that the potential for abiotic synthesis of CH4 in low-temperature serpentinizing environments may be much more limited than some recent studies have suggested. However, more extensive production of CH4 was observed in one experiment performed under conditions that allowed an H2-rich vapor phase to form, suggesting that shallow serpentinization environments where a separate gas phase is present may be more favorable for abiotic synthesis of CH4. PMID:27821742

Abiotic methane formation during experimental serpentinization of olivine.

PubMed

McCollom, Thomas M

2016-12-06

Fluids circulating through actively serpentinizing systems are often highly enriched in methane (CH 4 ). In many cases, the CH 4 in these fluids is thought to derive from abiotic reduction of inorganic carbon, but the conditions under which this process can occur in natural systems remain unclear. In recent years, several studies have reported abiotic formation of CH 4 during experimental serpentinization of olivine at temperatures at or below 200 °C. However, these results seem to contradict studies conducted at higher temperatures (300 °C to 400 °C), where substantial kinetic barriers to CH 4 synthesis have been observed. Here, the potential for abiotic formation of CH 4 from dissolved inorganic carbon during olivine serpentinization is reevaluated in a series of laboratory experiments conducted at 200 °C to 320 °C. A 13 C-labeled inorganic carbon source was used to unambiguously determine the origin of CH 4 generated in the experiments. Consistent with previous high-temperature studies, the results indicate that abiotic formation of CH 4 from reduction of dissolved inorganic carbon during the experiments is extremely limited, with nearly all of the observed CH 4 derived from background sources. The results indicate that the potential for abiotic synthesis of CH 4 in low-temperature serpentinizing environments may be much more limited than some recent studies have suggested. However, more extensive production of CH 4 was observed in one experiment performed under conditions that allowed an H 2 -rich vapor phase to form, suggesting that shallow serpentinization environments where a separate gas phase is present may be more favorable for abiotic synthesis of CH 4 .

Susceptibility and remanence studies in the quasi-1D mixed ferromagnet CoTAC : Mn

NASA Astrophysics Data System (ADS)

Cheikhrouhou, A.; Dupas, C.; Renard, J. P.; Veillet, P.

1985-03-01

The ac susceptibility and dc magnetization of CoTAC : Mn ((CH 3) 3NHCo 1- xMn xCl 3ṡ2H 2O) have been studied in the temperature range 1.3-4.2 K on two monocrystalline samples with x = 2.9 and 9.3%. In CoTAC : Mn (9.3%), the variation with the measuring frequency ν of the temperature of the susceptibility maximum Tg(ν) is well described over five decades of frequency by an Arrhenius law Tg-1(ν) = a - b log ν characteristic of superparamagnetic clusters. In CoTAC : Mn (2.9%) Tg(ν) does not differ significantly from that of pure CoTAC. Both compounds exhibit strong remanence effects below Tg. The variations with time, temperature and applied magnetic field of the IRM and TRM are similar to those observed in spin glasses. These experiments confirm the onset of spin-glass-like behaviour or superparamagnetism in quasi-1D insulators with random intrachain exchange at very low impurity concentration. Comparison with the previously studied mixed compound CHAC : Mn evidences the influence of the exchange anisotropy on the static properties of these systems.

Carbon isotope exchange between CO2 and CH4 in hydrothermal fluids from the Tuscan-Roman and Campanian degassing systems (central-southern Italy)

NASA Astrophysics Data System (ADS)

Tassi, F.; Fiebig, J.; Nocentini, M.; Vaselli, O.

2010-12-01

The carbon isotope composition in CO2 and CH4 are commonly used as exploration tools and diagnostic indicators to investigate the origin of endogenous gases. At temperature <200 °C both proportions and isotope ratios of these two gases are considered to be largely controlled by processes (i.e. bacterial activity, thermal hydrolysis, and cracking of organic matter) that are mainly dictated by kinetics. Recent investigations on abiogenic generation of CH4 suggest that at temperatures as low as 100 °C, CH4 production from CO2 has halftimes in the order of 1 year. The present work is based on the d13C-CO2 and d13C-CH4 values of more than 83 gas discharges from the Tuscan-Roman and Campanian degassing systems (central-southern Italy). The main aims are to i) investigate the processes regulating the chemical and isotopic compositions of CO2 and CH4 and ii) verify the use of the CO2-CH4 carbon isotopic equilibrium for evaluating the temperature of deep hydrothermal reservoirs. Our results show that the d13C-CH4 values, with few exceptions related to local production of biogenic CH4 at shallow depth, are > -40 ‰ V-PDB. The most intriguing feature of the measured d13C-CH4 values is that they progressively decrease from the peri-Tyrrhenian area, where productive geothermal systems and active volcanoes are located, to East, i.e. approaching the CH4-rich reservoirs that mark the Adriatic side of the Italian peninsula. The d13C-CO2 values are substantially spanning from a thermometamorphic to a mantle degassing CO2 and do not show any preferential spatial distribution. Secondary carbon isotope fractionation caused by interaction with relatively shallow aquifers may contribute to the scatter of d13C-CO2 values, considering the high solubility of CO2 in liquid water. However, the CO2-CH4 isotopic compositions of fluids from the high temperature geothermal systems characterizing the Tyrrhenian coast of central-southern Italy, i.e. Larderello, Mt. Amiata, Manziana and Phlegrean Fields, provide apparent equilibrium temperatures in the range of those directly measured in production wells and/or estimated on the basis of the CH4-CO2 chemical geothermometer. These results are consistent with the fact that the carbon isotopic equilibrium in the CO2-CH4 system has to be preceded by that of the chemical exchange because the latter has a kinetic rate 400 times faster than the isotopic partitioning. The observed agreement between measured and/or inferred aquifer temperatures with apparent carbon isotopic equilibration supports recent findings that CO2 and CH4 can attain carbon isotopic equilibrium in high-enthalpy hydrothermal systems. The d13C-CH4 values of gas discharges located eastward, toward the Appennine sedimentary chain, are likely produced by mixing of high temperature fluids from the geothermal areas and a relatively cold deep aquifer characterized by biogenic CH4: The higher distance from the geothermal-volcanic systems, the higher fraction of low temperature fluids.

Three-Dimensional Spin Texture in Hybrid Perovskites and Its Impact on Optical Transitions

DOE PAGES

Zhang, Xie; Shen, Jimmy -Xuan; Van de Walle, Chris G.

2018-05-15

Hybrid perovskites such as MAPbI 3 (MA = CH 3NH 3) exhibit a unique spin texture. The spin texture (as calculated within the Rashba model) has been suggested to be responsible for a suppression of radiative recombination due to a mismatch of spins at the band edges. Here we compute the spin texture from first principles and demonstrate that it does not suppress recombination. The exact spin texture is dominated by the inversion asymmetry of the local electrostatic potential, which is determined by the structural distortion induced by the MA molecule. In addition, the rotation of the MA molecule atmore » room temperature leads to a dynamic spin texture in MAPbI 3. Furthermore these insights call for a reconsideration of the scenario that radiative recombination is suppressed and provide an in-depth understanding of the origin of the spin texture in hybrid perovskites, which is crucial for designing spintronic devices.« less

Three-Dimensional Spin Texture in Hybrid Perovskites and Its Impact on Optical Transitions

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

Zhang, Xie; Shen, Jimmy -Xuan; Van de Walle, Chris G.

Hybrid perovskites such as MAPbI 3 (MA = CH 3NH 3) exhibit a unique spin texture. The spin texture (as calculated within the Rashba model) has been suggested to be responsible for a suppression of radiative recombination due to a mismatch of spins at the band edges. Here we compute the spin texture from first principles and demonstrate that it does not suppress recombination. The exact spin texture is dominated by the inversion asymmetry of the local electrostatic potential, which is determined by the structural distortion induced by the MA molecule. In addition, the rotation of the MA molecule atmore » room temperature leads to a dynamic spin texture in MAPbI 3. Furthermore these insights call for a reconsideration of the scenario that radiative recombination is suppressed and provide an in-depth understanding of the origin of the spin texture in hybrid perovskites, which is crucial for designing spintronic devices.« less

Low-Temperature Rate Coefficients of C2H with CH4 and CD4 from 154 to 359 K

NASA Technical Reports Server (NTRS)

Opansky, Brian J.; Leone, Stephen R.

1996-01-01

Rate coefficients for the reaction C2H + CH4 yields C2H2 + CH3 and C2H + CD4 yields C2HD + CD3 are measured over the temperature range 154-359 K using transient infrared laser absorption spectroscopy. Ethynyl radicals are produced by pulsed laser photolysis of C2H2 in a variable temperature flow cell, and a tunable color center laser probes the transient removal of C2H (Chi(exp 2) Sigma(+) (0,0,0)) in absorption. The rate coefficients for the reactions of C2H with CH4 and CD4 both show a positive temperature dependence over the range 154-359 K, which can be expressed as k(sub CH4) = (1.2 +/- 0.1) x 10(exp -11) exp((-491 +/- 12)/T) and k(sub CD4) = (8.7 +/- 1.8) x 10(exp -12) exp((-650 +/- 61)/T) cm(exp 3) molecule(exp -1) s(exp -1), respectively. The reaction of C2H + CH4 exhibits a significant kinetic isotope effect at 300 K of k(sub CH4)/k(sub CD4) = 2.5 +/- 0.2. Temperature dependent rate constants for C2H + C2H2 were also remeasured over an increased temperature range from 143 to 359 K and found to show a slight negative temperature dependence, which can be expressed as k(sub C2H2) = 8.6 x 10(exp -16) T(exp 1.8) exp((474 +/- 90)/T) cm(exp 3) molecule(exp -1) s(exp -1).

The Relative Abundances of Resolved 12CH2D2 and 13CH3D and Mechanisms Controlling Isotopic Bond Ordering in Abiotic and Biotic Methane Gases

NASA Astrophysics Data System (ADS)

Young, E. D.; Kohl, I. E.; Sherwood Lollar, B.; Etiope, G.; Rumble, D.; Li, S.; Haghnegahdar, M. A.; Schauble, E. A.; McCain, K.; Foustoukos, D.; Sutcliffe, C. N.; Warr, O.; Ballentine, C. J.; Onstott, T. C.; Hosgormez, H.; Neubeck, A.; Marques, J. M.; Perez-Rodriguez, I. M.; Rowe, A. R.; LaRowe, D.; Magnabosco, C.; Bryndzia, T.

2016-12-01

We report measurements of resolved 12CH2D2 and 13CH3D at natural abundances in a variety of methane gases produced naturally and in the laboratory. The ability to resolve 12CH2D2 from 13CH3D provides unprecedented insights into the origin and evolution of CH4. The results identify conditions under which either isotopic bond order disequilibrium or equilibrium are expected. Where equilibrium obtains, concordant Δ12CH2D2 and Δ13CH3D temperatures can be used reliably for thermometry. We find that concordant temperatures do not always match previous hypotheses based on indirect estimates of temperature of formation nor temperatures derived from CH4/H2 D/H exchange, underscoring the importance of reliable thermometry based on the CH4 molecules themselves. Where Δ12CH2D2 and Δ13CH3D values are inconsistent with thermodynamic equilibrium, temperatures of formation derived from these species are spurious. In such situations, while formation temperatures are unavailable, disequilibrium isotopologue ratios nonetheless provide important information about the formation mechanism of the gas and the presence or absence of multiple sources or sinks. In particular, disequilibrium isotopologue ratios may provide the means for differentiating between methane produced by abiotic synthesis versus biological processes. Deficits in 12CH2D2 compared with equilibrium values in CH4 gas made by surface-catalyzed abiotic reactions are so large as to point towards a quantum tunneling origin. Tunneling also accounts for the more moderate depletions in 13CH3D that accompany the low 12CH2D2 abundances produced by abiotic reactions. The tunneling signature of abiotic CH4 formation may prove to be an important tracer of abiotic methane formation, especially where it is preserved by dissolution of gas in cool hydrothermal systems (e.g., Mars). Isotopologue signatures of abiotic methane production can be erased by infiltration of microbial communities, and Δ12CH2D2 values are a key tracer of microbial recycling.

Disproportionation and thermochemical sulfate reduction reactions in S-H20-Ch4 and S-D2O-CH4 systems from 200 to 340 °C at elevated pressures

USGS Publications Warehouse

Yuan, Shunda; Chou, I-Ming; Burruss, Robert A.

2013-01-01

Elemental sulfur, as a transient intermediate compound, by-product, or catalyst, plays significant roles in thermochemical sulfate reduction (TSR) reactions. However, the mechanisms of the reactions in S-H2O-hydrocarbons systems are not clear. To improve our understanding of reaction mechanisms, we conducted a series of experiments between 200 and 340 °C for S-H2O-CH4, S-D2O-CH4, and S-CH4-1m ZnBr2 systems in fused silica capillary capsules (FSCC). After a heating period ranging from 24 to 2160 hours (hrs), the quenched samples were analyzed by Raman spectroscopy. Combined with the in situ Raman spectra collected at high temperatures and pressures in the S-H2O and S-H2O-CH4 systems, our results showed that (1) the disproportionation of sulfur in the S-H2O-CH4 system occurred at temperatures above 200 °C and produced H2S, SO42-, and possibly trace amount of HSO4-; (2) sulfate (and bisulfate), in the presence of sulfur, can be reduced by methane between 250 and 340 °C to produce CO2 and H2S, and these TSR temperatures are much closer to those of the natural system (2O-CH4 system may take place simultaneously, with TSR being favored at higher temperatures; and (4) in the system S-D2O-CH4, both TSR and the competitive disproportionation reactions occurred simultaneously at temperatures above 300 °C, but these reactions were very slow at lower temperatures. Our observation of methane reaction at 250 °C in a laboratory time scale suggests that, in a geologic time scale, methane may be destroyed by TSR reactions at temperatures > 200 °C that can be reached by deep drilling for hydrocarbon resources.

Factors influencing CO2 and CH4 emissions from coastal wetlands in the Liaohe Delta, Northeast China

NASA Astrophysics Data System (ADS)

Olsson, L.; Ye, S.; Yu, X.; Wei, M.; Krauss, K. W.; Brix, H.

2015-08-01

Many factors are known to influence greenhouse gas emissions from coastal wetlands, but it is still unclear which factors are most important under field conditions when they are all acting simultaneously. The objective of this study was to assess the effects of water table, salinity, soil temperature and vegetation on CH4 emissions and ecosystem respiration (Reco) from five coastal wetlands in the Liaohe Delta, Northeast China: two Phragmites australis (common reed) wetlands, two Suaeda salsa (sea blite) marshes and a rice (Oryza sativa) paddy. Throughout the growing season, the Suaeda wetlands were net CH4 sinks whereas the Phragmites wetlands and the rice paddy were net CH4 sources emitting 1.2-6.1 g CH4 m-2 yr-1. The Phragmites wetlands emitted the most CH4 per unit area and the most CH4 relative to CO2. The main controlling factors for the CH4 emissions were water table, temperature, soil organic carbon and salinity. The CH4 emission was accelerated at high and constant (or managed) water tables and decreased at water tables below the soil surface. High temperatures enhanced CH4 emissions, and emission rates were consistently low (< 1 mg CH4 m-2 h-1) at soil temperatures < 18 °C. At salinity levels > 18 ppt, the CH4 emission rates were always low (< 1 mg CH4 m-2 h-1) probably because methanogens were out-competed by sulphate-reducing bacteria. Saline Phragmites wetlands can, however, emit significant amounts of CH4 as CH4 produced in deep soil layers are transported through the air-space tissue of the plants to the atmosphere. The CH4 emission from coastal wetlands can be reduced by creating fluctuating water tables, including water tables below the soil surface, as well as by occasional flooding by high-salinity water. The effects of water management schemes on the biological communities in the wetlands must, however, be carefully studied prior to the management in order to avoid undesirable effects on the wetland communities.

Factors influencing CO2 and CH4 emissions from coastal wetlands in the Liaohe Delta, Northeast China

NASA Astrophysics Data System (ADS)

Olsson, L.; Ye, S.; Yu, X.; Wei, M.; Krauss, K. W.; Brix, H.

2015-02-01

Many factors are known to influence greenhouse gas emissions from coastal wetlands, but it is still unclear which factors are most important under field conditions when they are all acting simultaneously. The objective of this study was to assess the effects of water table, salinity, soil temperature and vegetation on CH4 emissions and ecosystem respiration (Reco) from five coastal wetlands in the Liaohe Delta, northeast China: two Phragmites australis (common reed) wetlands, two Suaeda salsa (sea blite) marshes and a rice (Oryza sativa) paddy. Throughout the growing season, the Suaeda wetlands were net CH4 sinks whereas the Phragmites wetlands and the rice paddy were net CH4 sources emitting 1.2-6.1 g CH4 m-2 y-1. The Phragmites wetlands emitted the most CH4 per unit area and the most CH4 relative to CO2. The main controlling factors for the CH4 emissions were water table, temperature and salinity. The CH4 emission was accelerated at high and constant (or managed) water tables and decreased at water tables below the soil surface. High temperatures enhanced CH4 emissions, and emission rates were consistently low (< 1 mg CH4 m-2 h) at soil temperatures <18 °C. At salinity levels > 18 ppt, the CH4 emission rates were always low (< 1 mg CH4 m-2 h-1) probably because methanogens were outcompeted by sulphate reducing bacteria. Saline Phragmites wetlands can, however, emit significant amounts of CH4 as CH4 produced in deep soil layers are transported through the air-space tissue of the plants to the atmosphere. The CH4 emission from coastal wetlands can be reduced by creating fluctuating water tables, including water tables below the soil surface, as well as by occasional flooding by high-salinity water. The effects of water management schemes on the biological communities in the wetlands must, however, be carefully studied prior to the management in order to avoid undesirable effects on the wetland communities.

An empirical equation with tables of smoothed solubilities of methane in water and aqueous sodium chloride solutions up to 25 weight percent, 360 degrees C, and 138 MPa

USGS Publications Warehouse

Haas, John L.

1978-01-01

The total pressure for the system H2O-CH 4 is given by p(total) = P(H2O,t) + exp10[log x(CH 4) - a - b x(CH4)], where P(H2O,t) is the vapor pressure of H2O liquid at the temperature t (?C) and x(CH 4) is the molal concentration of methane in the solution. The terms a and b are functions of temperature only. Where the total pressure and temperature are known, the concentration of methane, x(CH4), is found by iteration. The concentration of methane in a sodium chloride brine, y(CH4), is estimated using the function log y(CH4) = log x(CH4) - A I, where A is the salting out constant and I is the ionic strength. For sodium chloride solutions, the ionic strength is equal to the molality of the salt. The equations are valid to 360?C, 138 MPa, and 25 weight percent sodium chloride.

Plants, microorganisms, and soil temperatures contribute to a decrease in methane fluxes on a drained Arctic floodplain.

PubMed

Kwon, Min Jung; Beulig, Felix; Ilie, Iulia; Wildner, Marcus; Küsel, Kirsten; Merbold, Lutz; Mahecha, Miguel D; Zimov, Nikita; Zimov, Sergey A; Heimann, Martin; Schuur, Edward A G; Kostka, Joel E; Kolle, Olaf; Hilke, Ines; Göckede, Mathias

2017-06-01

As surface temperatures are expected to rise in the future, ice-rich permafrost may thaw, altering soil topography and hydrology and creating a mosaic of wet and dry soil surfaces in the Arctic. Arctic wetlands are large sources of CH 4 , and investigating effects of soil hydrology on CH 4 fluxes is of great importance for predicting ecosystem feedback in response to climate change. In this study, we investigate how a decade-long drying manipulation on an Arctic floodplain influences CH 4 -associated microorganisms, soil thermal regimes, and plant communities. Moreover, we examine how these drainage-induced changes may then modify CH 4 fluxes in the growing and nongrowing seasons. This study shows that drainage substantially lowered the abundance of methanogens along with methanotrophic bacteria, which may have reduced CH 4 cycling. Soil temperatures of the drained areas were lower in deep, anoxic soil layers (below 30 cm), but higher in oxic topsoil layers (0-15 cm) compared to the control wet areas. This pattern of soil temperatures may have reduced the rates of methanogenesis while elevating those of CH 4 oxidation, thereby decreasing net CH 4 fluxes. The abundance of Eriophorum angustifolium, an aerenchymatous plant species, diminished significantly in the drained areas. Due to this decrease, a higher fraction of CH 4 was alternatively emitted to the atmosphere by diffusion, possibly increasing the potential for CH 4 oxidation and leading to a decrease in net CH 4 fluxes compared to a control site. Drainage lowered CH 4 fluxes by a factor of 20 during the growing season, with postdrainage changes in microbial communities, soil temperatures, and plant communities also contributing to this reduction. In contrast, we observed CH 4 emissions increased by 10% in the drained areas during the nongrowing season, although this difference was insignificant given the small magnitudes of fluxes. This study showed that long-term drainage considerably reduced CH 4 fluxes through modified ecosystem properties. © 2016 John Wiley & Sons Ltd.

Molecular simulation of methane adsorption characteristics on coal macromolecule

NASA Astrophysics Data System (ADS)

Yang, Zhiyuan; He, Xiaoxiao; Meng, Zhuoyue; Xue, Wenying

2018-02-01

In this paper, the molecular model of anthracite named Wender2 was selected to study the adsorption behaviour of single component CH4 and the competitive adsorption of CH4/CO2, CH4/H2O and CH4/N2. The molecular model of anthracite was established by molecular simulation software (Materials Studio 8.0), and Grand Canonical Monte Carlo (GCMC) simulations were carried out to investigate the single and binary component adsorption. The effects of pressure and temperature on the adsorption position, adsorption energy and adsorption capacity were mainly discussed. The results show that for the single component adsorption, the adsorption capacity of CH4 increases rapidly with the pressure ascending, and then tends to be stable after the first step. The low temperature is favourable for the adsorption of CH4, and the high temperature promotes desorption quantity of CH4 from the coal. Adsorbent molecules are preferentially adsorbed on the edge of coal macromolecules. The order of adsorption capacity of CH4/CO2, CH4/H2O and CH4/N2 in the binary component is H2O>CO2>CH4>N2. The change of pressure has little effect on the adsorption capacity of the adsorbent in the competitive adsorption, but it has a great influence on the adsorption capacity of the adsorbent, and there is a positive correlation between them.

Remotely sensed MODIS wetland components for assessing the variability of methane emissions in Indian tropical/subtropical wetlands

NASA Astrophysics Data System (ADS)

Bansal, Sangeeta; Katyal, Deeksha; Saluja, Ridhi; Chakraborty, Monojit; Garg, J. K.

2018-02-01

Temperature and area fluctuations in wetlands greatly influence its various physico-chemical characteristics, nutrients dynamic, rates of biomass generation and decomposition, floral and faunal composition which in turn influence methane (CH4) emission rates. In view of this, the present study attempts to up-scale point CH4 flux from the wetlands of Uttar Pradesh (UP) by modifying two-factor empirical process based CH4 emission model for tropical wetlands by incorporating MODIS derived wetland components viz. wetland areal extent and corresponding temperature factors (Ft). This study further focuses on the utility of remotely sensed temperature response of CH4 emission in terms of Ft. Ft is generated using MODIS land surface temperature products and provides an important semi-empirical input for up-scaling CH4 emissions in wetlands. Results reveal that annual mean Ft values for UP wetlands vary from 0.69 (2010-2011) to 0.71(2011-2012). The total estimated area-wise CH4 emissions from the wetlands of UP varies from 66.47 Gg yr-1with wetland areal extent and Ft value of 2564.04 km2 and 0.69 respectively in 2010-2011 to 88.39 Gg yr-1with wetland areal extent and Ft value of 2720.16 km2 and 0.71 respectively in 2011-2012. Temporal analysis of estimated CH4 emissions showed that in monsoon season estimated CH4 emissions are more sensitive to wetland areal extent while in summer season sensitivity of estimated CH4 emissions is chiefly controlled by augmented methanogenic activities at high wetland surface temperatures.

Theoretical study on the reaction mechanism of CH 4 with CaO

NASA Astrophysics Data System (ADS)

Yang, Hua-Qing; Hu, Chang-Wei; Qin, Song

2006-11-01

The reaction pathways and energetics for the reaction of methane with CaO are discussed on the singlet spin state potential energy surface at the B3LYP/6-311+G(2df,2p) and QCISD/6-311++G(3df,3pd)//B3LYP/6-311+G(2df,2p) levels of theory. The reaction of methane with CaO is proposed to proceed in the following reaction pathways: CaO + CH 4 → CaOCH 4 → [TS] → CaOH + CH 3, CaO + CH 4 → OCaCH 4 → [TS] → HOCaCH 3 → CaOH + CH 3 or [TS] → CaCH 3OH → Ca + CH 3OH, and OCaCH 4 → [TS] → HCaOCH 3 → CaOCH 3 + H or [TS] → CaCH 3OH → Ca + CH 3OH. The gas-phase methane-methanol conversion by CaO is suggested to proceed via two kinds of important reaction intermediates, HOCaCH 3 and HCaOCH 3, and the reaction pathway via the hydroxy intermediate (HOCaCH 3) is energetically more favorable than the other one via the methoxy intermediate (HCaOCH 3). The hydroxy intermediate HOCaCH 3 is predicted to be the energetically most preferred configuration in the reaction of CaO + CH 4. Meanwhile, these three product channels (CaOH + CH 3, CaOCH 3 + H and Ca + CH 3OH) are expected to compete with each other, and the formation of methyl radical is the most preferable pathway energetically. On the other hand, the intermediates HCaOCH 3 and HOCaCH 3 are predicted to be the energetically preferred configuration in the reaction of Ca + CH 3OH, which is precisely the reverse reaction of methane hydroxylation.

Raman spectroscopic characterization of CH4 density over a wide range of temperature and pressure

USGS Publications Warehouse

Shang, Linbo; Chou, I-Ming; Burruss, Robert; Hu, Ruizhong; Bi, Xianwu

2014-01-01

The positions of the CH4 Raman ν1 symmetric stretching bands were measured in a wide range of temperature (from −180 °C to 350 °C) and density (up to 0.45 g/cm3) using high-pressure optical cell and fused silica capillary capsule. The results show that the Raman band shift is a function of both methane density and temperature; the band shifts to lower wavenumbers as the density increases and the temperature decreases. An equation representing the observed relationship among the CH4 ν1 band position, temperature, and density can be used to calculate the density in natural or synthetic CH4-bearing inclusions.

NMR investigation of the short-chain ionic surfactant-water systems.

PubMed

Popova, M V; Tchernyshev, Y S; Michel, D

2004-02-03

The structure and dynamics of surfactant molecules [CH3(CH2)7COOK] in heavy water solutions were investigated by 1H and 2H NMR. A double-exponential attenuation of the spin-echo amplitude in a Carr-Purcell-Meiboom-Gill experiment was found. We expect correspondence to both bounded and monomeric states. At high concentrations in the NMR self-diffusion measurements also a double-exponential decay of the spin-echo signal versus the square of the dc magnetic gradient was observed. The slow component of the diffusion process is caused by micellar aggregates, while the fast component is the result of the self-diffusion of the monomers through the micelles. The self-diffusion studies indicate that the form of micelles changes with increasing total surfactant concentration. The critical temperature range for self-association is reflected in the 1H transverse relaxation.

Soil methane oxidation in both dry and wet temperate eucalypt forests shows a near-identical relationship with soil air-filled porosity

NASA Astrophysics Data System (ADS)

Fest, Benedikt J.; Hinko-Najera, Nina; Wardlaw, Tim; Griffith, David W. T.; Livesley, Stephen J.; Arndt, Stefan K.

2017-01-01

Well-drained, aerated soils are important sinks for atmospheric methane (CH4) via the process of CH4 oxidation by methane-oxidising bacteria (MOB). This terrestrial CH4 sink may contribute towards climate change mitigation, but the impact of changing soil moisture and temperature regimes on CH4 uptake is not well understood in all ecosystems. Soils in temperate forest ecosystems are the greatest terrestrial CH4 sink globally. Under predicted climate change scenarios, temperate eucalypt forests in south-eastern Australia are predicted to experience rapid and extreme changes in rainfall patterns, temperatures and wild fires. To investigate the influence of environmental drivers on seasonal and inter-annual variation of soil-atmosphere CH4 exchange, we measured soil-atmosphere CH4 exchange at high-temporal resolution (< 2 h) in a dry temperate eucalypt forest in Victoria (Wombat State Forest, precipitation 870 mm yr-1) and in a wet temperature eucalypt forest in Tasmania (Warra Long-Term Ecological Research site, 1700 mm yr-1). Both forest soil systems were continuous CH4 sinks of -1.79 kg CH4 ha-1 yr-1 in Victoria and -3.83 kg CH4 ha-1 yr-1 in Tasmania. Soil CH4 uptake showed substantial temporal variation and was strongly controlled by soil moisture at both forest sites. Soil CH4 uptake increased when soil moisture decreased and this relationship explained up to 90 % of the temporal variability. Furthermore, the relationship between soil moisture and soil CH4 flux was near-identical at both forest sites when soil moisture was expressed as soil air-filled porosity (AFP). Soil temperature only had a minor influence on soil CH4 uptake. Soil nitrogen concentrations were generally low and fluctuations in nitrogen availability did not influence soil CH4 uptake at either forest site. Our data suggest that soil MOB activity in the two forests was similar and that differences in soil CH4 exchange between the two forests were related to differences in soil moisture and thereby soil gas diffusivity. The differences between forest sites and the variation in soil CH4 exchange over time could be explained by soil AFP as an indicator of soil moisture status.

Near-zero methane emission from an abandoned boreal peatland pasture based on eddy covariance measurements

PubMed Central

Wang, Mei; Luan, Junwei; Lafleur, Peter; Chen, Huai; Zhu, Xinbiao

2017-01-01

Although estimates of the annual methane (CH4) flux from agriculturally managed peatlands exist, knowledge of controls over the variation of CH4 at different time-scales is limited due to the lack of high temporal-resolution data. Here we present CH4 fluxes measured from May 2014 to April 2016 using the eddy covariance technique at an abandoned peatland pasture in western Newfoundland, Canada. The goals of the study were to identify the controls on the seasonal variations in CH4 flux and to quantify the annual CH4 flux. The seasonal variation in daily CH4 flux was not strong in the two study years, however a few periods of pronounced emissions occurred in the late growing season. The daily average CH4 flux was small relative to other studies, ranging from -4.1 to 9.9 nmol m-2 s-1 in 2014–15 and from -7.1 to 12.1 nmol m-2 s-1 in 2015–16. Stepwise multiple regression was used to investigate controls on CH4 flux and this analysis found shifting controls on CH4 flux at different periods of the growing season. During the early growing season CH4 flux was closely related to carbon dioxide fixation rates, suggesting substrate availability was the main control. The peak growing season CH4 flux was principally controlled by the CH4 oxidation in 2014, where the CH4 flux decreased and increased with soil temperature at 50 cm and soil water content at 10 cm, but a contrasting temperature-CH4 relation was found in 2015. The late growing season CH4 flux was found to be regulated by the variation in water table level and air temperature in 2014. The annual CH4 emission was near zero in both study years (0.36 ± 0.30 g CH4 m-2 yr-1 in 2014–15 and 0.13 ± 0.38 g CH4 m-2 yr-1 in 2015–16), but fell within the range of CH4 emissions reported for agriculturally managed peatlands elsewhere. PMID:29252998

Near-zero methane emission from an abandoned boreal peatland pasture based on eddy covariance measurements.

PubMed

Wang, Mei; Wu, Jianghua; Luan, Junwei; Lafleur, Peter; Chen, Huai; Zhu, Xinbiao

2017-01-01

Although estimates of the annual methane (CH4) flux from agriculturally managed peatlands exist, knowledge of controls over the variation of CH4 at different time-scales is limited due to the lack of high temporal-resolution data. Here we present CH4 fluxes measured from May 2014 to April 2016 using the eddy covariance technique at an abandoned peatland pasture in western Newfoundland, Canada. The goals of the study were to identify the controls on the seasonal variations in CH4 flux and to quantify the annual CH4 flux. The seasonal variation in daily CH4 flux was not strong in the two study years, however a few periods of pronounced emissions occurred in the late growing season. The daily average CH4 flux was small relative to other studies, ranging from -4.1 to 9.9 nmol m-2 s-1 in 2014-15 and from -7.1 to 12.1 nmol m-2 s-1 in 2015-16. Stepwise multiple regression was used to investigate controls on CH4 flux and this analysis found shifting controls on CH4 flux at different periods of the growing season. During the early growing season CH4 flux was closely related to carbon dioxide fixation rates, suggesting substrate availability was the main control. The peak growing season CH4 flux was principally controlled by the CH4 oxidation in 2014, where the CH4 flux decreased and increased with soil temperature at 50 cm and soil water content at 10 cm, but a contrasting temperature-CH4 relation was found in 2015. The late growing season CH4 flux was found to be regulated by the variation in water table level and air temperature in 2014. The annual CH4 emission was near zero in both study years (0.36 ± 0.30 g CH4 m-2 yr-1 in 2014-15 and 0.13 ± 0.38 g CH4 m-2 yr-1 in 2015-16), but fell within the range of CH4 emissions reported for agriculturally managed peatlands elsewhere.

Radiolysis of carbohydrates as studied by ESR and spin-trapping—II. Glycerol- d8 xylitol, dulcitol, d-sorbitol and d-mannitol

NASA Astrophysics Data System (ADS)

Kuwabara, M.; Zhang, Z.-Y.; Inanami, O.; Yoshii, G.

Studies concerning the radicals produced in glycerol by reactions with OH radicals have been carried out by investigating deuterated glycerol (glycerol-d 8) by spin-trapping with 2-methyl-2-nitrosopropane. Free radicals produced in linear carbohydrates such as xylitol, dulcitol, D-sorbitol and D-mannitol by reactions with OH radicals as well as by direct γ-radiolysis have been also investigated by spin-trapping. The ESR spectra of the spin-trapped radicals were analysed on the basis of the results from ESR and spin-trapping experiments on glycerol and deuterated glycerol, and the formation of three radical species, CHO-CH-, CH 2-CO- and HO-CH-, due to both OH reactions and direct γ-radiolysis was confirmed for all compounds. The presence of a radical, -CO-CH-, was detected for xylitol, D-sorbitol and D-mannitol. General reactions processes induced by OH reactions or γ-radiolysis in the solid state are discussed.

Simulations and experimental investigations of the competitive adsorption of CH4 and CO2 on low-rank coal vitrinite.

PubMed

Yu, Song; Bo, Jiang; Jiahong, Li

2017-09-16

The mechanism for the competitive adsorption of CH 4 and CO 2 on coal vitrinite (DV-8, maximum vitrinite reflectance R o,max  = 0.58%) was revealed through simulation and experimental methods. A saturated state was reached after absorbing 17 CH 4 or 22 CO 2 molecules per DV-8 molecule. The functional groups (FGs) on the surface of the vitrinite can be ranked in order of decreasing CH 4 and CO 2 adsorption ability as follows: [-CH 3 ] > [-C=O] > [-C-O-C-] > [-COOH] and [-C-O-C-] > [-C=O] > [-CH 3 ] > [-COOH]. CH 4 and CO 2 distributed as aggregations and they were both adsorbed at the same sites on vitrinite, indicating that CO 2 can replace CH 4 by occupying the main adsorption sites for CH 4 -vitrinite. High temperatures are not conducive to the adsorption of CH 4 and CO 2 on vitrinite. According to the results of density functional theory (DFT) and grand canonical Monte Carlo (GCMC) calculations, vitrinite has a higher adsorption capacity for CO 2 than for CH 4 , regardless of whether a single-component or binary adsorbate is considered. The equivalent adsorption heat (EAH) of CO 2 -vitrinite (23.02-23.17) is higher than that of CH 4 -vitrinite (9.04-9.40 kJ/mol). The EAH of CO 2 -vitrinite decreases more rapidly with increasing temperature than the EAH of CH 4 -vitrinite does, indicating in turn that the CO 2 -vitrinite bond weakens more quickly with increasing temperature than the CH 4 -vitrinite bond does. Simulation data were found to be in good accord with the corresponding experimental results.

Slow relaxation in a one-dimensional rational assembly of antiferromagnetically coupled [Mn4] single-molecule magnets.

PubMed

Lecren, Lollita; Roubeau, Olivier; Coulon, Claude; Li, Yang-Guang; Le Goff, Xavier F; Wernsdorfer, Wolfgang; Miyasaka, Hitoshi; Clérac, Rodolphe

2005-12-14

Four discrete Mn(III)/Mn(II) tetranuclear complexes with a double-cuboidal core, [Mn(4)(hmp)(6)(CH(3)CN)(2)(H(2)O)(4)](ClO(4))(4).2CH(3)CN (1), [Mn(4)(hmp)(6)(H(2)O)(4)](ClO(4))(4).2H(2)O (2), [Mn(4)(hmp)(6)(H(2)O)(2)(NO(3))(2)](ClO(4))(2).4H(2)O (3), and [Mn(4)(hmp)(6)(Hhmp)(2)](ClO(4))(4).2CH(3)CN (4), were synthesized by reaction of Hhmp (2-hydroxymethylpyridine) with Mn(ClO(4))(2).6H(2)O in the presence of tetraethylammonium hydroxide and subsequent addition of NaNO(3) (3) or an excess of Hhmp (4). Direct current (dc) magnetic measurements show that both Mn(2+)-Mn(3+) and Mn(3+)-Mn(3+) magnetic interactions are ferromagnetic in 1-3 leading to an S(T) = 9 ground state for the Mn(4) unit. Furthermore, these complexes are single-molecule magnets (SMMs) clearly showing both thermally activated and ground-state tunneling regimes. Slight changes in the [Mn(4)] core geometry result in an S(T) = 1 ground state in 4. A one-dimensional assembly of [Mn(4)] units, catena-{[Mn(4)(hmp)(6)(N(3))(2)](ClO(4))(2)} (5), was obtained in the same synthetic conditions with the subsequent addition of NaN(3). Double chairlike N(3)(-) bridges connect identical [Mn(4)] units into a chain arrangement. This material behaves as an Ising assembly of S(T) = 9 tetramers weakly antiferromagnetically coupled. Slow relaxation of the magnetization is observed at low temperature for the first time in an antiferromagnetic chain, following an activated behavior with Delta(tau)/k(B) = 47 K and tau(0) = 7 x 10(-)(11) s. The observation of this original thermally activated relaxation process is induced by finite-size effects and in particular by the noncompensation of spins in segments of odd-number units. Generalizing the known theories on the dynamic properties of polydisperse finite segments of antiferromagnetically coupled Ising spins, the theoretical expressions of the characteristic energy gaps Delta(xi) and Delta(tau) were estimated and successfully compared to the experimental values.

Dual stable isotopes of CH 4 from Yellowstone hot-springs suggest hydrothermal processes involving magmatic CO 2

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

Moran, James J.; Whitmore, Laura M.; Jay, Zackary J.

Volcanism and post-magmatism contribute significant annual methane (CH 4) fluxes to the atmosphere (on par with other natural sources such as forest fire and wild animal emissions) and have been implicated in past climate-change events. The Yellowstone hot spot is one of the largest volcanic systems on Earth and is known to emit CH 4 (as well as carbon dioxide (CO 2) and other gases), but the ultimate sources of this CH 4 flux have not been elucidated. In this paper, we use dual stable isotope analysis (δ 2H and δ 13C) of CH 4 sampled from ten high-temperature geothermalmore » pools in Yellowstone National Park along with other isotopic and gas analyses to evaluate potential sources of methane. The average δ 13C and δ 2H values of CH 4 emitted from hot springs ( 26.7 (± 2.4) and - 236.9 (± 12.0) ‰, respectively) are inconsistent with microbial methanogenesis but do not allow distinction between thermogenic and abiotic sources. Correlation between δ 13C CH4 and δ 13C of dissolved inorganic C (DIC) is consistent with DIC as the parent C source for the observed CH 4, or with equilibration of CH 4 and DIC. Methane formation temperatures estimated by isotopic geothermometry based on δ 13C CH4 and δ 13C CO2 ranged from ~ 250–350 °C, which is just below previous temperature estimates for the hydrothermal reservoir. Further, the δ 2H H2O of the thermal springs and the measured δ 2H CH4 values are consistent with equilibration between the source water and the CH 4 at the formation temperatures. Though the ultimate origin of the CH 4 could be attributed to either abiotic of themorgenic processes with subsequent isotopic equilibration, the C 1/C 2+ composition of the gases is more consistent with abiotic origins for most of the samples. Finally, our data support the hypothesis that subsurface rock-water interactions are responsible for at least a significant fraction of the CH 4 flux from the Yellowstone National Park volcanic system.« less

Dual stable isotopes of CH 4 from Yellowstone hot-springs suggest hydrothermal processes involving magmatic CO 2

DOE PAGES

Moran, James J.; Whitmore, Laura M.; Jay, Zackary J.; ...

2017-05-16

Volcanism and post-magmatism contribute significant annual methane (CH 4) fluxes to the atmosphere (on par with other natural sources such as forest fire and wild animal emissions) and have been implicated in past climate-change events. The Yellowstone hot spot is one of the largest volcanic systems on Earth and is known to emit CH 4 (as well as carbon dioxide (CO 2) and other gases), but the ultimate sources of this CH 4 flux have not been elucidated. In this paper, we use dual stable isotope analysis (δ 2H and δ 13C) of CH 4 sampled from ten high-temperature geothermalmore » pools in Yellowstone National Park along with other isotopic and gas analyses to evaluate potential sources of methane. The average δ 13C and δ 2H values of CH 4 emitted from hot springs ( 26.7 (± 2.4) and - 236.9 (± 12.0) ‰, respectively) are inconsistent with microbial methanogenesis but do not allow distinction between thermogenic and abiotic sources. Correlation between δ 13C CH4 and δ 13C of dissolved inorganic C (DIC) is consistent with DIC as the parent C source for the observed CH 4, or with equilibration of CH 4 and DIC. Methane formation temperatures estimated by isotopic geothermometry based on δ 13C CH4 and δ 13C CO2 ranged from ~ 250–350 °C, which is just below previous temperature estimates for the hydrothermal reservoir. Further, the δ 2H H2O of the thermal springs and the measured δ 2H CH4 values are consistent with equilibration between the source water and the CH 4 at the formation temperatures. Though the ultimate origin of the CH 4 could be attributed to either abiotic of themorgenic processes with subsequent isotopic equilibration, the C 1/C 2+ composition of the gases is more consistent with abiotic origins for most of the samples. Finally, our data support the hypothesis that subsurface rock-water interactions are responsible for at least a significant fraction of the CH 4 flux from the Yellowstone National Park volcanic system.« less

CH4 dissociation in the early stage of graphene growth on Fe-Cu(100) surface: Theoretical insights

NASA Astrophysics Data System (ADS)

Tian, Baoyang; Liu, Tianhui; Yang, YanYan; Li, Kai; Wu, Zhijian; Wang, Ying

2018-01-01

The mechanism of CH4 dissociation and carbon nucleation process on the Fe doped Cu(100) surface were investigated systematically by using the density functional theory (DFT) calculations and microkinetic model. The activity of the Cu(100) surface was improved by the doped Fe atom and the atomic Fe on the Fe-Cu(100) surface was the reaction center due to the synergistic effect. In the dissociation process of CH4, CH3 → CH2 + H was regarded as the rate-determining step. The results obtained from the microkinetic model showed that the coverage of CHx(x = 1-3) was gradually decreased with the temperature increasing and CH3 was always the major intermediate at the broad range of the temperature (from 1035 to 1080 °C) and the ratio of H2/CH4 (from 0 to 5). It is also found that the reaction rates were increased with the temperature increasing. However, the reaction rates were reduced (or increased) at the range of H2/CH4 = 0-0.2 (or H2/CH4 > 0.2). It is noted that controlling the H2 partial pressure was an effective method to regulate the major intermediates and reaction rates of CH4 dissociation and further influence the growing process of graphene.

Factors influencing CO2 and CH4 emissions from coastal wetlands in the Liaohe Delta, northeast China

USGS Publications Warehouse

Olsson, Linda; Ye, Siyuan; Yu, Xueyang; Wei, Mengjie; Krauss, Ken W.; Brix, Hans

2015-01-01

Many factors are known to influence greenhouse gas emissions from coastal wetlands, but it is still unclear which factors are most important under field conditions when they are all acting simultaneously. The objective of this study was to assess the effects of water table, salinity, soil temperature and vegetation on CH4 emissions and ecosystem respiration (Reco) from five coastal wetlands in the Liaohe Delta, northeast China: two Phragmites australis (common reed) wetlands, two Suaeda salsa (sea blite) marshes and a rice (Oryza sativa) paddy. Throughout the growing season, the Suaeda wetlands were net CH4 sinks whereas the Phragmites wetlands and the rice paddy were net CH4sources emitting 1.2–6.1 g CH4 m−2 y−1. The Phragmites wetlands emitted the most CH4 per unit area and the most CH4 relative to CO2. The main controlling factors for the CH4 emissions were water table, temperature and salinity. The CH4 emission was accelerated at high and constant (or managed) water tables and decreased at water tables below the soil surface. High temperatures enhanced CH4 emissions, and emission rates were consistently low (< 1 mg CH4 m−2 h) at soil temperatures <18 °C. At salinity levels > 18 ppt, the CH4 emission rates were always low (< 1 mg CH4 m−2 h−1) probably because methanogens were outcompeted by sulphate reducing bacteria. Saline Phragmites wetlands can, however, emit significant amounts of CH4 as CH4 produced in deep soil layers are transported through the air-space tissue of the plants to the atmosphere. The CH4 emission from coastal wetlands can be reduced by creating fluctuating water tables, including water tables below the soil surface, as well as by occasional flooding by high-salinity water. The effects of water management schemes on the biological communities in the wetlands must, however, be carefully studied prior to the management in order to avoid undesirable effects on the wetland communities.

The relative abundances of resolved l2CH2D2 and 13CH3D and mechanisms controlling isotopic bond ordering in abiotic and biotic methane gases

NASA Astrophysics Data System (ADS)

Young, E. D.; Kohl, I. E.; Lollar, B. Sherwood; Etiope, G.; Rumble, D.; Li, S.; Haghnegahdar, M. A.; Schauble, E. A.; McCain, K. A.; Foustoukos, D. I.; Sutclife, C.; Warr, O.; Ballentine, C. J.; Onstott, T. C.; Hosgormez, H.; Neubeck, A.; Marques, J. M.; Pérez-Rodríguez, I.; Rowe, A. R.; LaRowe, D. E.; Magnabosco, C.; Yeung, L. Y.; Ash, J. L.; Bryndzia, L. T.

2017-04-01

We report measurements of resolved 12CH2D2 and 13CH3D at natural abundances in a variety of methane gases produced naturally and in the laboratory. The ability to resolve 12CH2D2 from 13CH3D provides unprecedented insights into the origin and evolution of CH4. The results identify conditions under which either isotopic bond order disequilibrium or equilibrium are expected. Where equilibrium obtains, concordant Δ12CH2D2 and Δ13CH3D temperatures can be used reliably for thermometry. We find that concordant temperatures do not always match previous hypotheses based on indirect estimates of temperature of formation nor temperatures derived from CH4/H2 D/H exchange, underscoring the importance of reliable thermometry based on the CH4 molecules themselves. Where Δ12CH2D2 and Δ13CH3D values are inconsistent with thermodynamic equilibrium, temperatures of formation derived from these species are spurious. In such situations, while formation temperatures are unavailable, disequilibrium isotopologue ratios nonetheless provide novel information about the formation mechanism of the gas and the presence or absence of multiple sources or sinks. In particular, disequilibrium isotopologue ratios may provide the means for differentiating between methane produced by abiotic synthesis vs. biological processes. Deficits in 12CH2D2 compared with equilibrium values in CH4 gas made by surface-catalyzed abiotic reactions are so large as to point towards a quantum tunneling origin. Tunneling also accounts for the more moderate depletions in 13CH3D that accompany the low 12CH2D2 abundances produced by abiotic reactions. The tunneling signature may prove to be an important tracer of abiotic methane formation, especially where it is preserved by dissolution of gas in cool hydrothermal systems (e.g., Mars). Isotopologue signatures of abiotic methane production can be erased by infiltration of microbial communities, and Δ12CH2D2 values are a key tracer of microbial recycling.

Shifts in identity and activity of methanotrophs in arctic lake sediments in response to temperature changes

USGS Publications Warehouse

He, Ruo; Wooller, Matthew J.; Pohlman, John W.; Quensen, John; Tiedje, James M.; Leigh, Mary Beth

2012-01-01

Methane (CH4) flux to the atmosphere is mitigated via microbial CH4 oxidation in sediments and water. As arctic temperaturesincrease, understanding the effects of temperature on the activity and identity of methanotrophs in arctic lake sediments is importantto predicting future CH4 emissions. We used DNA-based stable-isotope probing (SIP), quantitative PCR (Q-PCR), andpyrosequencing analyses to identify and characterize methanotrophic communities active at a range of temperatures (4°C, 10°C,and 21°C) in sediments (to a depth of 25 cm) sampled from Lake Qalluuraq on the North Slope of Alaska. CH4 oxidation activitywas measured in microcosm incubations containing sediments at all temperatures, with the highest CH4 oxidation potential of37.5 mol g1 day1 in the uppermost (depth, 0 to 1 cm) sediment at 21°C after 2 to 5 days of incubation. Q-PCR of pmoA and ofthe 16S rRNA genes of type I and type II methanotrophs, and pyrosequencing of 16S rRNA genes in 13C-labeled DNA obtained bySIP demonstrated that the type I methanotrophs Methylobacter, Methylomonas, and Methylosoma dominated carbon acquisitionfrom CH4 in the sediments. The identity and relative abundance of active methanotrophs differed with the incubation temperature.Methylotrophs were also abundant in the microbial community that derived carbon from CH4, especially in the deeper sediments(depth, 15 to 20 cm) at low temperatures (4°C and 10°C), and showed a good linear relationship (R0.82) with the relativeabundances of methanotrophs in pyrosequencing reads. This study describes for the first time how methanotrophiccommunities in arctic lake sediments respond to temperature variations.

Controllable Growth of Perovskite Films by Room-Temperature Air Exposure for Efficient Planar Heterojunction Photovoltaic Cells.

PubMed

Yang, Bin; Dyck, Ondrej; Poplawsky, Jonathan; Keum, Jong; Das, Sanjib; Puretzky, Alexander; Aytug, Tolga; Joshi, Pooran C; Rouleau, Christopher M; Duscher, Gerd; Geohegan, David B; Xiao, Kai

2015-12-01

A two-step solution processing approach has been established to grow void-free perovskite films for low-cost high-performance planar heterojunction photovoltaic devices. A high-temperature thermal annealing treatment was applied to drive the diffusion of CH3NH3I precursor molecules into a compact PbI2 layer to form perovskite films. However, thermal annealing for extended periods led to degraded device performance owing to the defects generated by decomposition of perovskite into PbI2. A controllable layer-by-layer spin-coating method was used to grow "bilayer" CH3NH3I/PbI2 films, and then drive the interdiffusion between PbI2 and CH3NH3I layers by a simple air exposure at room temperature for making well-oriented, highly crystalline perovskite films without thermal annealing. This high degree of crystallinity resulted in a carrier diffusion length of ca. 800 nm and a high device efficiency of 15.6%, which is comparable to values reported for thermally annealed perovskite films. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficient calculation of nuclear spin-rotation constants from auxiliary density functional theory.

PubMed

Zuniga-Gutierrez, Bernardo; Camacho-Gonzalez, Monica; Bendana-Castillo, Alfonso; Simon-Bastida, Patricia; Calaminici, Patrizia; Köster, Andreas M

2015-09-14

The computation of the spin-rotation tensor within the framework of auxiliary density functional theory (ADFT) in combination with the gauge including atomic orbital (GIAO) scheme, to treat the gauge origin problem, is presented. For the spin-rotation tensor, the calculation of the magnetic shielding tensor represents the most demanding computational task. Employing the ADFT-GIAO methodology, the central processing unit time for the magnetic shielding tensor calculation can be dramatically reduced. In this work, the quality of spin-rotation constants obtained with the ADFT-GIAO methodology is compared with available experimental data as well as with other theoretical results at the Hartree-Fock and coupled-cluster level of theory. It is found that the agreement between the ADFT-GIAO results and the experiment is good and very similar to the ones obtained by the coupled-cluster single-doubles-perturbative triples-GIAO methodology. With the improved computational performance achieved, the computation of the spin-rotation tensors of large systems or along Born-Oppenheimer molecular dynamics trajectories becomes feasible in reasonable times. Three models of carbon fullerenes containing hundreds of atoms and thousands of basis functions are used for benchmarking the performance. Furthermore, a theoretical study of temperature effects on the structure and spin-rotation tensor of the H(12)C-(12)CH-DF complex is presented. Here, the temperature dependency of the spin-rotation tensor of the fluorine nucleus can be used to identify experimentally the so far unknown bent isomer of this complex. To the best of our knowledge this is the first time that temperature effects on the spin-rotation tensor are investigated.

Assessing diel variation of CH4 flux from rice paddies through temperature patterns

NASA Astrophysics Data System (ADS)

Centeno, Caesar Arloo R.; Alberto, Ma Carmelita R.; Wassmann, Reiner; Sander, Bjoern Ole

2017-10-01

The diel variation in methane (CH4) flux from irrigated rice was characterized during the dry and wet cropping seasons in 2013 and 2014 using the eddy covariance (EC) technique. The EC technique has the advantage of obtaining measurements of fluxes at an extremely high temporal resolution (10Hz), meaning it records 36,000 measurements per hour. The EC measurements can very well capture the temporal variations of the diel (both diurnal and nocturnal) fluxes of CH4 and the environmental factors (temperature, surface energy flux, and gross ecosystem photosynthesis) at 30-min intervals. The information generated by this technique is important to enhance our mechanistic understanding of the different factors affecting the landscape scale diel CH4 flux. Distinct diel patterns of CH4 flux were observed when the data were partitioned into different cropping periods (pre-planting, growth, and fallow). The temporal variations of the diel CH4 flux during the dry seasons were more pronounced than during the wet seasons because the latter had so much climatic disturbance from heavy monsoon rains and occasional typhoons. Pearson correlation analysis and Granger causality test were used to confirm if the environmental factors evaluated were not only correlated with but also Granger-causing the diel CH4 flux. Soil temperature at 2.5 cm depth (Ts 2.5 cm) can be used as simple proxy for predicting diel variations of CH4 fluxes in rice paddies using simple linear regression during both the dry and wet seasons. This simple site-specific temperature response function can be used for gap-filling CH4 flux data for improving the estimates of CH4 source strength from irrigated rice production.

Pin-Hole Free Perovskite Film for Solar Cells Application Prepared by Controlled Two-Step Spin-Coating Method

NASA Astrophysics Data System (ADS)

Bahtiar, A.; Rahmanita, S.; Inayatie, Y. D.

2017-05-01

Morphology of perovskite film is a key important for achieving high performance perovskite solar cells. Perovskite films are commonly prepared by two-step spin-coating method. However, pin-holes are frequently formed in perovskite films due to incomplete conversion of lead-iodide (PbI2) into perovskite CH3NH3PbI3. Pin-holes in perovskite film cause large hysteresis in current-voltage curve of solar cells due to large series resistance between perovskite layer-hole transport material. Moreover, crystal structure and grain size of perovskite crystal are also other important parameters for achieving high performance solar cells, which are significantly affected by preparation of perovskite film. We studied the effect of preparation of perovskite film using controlled spin-coating parameters on crystal structure and morphological properties of perovskite film. We used two-step spin-coating method for preparation of perovskite film with varied spinning speed, spinning time and temperature of spin-coating process to control growth of perovskite crystal aimed to produce high quality perovskite crystal with pin-hole free and large grain size. All experiment was performed in air with high humidity (larger than 80%). The best crystal structure, pin-hole free with large grain crystal size of perovskite film was obtained from film prepared at room temperature with spinning speed 1000 rpm for 20 seconds and annealed at 100°C for 300 seconds.

Assessment of methane production from shredder waste in landfills: The influence of temperature, moisture and metals.

PubMed

Fathi Aghdam, Ehsan; Scheutz, Charlotte; Kjeldsen, Peter

2017-05-01

In this study, methane (CH 4 ) production rates from shredder waste (SW) were determined by incubation of waste samples over a period of 230days under different operating conditions, and first-order decay kinetic constants (k-values) were calculated. SW and sterilized SW were incubated under different temperatures (20-25°C, 37°C, and 55°C), moisture contents (35% and 75% w/w) and amounts of inoculum (5% and 30% of the samples wet weight). The biochemical methane potential (BMP) from different types of SW (fresh, old and sieved) was determined and compared. The ability of metals (iron, aluminum, zinc, and copper) contained in SW to provide electrons for methanogens resulting in gas compositions with high CH 4 contents and very low CO 2 contents was investigated. The BMP of SW was 1.5-6.2kg CH 4 /ton waste. The highest BMP was observed in fresh SW samples, while the lowest was observed in sieved samples (fine fraction of SW). Abiotic production of CH 4 was not observed in laboratory incubations. The biotic experiments showed that when the moisture content was 35% w/w and the temperature was 20-25°C, CH 4 production was extremely low. Increasing the temperature from 20-25°C to 37°C resulted in significantly higher CH 4 production while increasing the temperature from 37°C to 55°C resulted in higher CH 4 production, but to a lower extent. Increasing the moisture and inoculum content also increased CH 4 production. The k-values were 0.033-0.075yr -1 at room temperature, 0.220-0.429yr -1 at 37°C and 0.235-0.488yr -1 at 55°C, indicating that higher temperatures resulted in higher k-values. It was observed that H 2 can be produced by biocorrosion of iron, aluminum, and zinc and it was shown that produced H 2 can be utilized by hydrogenotrophic methanogens to convert CO 2 to CH 4 . Addition of iron and copper to SW resulted in inhibition of CH 4 production, while addition of aluminum and zinc resulted in higher CH 4 production. This suggested that aluminum and zinc contribute to high CH 4 production from SW by providing H 2 for hydrogenotrophic methanogens. Gas compositions with higher CH 4 and lower CO 2 observed in landfilled SW are thus most likely due to the consumption of existing CO 2 in the produced biogas and the produced H 2 by biocorrosion of aluminum and zinc by methanogens. Copyright © 2016 Elsevier Ltd. All rights reserved.

Photodissociation of the CH3O and CH3S radical molecules: An ab initio electronic structure study

PubMed Central

Bouallagui, A.; Zanchet, A.; Yazidi, O.; Jaïdane, N.; Bañares, L.; Senent, M.L.; García-Vela, A.

2018-01-01

The electronic states and the spin-orbit couplings between them involved in the photodissociation process of the radical molecules CH3X, CH3X → CH3 + X(X = O, S), taking place after the Ā(2A1) ← X̄(2E) transition, have been investigated using highly correlated ab initio techniques. A two-dimensional representation of both the potential-energy surfaces (PESs) and the couplings is generated. This description includes the C-X dissociative mode and the CH3 umbrella mode. Spin-orbit effects are found to play a relevant role on the shape of the excited state potential-energy surfaces, particularly in the CH3S case where the spin-orbit couplings are more than twice more intense than in CH3O. The potential surfaces and couplings reported here for the present set of electronic states allow for the first complete description of the above photodissociation process. The different photodissociation mechanisms are analyzed and discussed in the light of the results obtained. PMID:29143005

Complexes and saddle point structures, vibrational frequencies and relative energies of intermediates for CH2Br + HBr «-» CH3Br + Br

NASA Astrophysics Data System (ADS)

Espinosa-Garcia, J.

Ab initio molecular orbital theory was used to study parts of the reaction between the CH2Br radical and the HBr molecule, and two possibilities were analysed: attack on the hydrogen and attack on the bromine of the HBr molecule. Optimized geometries and harmonic vibrational frequencies were calculated at the second-order Moller-Plesset perturbation theory levels, and comparison with available experimental data was favourable. Then single-point calculations were performed at several higher levels of calculation. In the attack on the hydrogen of HBr, two stationary points were located on the direct hydrogen abstraction reaction path: a very weak hydrogen bonded complex of reactants, C···HBr, close to the reactants, followed by the saddle point (SP). The effects of level of calculation (method + basis set), spin projection, zeropoint energy, thermal corrections (298K), spin-orbit coupling and basis set superposition error (BSSE) on the energy changes were analysed. Taking the reaction enthalpy (298K) as reference, agreement with experiment was obtained only when high correlation energy and large basis sets were used. It was concluded that at room temperature (i.e., with zero-point energy and thermal corrections), when the BSSE was included, the complex disappears and the activation enthalpy (298K) ranges from 0.8kcal mol-1 to 1.4kcal mol-1 above the reactants, depending on the level of calculation. It was concluded also that this result is the balance of a complicated interplay of many factors, which are affected by uncertainties in the theoretical calculations. Finally, another possible complex (X complex), which involves the alkyl radical being attracted to the halogen end of HBr (C···BrH), was explored also. It was concluded that this X complex does not exist at room temperature.

A laser flash photolysis-resonance fluorescence kinetics study of the reaction Cl/2P/ + CH4 yields CH3 + HCl

NASA Technical Reports Server (NTRS)

Ravishankara, A. R.; Wine, P. H.

1980-01-01

The technique of laser flash photolysis-resonance fluorescence is employed to study the kinetics of the reaction Cl(2P) + CH4 yields CH3 + HCl over the temperature range 221-375 K. At temperatures less than or equal to 241 K the apparent bimolecular rate constant is found to be dependent upon the identity of the chemically inert gases in the reaction mixture. For Cl2/CH4/He reaction mixtures (total pressure = 50 torr) different bimolecular rate constants are measured at low and high methane concentrations. For Cl2/CH4/CCl/He and Cl2/CH4/Ar reaction mixtures, the bimolecular rate constant is independent of methane concentration, being approximately equal to the rate constant measured at low methane concentrations for Cl2/CH4/He mixtures. These rate constants are in good agreement with previous results obtained using the discharge flow-resonance fluorescence and competitive chlorination techniques. At 298 K the measured bimolecular rate constant is independent of the identity of the chemically inert gases in the reaction mixture and in good agreement with all previous investigations. The low-temperature results obtained in this investigation and all previous investigations can be rationalized in terms of a model which assumes that the Cl(2P 1/2) state reacts with CH4 much faster than the Cl(2P 3/2) state. Extrapolation of this model to higher temperatures, however, is not straightforward.

CO2 CH4 flux Air temperature Soil temperature and Soil moisture, Barrow, Alaska 2013 ver. 1

DOE Data Explorer

Margaret Torn

2015-01-14

This dataset consists of field measurements of CO2 and CH4 flux, as well as soil properties made during 2013 in Areas A-D of Intensive Site 1 at the Next-Generation Ecosystem Experiments (NGEE) Arctic site near Barrow, Alaska. Included are i) measurements of CO2 and CH4 flux made from June to September (ii) Calculation of corresponding Gross Primary Productivity (GPP) and CH4 exchange (transparent minus opaque) between atmosphere and the ecosystem (ii) Measurements of Los Gatos Research (LGR) chamber air temperature made from June to September (ii) measurements of surface layer depth, type of surface layer, soil temperature and soil moisture from June to September.

A five-year study of the impact of nitrogen addition on methane uptake in alpine grassland.

PubMed

Yue, Ping; Li, Kaihui; Gong, Yanming; Hu, Yukun; Mohammat, Anwar; Christie, Peter; Liu, Xuejun

2016-08-30

It remains unclear how nitrogen (N) deposition affects soil methane (CH4) uptake in semiarid and arid zones. An in situ field experiment was conducted from 2010 to 2014 to systematically study the effect of various N application rates (0, 10, 30, and 90 kg N ha(-1) yr(-1)) on CH4 flux in alpine grassland in the Tianshan Mountains. No significant influence of N addition on CH4 uptake was found. Initially the CH4 uptake rate increased with increasing N application rate by up to 11.5% in 2011 and then there was gradual inhibition by 2014. However, the between-year variability in CH4 uptake was very highly significant with average uptake ranging from 52.9 to 106.6 μg C m(-2) h(-1) and the rate depended largely on seasonal variability in precipitation and temperature. CH4 uptake was positively correlated with soil temperature, air temperature and to a lesser extent with precipitation, and was negatively correlated with soil moisture and NO3(-)-N content. The results indicate that between-year variability in CH4 uptake was impacted by precipitation and temperature and was not sensitive to elevated N deposition in alpine grassland.

A five-year study of the impact of nitrogen addition on methane uptake in alpine grassland

PubMed Central

Yue, Ping; Li, Kaihui; Gong, Yanming; Hu, Yukun; Mohammat, Anwar; Christie, Peter; Liu, Xuejun

2016-01-01

It remains unclear how nitrogen (N) deposition affects soil methane (CH4) uptake in semiarid and arid zones. An in situ field experiment was conducted from 2010 to 2014 to systematically study the effect of various N application rates (0, 10, 30, and 90 kg N ha−1 yr−1) on CH4 flux in alpine grassland in the Tianshan Mountains. No significant influence of N addition on CH4 uptake was found. Initially the CH4 uptake rate increased with increasing N application rate by up to 11.5% in 2011 and then there was gradual inhibition by 2014. However, the between-year variability in CH4 uptake was very highly significant with average uptake ranging from 52.9 to 106.6 μg C m−2 h−1 and the rate depended largely on seasonal variability in precipitation and temperature. CH4 uptake was positively correlated with soil temperature, air temperature and to a lesser extent with precipitation, and was negatively correlated with soil moisture and NO3−-N content. The results indicate that between-year variability in CH4 uptake was impacted by precipitation and temperature and was not sensitive to elevated N deposition in alpine grassland. PMID:27571892

Interplay of Electronic Cooperativity and Exchange Coupling in Regulating the Reactivity of Diiron(IV)-oxo Complexes towards C-H and O-H Bond Activation.

PubMed

Ansari, Azaj; Ansari, Mursaleem; Singha, Asmita; Rajaraman, Gopalan

2017-07-26

Activation of inert C-H bonds such as those of methane are extremely challenging for chemists but in nature, the soluble methane monooxygenase (sMMO) enzyme readily oxidizes methane to methanol by using a diiron(IV) species. This has prompted chemists to look for similar model systems. Recently, a (μ-oxo)bis(μ-carboxamido)diiron(IV) ([Fe IV 2 O(L) 2 ] 2+ L=N,N-bis-(3',5'-dimethyl-4'-methoxypyridyl-2'-methyl)-N'-acetyl-1,2-diaminoethane) complex has been generated by bulk electrolysis and this species activates inert C-H bonds almost 1000 times faster than mononuclear Fe IV =O species and at the same time selectively activates O-H bonds of alcohols. The very high reactivity and selectivity of this species is puzzling and herein we use extensive DFT calculations to shed light on this aspect. We have studied the electronic and spectral features of diiron {Fe III -μ(O)-Fe III } +2 (complex I), {Fe III -μ(O)-Fe IV } +3 (II), and {Fe IV -μ(O)-Fe IV } +4 (III) complexes. Strong antiferromagnetic coupling between the Fe centers leads to spin-coupled S=0, S=3/2, and S=0 ground state for species I-III respectively. The mechanistic study of the C-H and O-H bond activation reveals a multistate reactivity scenario where C-H bond activation is found to occur through the S=4 spin-coupled state corresponding to the high-spin state of individual Fe IV centers. The O-H bond activation on the other hand, occurs through the S=2 spin-coupled state corresponding to an intermediate state of individual Fe IV centers. Molecular orbital analysis reveals σ-π/π-π channels for the reactivity. The nature of the magnetic exchange interaction is found to be switched during the course of the reaction and this offers lower energy pathways. Significant electronic cooperativity between two metal centers during the course of the reaction has been witnessed and this uncovers the reason behind the efficiency and selectivity observed. The catalyst is found to prudently choose the desired spin states based on the nature of the substrate to effect the catalytic transformations. These findings suggest that the presence of such factors play a role in the reactivity of dinuclear metalloenzymes such as sMMO. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Magnetite nano-islands on Graphene

NASA Astrophysics Data System (ADS)

Anderson, Nathaniel; Zhang, Qiang; Rosenberg, Richard; Vaknin, David

X-ray magnetic circular dichroism (XMCD) of ex-situ iron nano-islands grown on graphene reveals that iron oxidation spontaneously leads to the formation of magnetite nano-particles - i.e, the formation of the inverse spinel Fe3O4. Fe islands have been grown with two different heights (20 and 75 MLs) on epitaxial graphene and we have determined their magnetic behavior both as function of temperature and applied external field. Our XAS and XMCD at an applied magnetic field of B = 5 T show that the thin film (20 MLs) is totally converted to magnetite whereas the thicker film (75 MLs) exhibits magnetite properties but also those of pure metal iron. For both samples, temperature dependence of the XMCD shows clear transitions at ~120 K consistent with the Verwey transition of bulk magnetite. XMCD at low temperatures shows a weak hysteresis and provide the average spin and angular-momentum moments, the dipolar term, and the total moment . In addition, manipulation and comparison of the XMCD data from both samples allows us to extract information about the pure iron nano-islands from the thicker sample. Ames Laboratory is supported by the U.S. DOE, BES, MSE Contract No. DE-AC02-07CH11358. APS is supported by U.S. DOE Contract No. DE-AC02-06CH11357.

Effect of water and heat transport processes on methane emissions from paddy soils: a process-based model analysis

NASA Astrophysics Data System (ADS)

Rizzo, Anacleto; Boano, Fulvio; Revelli, Roberto; Ridolfi, Luca

2013-04-01

High CH4 fluxes are emitted from paddy fields worldwide and represent a considerable issue for the rice production eco-sustainability. Water and heat transport fluxes are known to strongly influence biogeochemical cycles in wetland environments, and therefore also CH4 emissions from paddy soils. Water percolation affects the dynamics of many compounds (e.g. DOC, O2) influencing CH4 fate. On the other hand, heat fluxes strongly influence CH4 production in submerged rice crops, and lowering ponding water temperature (LPWT) can reduce microbial activities and consequently decrease CH4 emissions. Moreover, as long as the optimal temperature range for rice growth is maintained, LPWT can lower CH4 emissions without rice yield limitation. Hence, a process-based model is proposed and applied to investigate the role of water flow on CH4 emissions, and to analyse the efficiency of LPWT as mitigation strategy for CH4 production and release. The process-based model relies on a system of partial differential mass balance equations to describe the vertical dynamics of the chemical compounds leading to CH4 production. Many physico-chemical processes and features characteristic of paddy soil are included: paddy soil stratigraphy; spatio-temporal variations of plant-root compartment; water and heat transport; SOC decomposition; heterotrophic reactions in both aerobic and anaerobic conditions; root radial oxygen loss; root solute uptake; DOC root exudation; plant-mediated, ebullition, and diffusion gas exchange pathways. LPWT is included as a temperature shift subtracted directly to the ponding water temperature. Model results confirm the importance of water flow on CH4 emission, since simulations that do not include water fluxes show a considerable overestimation of CH4 emissions due to a different DOC spatio-temporal dynamics. Particularly, when water fluxes are not modeled the overestimation can reach 67 % of the total CH4 emission over the whole growing season. Moreover, model results also suggest that roots influence CH4 dynamics principally due to their solute uptake, while root effect on advective flow plays a minor role. In addition, the analysis of CH4 transport fluxes show the limiting effect of upward dispersive transport fluxes on the downward CH4 percolation. Finally, LPWT is confirmed to be a valid mitigation strategy for CH4 emissions from paddy soils, since the reduction of CH4 emission reach about -50 % with a LPWT equal to only 2°C over the whole growing season.

Landscape patterns of CH4 fluxes in an alpine tundra ecosystem

USGS Publications Warehouse

West, A.E.; Brooks, P.D.; Fisk, M.C.; Smith, Lesley K.; Holland, E.A.; Jaeger, C. H.; Babcock, S.; Lai, R.S.; Schmidt, S.K.

1999-01-01

We measured CH4 fluxes from three major plant communities characteristic of alpine tundra in the Colorado Front Range. Plant communities in this ecosystem are determined by soil moisture regimes induced by winter snowpack distribution. Spatial patterns of CH4 flux during the snow-free season corresponded roughly with these plant communities. In Carex-dominated meadows, which receive the most moisture from snowmelt, net CH4 production occurred. However, CH4 production in one Carex site (seasonal mean = +8.45 mg CH4 m-2 d-1) was significantly larger than in the other Carex sites (seasonal means = -0.06 and +0.05 mg CH4 m-2 d-1). This high CH4 flux may have resulted from shallower snowpack during the winter. In Acomastylis meadows, which have an intermediate moisture regime, CH4 oxidation dominated (seasonal mean = -0.43 mg CH4 m-2 d-1). In the windswept Kobresia meadow plant community, which receive the least amount of moisture from snowmelt, only CH4 oxidation was observed (seasonal mean = -0.77 mg CH4 m-2 d-1). Methane fluxes correlated with a different set of environmental factors within each plant community. In the Carex plant community, CH4 emission was limited by soil temperature. In the Acomastylis meadows, CH4 oxidation rates correlated positively with soil temperature and negatively with soil moisture. In the Kobresia community, CH4 oxidation was stimulated by precipitation. Thus, both snow-free season CH4 fluxes and the controls on those CH4 fluxes were related to the plant communities determined by winter snowpack.

Effects of prolonged soil drought on CH4 oxidation in a temperate spruce forest

NASA Astrophysics Data System (ADS)

Borken, W.; Brumme, R.; Xu, Y.-J.

2000-03-01

Our objective was to determine potential impacts of changes in rainfall amount and distribution on soil CH4 oxidation in a temperate forest ecosystem. We constructed a roof below the canopy of a 65-year-old Norway spruce forest (Picea abies (L.) Karst.) and simulated two climate change scenarios: (1) an extensively prolonged summer drought of 172 days followed by a rewetting period of 19 days in 1993 and (2) a less intensive summer drought of 108 days followed by a rewetting period of 33 days in 1994. CH4 oxidation, soil matric potential, and soil temperature were measured hourly to daily over a 2-year period. The results showed that annual CH4 oxidation in the drought experiment increased by 102% for the climate change scenario 1 and by 41% for the climate change scenario 2, compared to those of the ambient plot (1.33 kg CH4 ha-1 in 1993 and 1.65 kg CH4 ha-1 in 1994). We tested the relationships between CH4 oxidation rates, water-filled pore space (WFPS), soil matric potential, gas diffusivity, and soil temperature. Temporal variability in the CH4 oxidation rates corresponded most closely to soil matric potential. Employing soil matric potential and soil temperature, we developed a nonlinear model for estimating CH4 oxidation rates. Modeled results were in strong agreement with the measured CH4 oxidation for the ambient (r2 = 0.80) and drought plots (r2 = 0.89) over two experimental years, suggesting that soil matric potential is a highly reliable parameter for modeling CH4 oxidation rate.

Hot filament-dissociation of (CH3)3SiH and (CH3)4Si, probed by vacuum ultra violet laser time of flight mass spectroscopy.

PubMed

Sharma, Ramesh C; Koshi, Mitsuo

2006-11-01

The decomposition of trimethylsilane and tetramethylsilane has been investigated for the first time, using hot wire (catalytic) at various temperatures. Trimethylsilane is catalytic-dissociated in these species SiH(2), CH(3)SiH, CH(3), CH(2)Si. Time of flight mass spectroscopy signal of these species are linearly increasing with increasing catalytic-temperature. Time of flight mass spectroscopy (TOFMS) signals of (CH(3))(3)SiH and photodissociated into (CH(3))(2)SiH are decreasing with increasing hot filament temperature. TOFMS signal of (CH(3))(4)Si is decreasing with increasing hot wire temperature, but (CH(3))(3)Si signal is almost constant with increasing the temperature. We calculated activation energies of dissociated species of the parental molecules for fundamental information of reaction kinetics for the first time. Catalytic-dissociation of trimethylsilane, and tetramethylsilane single source time of flight coupled single photon VUV (118 nm) photoionization collisionless radicals at temperature range of tungsten filament 800-2360 K. The study is focused to understand the fundamental information on reaction kinetics of these molecules at hot wire temperature, and processes of catalytic-chemical vapour deposition (Cat-CVD) technique which could be implemented in amorphous and crystalline SiC semiconductors thin films.

The Effects of Nonzero Total Electron Spin in the X˜3B1State of Methylene CH 2

NASA Astrophysics Data System (ADS)

Kozin, Igor N.; Jensen, Per

1997-06-01

We report here how we have incorporated the effects of a nonzero total electron spin in the MORBID Hamiltonian and computer program [P. Jensen,J. Mol. Spectrosc.128,478-501 (1988);J. Chem. Soc. Faraday Trans. 284,1315-1340 (1988);in"Methods in Computational Molecular Physics" (S. Wilson and G. H. F. Diercksen, Eds.), Plenum Press, New York, 1992] for calculating the rovibronic energies of a triatomic molecule directly from the potential energy function. The spin-spin and spin-rotation Hamiltonian terms, given in a form depending on the vibrational coordinates, have been expressed in terms of isotope-independent functions and added to the MORBID rotation-vibration Hamiltonian. The eigenvalues of the resulting Hamiltonian are obtained in a variational procedure. This method is tested on the methylene radical CH2in theX˜3B1electronic ground state for which we describe simultaneously the splittings due to electron spin for the isotopomers12CH2,12CD2, and13CH2. For these molecules, experimental data are available, and we compare the results of least-squares fits to these data with predictions fromab initiotheory.

Methane to methanol conversion induced by thorium oxide through the CH3Th(O)H intermediate in solid argon.

PubMed

Gong, Yu; Andrews, Lester; Jackson, Virgil E; Dixon, David A

2012-10-15

Reactions of ThO molecules and CH(4) have been investigated in solid argon near 4 K. The CH(3)Th(O)H molecule is produced when the sample is exposed to UV irradiation. Identification of this new intermediate is substantiated by observation of the Th═O and Th-H stretching vibrational modes with isotopic substitution via matrix infrared spectroscopy, and the assignments are supported by electronic structure frequency calculations. Methanol absorptions increase together with formation of the CH(3)Th(O)H molecule, suggesting a methane to methanol conversion induced by thorium oxide proceeding through the CH(3)Th(O)H intermediate. The formation of CH(3)Th(O)H from ThO + CH(4) is exothermic (ΔH(rxn) = -11 kcal/mol) with an energy barrier of 30 kcal/mol at the CCSD(T)//B3LYP level. Decomposition of this intermediate to form methanol involves spin crossing, and the overall reaction from the intermediate is endothermic by 127 kcal/mol. There is no activation energy for the reaction of thorium atoms with methanol to give CH(3)Th(O)H, as observed in separate experiments with Th and CH(3)OH.

Seasonal variation in CH4 emissions and production and oxidation potentials at microsites on an oligotrophic pine fen.

PubMed

Saarnio, S; Alm, Jukka; Silvola, Jouko; Lohila, Annalea; Nykänen, Hannu; Martikainen, Pertti J

1997-04-01

 Temporal and spatial variation in CH 4 emissions was studied at hummock, Eriophorum lawn, flark and Carex lawn microsites in an oligotrophic pine fen over the growing season using a static chamber method, and CH 4 production and oxidation potentials in peat profiles from hummock and flark were determined in laboratory incubation experiments. Emissions were lowest in the hummocks, and decreased with increasing hummock height, while in the lawns and flarks they increased with increasing sedge cover. Statistical response functions with water table and peat temperature as independent variables were calculated in order to reconstruct seasonal CH 4 emissions by reference to the time series for peat temperature and water table specific to each microsite type. Mean CH 4 emissions in the whole area in the snow-free period of 1993, weighted in terms of the proportions of the microsites, were 1.7 mol CH 4 m -2 . Potential CH 4 production and oxidation rates were very low in the hummocks rising above the groundwater table, but were relatively similar when expressed per dry weight of peat both in the hummocks and flarks below the water table. The CH 4 production potential increased in autumn at both microsites and CH 4 oxidation potential seemed to decrease. The decrease in temperature in autumn certainly reduced in situ decomposition processes, possibly leaving unused substrates in the peat, which would explain the increase in CH 4 production potential.

Mitigating methane emission from paddy soil with rice-straw biochar amendment under projected climate change

PubMed Central

Han, Xingguo; Sun, Xue; Wang, Cheng; Wu, Mengxiong; Dong, Da; Zhong, Ting; Thies, Janice E.; Wu, Weixiang

2016-01-01

Elevated global temperatures and increased concentrations of carbon dioxide (CO2) in the atmosphere associated with climate change will exert profound effects on rice cropping systems, particularly on their greenhouse gas emitting potential. Incorporating biochar into paddy soil has been shown previously to reduce methane (CH4) emission from paddy rice under ambient temperature and CO2. We examined the ability of rice straw-derived biochar to reduce CH4 emission from paddy soil under elevated temperature and CO2 concentrations expected in the future. Adding biochar to paddy soil reduced CH4 emission under ambient conditions and significantly reduced emissions by 39.5% (ranging from 185.4 mg kg−1 dry weight soil, dws season−1 to 112.2 mg kg−1 dws season−1) under simultaneously elevated temperature and CO2. Reduced CH4 release was mainly attributable to the decreased activity of methanogens along with the increased CH4 oxidation activity and pmoA gene abundance of methanotrophs. Our findings highlight the valuable services of biochar amendment for CH4 control from paddy soil in a future that will be shaped by climate change. PMID:27090814

Seasonal variation in methane emission from stored slurry and solid manures

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

Husted, S.

1994-05-01

Methane (CH{sub 4}) is an important greenhouse gas and recent inventories have suggested that livestock manure makes a significant contribution to global CH{sub 4} emissions. The emission of CH{sub 4} from stored pig slurry, cattle slurry, pig solid manure, and cattle solid manure was followed during a 1-yr period. Methane emission was determined by dynamic chambers. Emission rates followed a ln-normal distribution for all four manures, Indicating large spatial and seasonal variation& Monthly geometric means for pig slurry, cattle slurry, pig solid manure, and cattle solid manure varied from 0.4 to 35.8, 0.0 to 34.5, 0.4 to 142.1, and 0.1more » to 42.7 g CH{sub 4} m{sup -3} d{sup -1}, respectively. For slurries CH{sub 4} emission rates increased significantly with storage temperatures, the Q{sub 10} value ranging from 14 to 5.7 depending on slurry type. The presence of a natural surface crust reduced CH{sub 4} emission from slurry by a factor of 11 to 12. Surface crust effects declined with increasing slurry temperature. Solid manures stored in dungheaps showed significant heat production. Pig solid manure temperatures were maintained at 30 to 60{degrees}C throughout most of the year, while cattle solid manure temperatures were close to ambient levels until late spring, when heat production was initiated. Methanogenesis in solid manure also increased with increasing temperatures. For pig solid manure, CH{sub 4} emission rates peaked at 35 to 45{degrees}C. No distinct temperature optimum could be detected for cattle solid manure, however, temperatures rarely exceeded 45{degrees}C. The Q{sub 10} values for dungheaps ranged from 2.7 to 10.3 depending on-manure type and Q{sub 10} temperature interval. Annual CH{sub 4} emissions from pig slurry, cattle slurry, pig solid manure, and cattle solid manure were estimated at 8.9, 15.5, 27.3, and 5.3 kg animal{sup -1} yr{sup -1}, respectively. 27 refs., 6 figs., 2 tabs.« less

Fall season atypically warm weather event leads to substantial CH4 loss in Arctic ecosystems?

NASA Astrophysics Data System (ADS)

Zona, Donatella; Moreaux, Virginie; Liljedahl, Anna; Losacco, Salvatore; Murphy, Patrick; Oechel, Walter

2014-05-01

In the last century (during 1875-2008) high-latitudes are warming at a rate of 1.360C century-1, almost 2 times faster than the Northern Hemisphere trend (Bekryaev et al., 2010). This warming has been more intense outside of the summer season, with anomalies of 1.09, 1.59, 1.730C in the fall, winter, and spring season respectively (Bekryaev et al., 2010). This substantial temperature anomalies have the potential to increase the emission of greenhouse gas (CO2 and CH4) fluxes from arctic tundra ecosystems. In particular, CH4 emissions, which are primarily controlled by temperature (in addition to water table), can steeply increase with warming. Despite the potential relevance of CH4 emissions, very few measurements have been performed outside of the growing season across the entire Arctic, due to logistic constrains. Importantly, no flux measurements achieved a temporal and spatial data coverage sufficient to estimate with confidence an annual CH4 emissions from tundra ecosystem in Alaska, and its sensitivity to warming. Fall 2013 was unusually warm in central and northern Alaska. Following a relatively warm summer with dramatically above-average rainfall, the October mean monthly temperatures was the 4th and top warmest in Barrow (1949-2013) and Ivotuk (1998-2013), respectively. As we just upgraded several eddy covariance towers to measure CO2 and CH4 fluxes year-round, the atypical weather conditions of fall 2013 represented a unique chance for testing the sensitivity of CH4 loss to these atypically warm temperatures. All our sites across a latitudinal gradient (from the northern site, Barrow, to the southern site, Ivotuk), presented substantial CH4 loss in the fall. Importantly, in two of these sites (Barrow, Ivotuk) where the fall weather was substantially warmer than the long term trend, fall CH4 emission represented between 44-63% of the June-November cumulative emission. Surprisingly, in the southernmost site (Ivotuk), when the temperature anomaly was the highest, cumulative fall CH4 emission outpaced even the summer emission. This shows the sensitivity of CH4 loss to abnormal conditions, and the importance of fall periods for the annual CH4 budget in these Arctic ecosystems. Bekryaev, R. V., I. V. Polyakov, and V. A. Alexeev. 2010. Role of polar amplification in long-term surface air temperature variations and modern Arctic warming. Journal of Climate 23(14):3888-3906.

Carbon dioxide and methane emissions from the scale model of open dairy lots.

PubMed

Ding, Luyu; Cao, Wei; Shi, Zhengxiang; Li, Baoming; Wang, Chaoyuan; Zhang, Guoqiang; Kristensen, Simon

2016-07-01

To investigate the impacts of major factors on carbon loss via gaseous emissions, carbon dioxide (CO2) and methane (CH4) emissions from the ground of open dairy lots were tested by a scale model experiment at various air temperatures (15, 25, and 35 °C), surface velocities (0.4, 0.7, 1.0, and 1.2 m sec(-1)), and floor types (unpaved soil floor and brick-paved floor) in controlled laboratory conditions using the wind tunnel method. Generally, CO2 and CH4 emissions were significantly enhanced with the increase of air temperature and velocity (P < 0.05). Floor type had different effects on the CO2 and CH4 emissions, which were also affected by air temperature and soil characteristics of the floor. Although different patterns were observed on CH4 emission from the soil and brick floors at different air temperature-velocity combinations, statistical analysis showed no significant difference in CH4 emissions from different floors (P > 0.05). For CO2, similar emissions were found from the soil and brick floors at 15 and 25 °C, whereas higher rates were detected from the brick floor at 35 °C (P < 0.05). Results showed that CH4 emission from the scale model was exponentially related to CO2 flux, which might be helpful in CH4 emission estimation from manure management. Gaseous emissions from the open lots are largely dependent on outdoor climate, floor systems, and management practices, which are quite different from those indoors. This study assessed the effects of floor types and air velocities on CO2 and CH4 emissions from the open dairy lots at various temperatures by a wind tunnel. It provided some valuable information for decision-making and further studies on gaseous emissions from open lots.

Exploring sub-daily to seasonal variations in methane exchange in a single-crop rice paddy in central Japan

NASA Astrophysics Data System (ADS)

Iwata, Hiroki; Mano, Masayoshi; Ono, Keisuke; Tokida, Takeshi; Kawazoe, Takahiro; Kosugi, Yoshiko; Sakabe, Ayaka; Takahashi, Kenshi; Miyata, Akira

2018-04-01

Season-long methane (CH4) exchange was observed in a rice paddy field in central Japan (Kanto Region) using the eddy covariance technique to clarify the variations in environmental controls on CH4 exchange in different stages of cultivation. Before heading of rice plant, the CH4 emission depended on wind speed and soil temperature. The soil temperature dependence can be due to an increase in CH4 production, higher molecular diffusion, and higher conductance within rice plant at higher soil temperature. An occurrence of ebullitive emission was also suggested from the wind speed dependence. After heading was completed, relative humidity and water temperature influenced CH4 emission. The amplitude of the diurnal variation in emission increased from 0.03 μmolm-2s-1 in the late pre-heading stage to 0.13 μmolm-2s-1 in the post-heading stage. Induced convective throughflow within the rice aerenchyma after the change in plant structure was attributable to this variation in environmental controls after the heading. After drainage, CH4 emission was confined to short periods after strong rain events. The water level controlled the timing of emission, most likely by influencing the diffusion efficiency from the anoxic soil to the atmosphere and CH4 oxidation in the surface oxic zone. The variation in the dominant transport pathway needs to be accounted for in terrestrial ecosystem models to accurately predict CH4 emission from rice paddies.

Review of NMR studies of nanoscale molecular magnets composed of geometrically frustrated antiferromagnetic triangles

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

Furukawa, Yuji

This paper presents a comprehensive review of nuclear magnetic resonance (NMR) studies performed on three nanoscale molecular magnets with different novel configurations of geometrically frustrated antiferromagnetic (AFM) triangles: (1) the isolated single AFM triangle K 6[V 15As 6O 42(H 2O)]·8H 2O (in short V15), (2) the spin ball [Mo 72Fe 30O 252(Mo 2O 7(H 2O)) 2(Mo 2O 8H 2(H 2O)) (CH 3COO) 12(H 2O) 91]·150H 2O (in short Fe30 spin ball), and (3) the twisted triangular spin tube [(CuCl 2tachH) 3Cl]Cl 2 (in short Cu3 spin tube). In V15t, from 51V NMR spectra, the local spin configurations were directly determinedmore » in both the nonfrustrated total spin S T = 3/2 state at higher magnetic fields (H ge; 2.7 T) and the two nearly degenerate S T = 1/2 ground states at lower magnetic fields (H ≤ 2.7 T). The dynamical magnetic properties of V15 were investigated by proton spin-lattice relaxation rate (1/T 1) measurements. In the S T = 3/2 state, 1/T 1 shows thermally activated behaviour as a function of temperature. On the other hand, the temperature independent behaviour of 1/T 1 at very low temperatures is observed in the frustrated S T = 1/2 ground state. Possible origins for the peculiar behaviour of 1/T 1 will be discussed in terms of magnetic fluctuations due to spin frustrations. In Fe30, static and dynamical properties of Fe 3+ (s = 5/2) have been investigated by proton NMR spectra and 1/T 1 measurements. From the temperature dependence of 1/T 1, the fluctuation frequency of the Fe 3+ spins is found to decrease with decreasing temperature, indicating spin freezing at low temperatures. The spin freezing is also evidenced by the observation of a sudden broadening of 1H NMR spectra below 0.6 K. Finally, 1H NMR data in Cu3 will be described. An observation of magnetic broadening of 1H NMR spectra at low temperatures below 1 K directly revealed a gapless ground state. The 1/T 1 measurements revealed a usual slow spin dynamics in the Cu3 spin tube.« less

Review of NMR studies of nanoscale molecular magnets composed of geometrically frustrated antiferromagnetic triangles

DOE PAGES

Furukawa, Yuji

2016-10-01

This paper presents a comprehensive review of nuclear magnetic resonance (NMR) studies performed on three nanoscale molecular magnets with different novel configurations of geometrically frustrated antiferromagnetic (AFM) triangles: (1) the isolated single AFM triangle K 6[V 15As 6O 42(H 2O)]·8H 2O (in short V15), (2) the spin ball [Mo 72Fe 30O 252(Mo 2O 7(H 2O)) 2(Mo 2O 8H 2(H 2O)) (CH 3COO) 12(H 2O) 91]·150H 2O (in short Fe30 spin ball), and (3) the twisted triangular spin tube [(CuCl 2tachH) 3Cl]Cl 2 (in short Cu3 spin tube). In V15t, from 51V NMR spectra, the local spin configurations were directly determinedmore » in both the nonfrustrated total spin S T = 3/2 state at higher magnetic fields (H ge; 2.7 T) and the two nearly degenerate S T = 1/2 ground states at lower magnetic fields (H ≤ 2.7 T). The dynamical magnetic properties of V15 were investigated by proton spin-lattice relaxation rate (1/T 1) measurements. In the S T = 3/2 state, 1/T 1 shows thermally activated behaviour as a function of temperature. On the other hand, the temperature independent behaviour of 1/T 1 at very low temperatures is observed in the frustrated S T = 1/2 ground state. Possible origins for the peculiar behaviour of 1/T 1 will be discussed in terms of magnetic fluctuations due to spin frustrations. In Fe30, static and dynamical properties of Fe 3+ (s = 5/2) have been investigated by proton NMR spectra and 1/T 1 measurements. From the temperature dependence of 1/T 1, the fluctuation frequency of the Fe 3+ spins is found to decrease with decreasing temperature, indicating spin freezing at low temperatures. The spin freezing is also evidenced by the observation of a sudden broadening of 1H NMR spectra below 0.6 K. Finally, 1H NMR data in Cu3 will be described. An observation of magnetic broadening of 1H NMR spectra at low temperatures below 1 K directly revealed a gapless ground state. The 1/T 1 measurements revealed a usual slow spin dynamics in the Cu3 spin tube.« less

Factors Related with CH4 and N2O Emissions from a Paddy Field: Clues for Management implications

PubMed Central

Wang, Chun; Lai, Derrick Y. F.; Sardans, Jordi; Wang, Weiqi; Zeng, Congsheng; Peñuelas, Josep

2017-01-01

Paddy fields are major sources of global atmospheric greenhouse gases, including methane (CH4) and nitrous oxide (N2O). The different phases previous to emission (production, transport, diffusion, dissolution in pore water and ebullition) despite well-established have rarely been measured in field conditions. We examined them and their relationships with temperature, soil traits and plant biomass in a paddy field in Fujian, southeastern China. CH4 emission was positively correlated with CH4 production, plant-mediated transport, ebullition, diffusion, and concentration of dissolved CH4 in porewater and negatively correlated with sulfate concentration, suggesting the potential use of sulfate fertilizers to mitigate CH4 release. Air temperature and humidity, plant stem biomass, and concentrations of soil sulfate, available N, and DOC together accounted for 92% of the variance in CH4 emission, and Eh, pH, and the concentrations of available N and Fe3+, leaf biomass, and air temperature 95% of the N2O emission. Given the positive correlations between CH4 emission and DOC content and plant biomass, reduce the addition of a carbon substrate such as straw and the development of smaller but higher yielding rice genotypes could be viable options for reducing the release of greenhouse gases from paddy fields to the atmosphere. PMID:28081161

Response of surface CH4 and CO2 fluxes to whole ecosystem warming and elevated CO2 in a boreal black spruce peatland, northern Minnesota

NASA Astrophysics Data System (ADS)

Hsieh, I. F.; Gill, A. L.; Finzi, A.

2017-12-01

Potential increase in peatland C losses by environmental change has been presented by impacting the balance of CO2 and CH4 sequestration and release. While temperature warming may accelerate the temperature-sensitive processes and release CO2 and CH4 from peat C stores, factors associated with warming and that associated with elevated CO2 concentration may alter the intrinsic characteristics of CO2 and CH4 emission from peatland. By leveraging Spruce and Peatland Responses Under Changing Environments (SPRUCE) experiment, we measured peat surface CO2 and CH4 fluxes and their i13C signatures across a gradient of warming temperatures in a boreal black spruce peat bog in 2015 and 2016 growing seasons. Elevated CO2 (eCO2) treatment was added to the warming experiment in June, 2016. Our results show both CH4 and CO2 flux increased with warming temperature in the two-year measurement period. Total emission for both gases were higher in 2016 with whole ecosystem warming than that in 2015 with deep peat heat warming. The 2016 increase in CO2 emission was significantly larger in the hummock microtopographic position compared to hollows. The opposite was true for CH4 fluxes, where the increase was strongest in the hollows. In fact, CH4 flux from hummocks declined in 2016 compared to 2015, suggesting lower overall rates of CH4 production and/or greater rates of methanotrophy. The increase (less depleted) in i13C -CH4 signatures suggest acetoclastic methanogensis increased its contribution to total CH4 production across the growing season and in response to experimental warming, while hydrogenotrophic methanogenesis dominated total CH4 production. On the contrary, results of i13C-CO2 show no significant change in the contribution of different sources to total CO2 emission through time or across warming temperature. On the other hand, i13C-CO2 signatures under CO2 fumigation in 2016 was significantly depleted since the eCO2 initiation, indicating a rapid increase in plant productivity and the subsequent belowground transfer of photosynthate. Our results emphasize the susceptibleness of northern peat bog to changes in the environment by illustrating measureable influences of whole ecosystem warming and elevated CO2 on greenhouse gases emission.

Eutrophication exacerbates the impact of climate warming on lake methane emission.

PubMed

Sepulveda-Jauregui, Armando; Hoyos-Santillan, Jorge; Martinez-Cruz, Karla; Walter Anthony, Katey M; Casper, Peter; Belmonte-Izquierdo, Yadira; Thalasso, Frédéric

2018-04-27

Net methane (CH 4 ) emission from lakes depends on two antagonistic processes: CH 4 production (methanogenesis) and CH 4 oxidation (methanotrophy). It is unclear how climate warming will affect the balance between these processes, particularly among lakes of different trophic status. Here we show that methanogenesis is more sensitive to temperature than methanotrophy, and that eutrophication magnifies this temperature sensitivity. Using laboratory incubations of water and sediment from ten tropical, temperate and subarctic lakes with contrasting trophic states, ranging from oligotrophic to hypereutrophic, we explored the temperature sensitivity of methanogenesis and methanotrophy. We found that both processes presented a higher temperature sensitivity in tropical lakes, followed by temperate, and subarctic lakes; but more importantly, we found that eutrophication triggered a higher temperature sensitivity. A model fed by our empirical data revealed that increasing lake water temperature by 2 °C leads to a net increase in CH 4 emissions by 101-183% in hypereutrophic lakes and 47-56% in oligotrophic lakes. We conclude that climate warming will tilt the CH 4 balance towards higher lake emission and that this impact will be exacerbated by the eutrophication of the lakes. Copyright © 2018 Elsevier B.V. All rights reserved.

Effects of H{sub 2} and H preferential diffusion and unity Lewis number on superadiabatic flame temperatures in rich premixed methane flames

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

Liu, Fengshan; Guelder, OEmer L.

2005-11-01

The structures of freely propagating rich CH{sub 4}/air and CH{sub 4}/O{sub 2} flames were studied numerically using a relatively detailed reaction mechanism. Species diffusion was modeled using five different methods/assumptions to investigate the effects of species diffusion, in particular H{sub 2} and H, on superadiabatic flame temperature. With the preferential diffusion of H{sub 2} and H accounted for, significant amount of H{sub 2} and H produced in the flame front diffuse from the reaction zone to the preheat zone. The preferential diffusion of H{sub 2} from the reaction zone to the preheat zone has negligible effects on the phenomenon ofmore » superadiabatic flame temperature in both CH{sub 4}/air and CH{sub 4}/O{sub 2} flames. It is therefore demonstrated that the superadiabatic flame temperature phenomenon in rich hydrocarbon flames is not due to the preferential diffusion of H{sub 2} from the reaction zone to the preheat zone as recently suggested by Zamashchikov et al. [V.V. Zamashchikov, I.G. Namyatov, V.A. Bunev, V.S. Babkin, Combust. Explosion Shock Waves 40 (2004) 32]. The suppression of the preferential diffusion of H radicals from the reaction zone to the preheat zone drastically reduces the degree of superadiabaticity in rich CH{sub 4}/O{sub 2} flames. The preferential diffusion of H radicals plays an important role in the occurrence of superadiabatic flame temperature. The assumption of unity Lewis number for all species leads to the suppression of H radical diffusion from the reaction zone to the preheat zone and significant diffusion of CO{sub 2} from the postflame zone to the reaction zone. Consequently, the degree of superadiabaticity of flame temperature is also significantly reduced. Through reaction flux analyses and numerical experiments, the chemical nature of the superadiabatic flame temperature phenomenon in rich CH{sub 4}/air and CH{sub 4}/O{sub 2} flames was identified to be the relative scarcity of H radical, which leads to overshoot of H{sub 2}O and CH{sub 2}CO in CH{sub 4}/air flames and overshoot of H{sub 2}O in CH{sub 4}/O{sub 2} flames.« less

Spectroscopic line parameters of 12CH4 for atmospheric composition retrievals in the 4300-4500 cm-1 region

NASA Astrophysics Data System (ADS)

Hashemi, R.; Predoi-Cross, A.; Nikitin, A. V.; Tyuterev, Vl. G.; Sung, K.; Smith, M. A. H.; Malathy Devi, V.

2017-01-01

Due to the importance of methane as a trace atmospheric gas and a greenhouse gas, we have carried out a precise line-shape study to obtain the CH4-CH4 and CH4-air half-width coefficients, CH4-CH4 and CH4-air shift coefficients and off-diagonal relaxation matrix element coefficients for methane transitions in the spectral range known as the "methane Octad". In addition, the associated temperature dependences of these coefficients have been measured in the 4300-4500 cm-1 region of the Octad. The high signal to noise ratio spectra of pure methane and of dilute mixtures of methane in dry air with high resolution have been recorded at temperatures from 148 K to room temperature using the Bruker IFS 125 HR Fourier transform spectrometer (FTS) at the Jet Propulsion Laboratory, Pasadena, California. The analysis of spectra was done using a multispectrum non-linear least-squares curve fitting technique. Theoretical calculations have been performed and the results are compared with the previously published line positions, intensities and with the line parameters available in the GEISA and HITRAN2012 databases.

HSO2+ Formation from Ion-Molecule Reactions of SO2⋅+ with Water and Methane: Two Fast Reactions with Reverse Temperature-Dependent Kinetic Trend.

PubMed

Cartoni, Antonella; Catone, Daniele; Bolognesi, Paola; Satta, Mauro; Markus, Pal; Avaldi, Lorenzo

2017-05-17

In this work an experimental and theoretical study on the formation of HSO 2 + ion from the SO 2 ⋅+ +CH 4 and SO 2 ⋅+ +H 2 O ion-molecule reactions at different temperatures is reported. Tunable synchrotron radiation was used to produce the SO 2 ⋅+ ion in excited ro-vibrational levels of the ionic ground state X 2 A 1 and mass spectrometry was employed to identify the product ions. Calculations in the frame of the density functional theory and variational transition state theory were combined to explore the dynamics of the reactions. The experimental results show that HSO 2 + is the only product in both reactions. Its yield decreases monotonically with photon energy in the SO 2 ⋅+ +H 2 O reaction, while it decreases at first and then increases in the SO 2 ⋅+ +CH 4 reaction. Theory confirms this trend by calculating the rate constants at different temperatures and explains the results by means of the polar, spin and charge effects as well as structural reorganization occurring in the reaction coordinate. The dynamic behavior observed in these two reactions is of general and fundamental interest. It can also provide some insights on the role of these reactions in astrochemistry as well as in their use as models for bond-activation reactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Implanted bismuth donors in 28-Si: Process development and electron spin resonance measurements

NASA Astrophysics Data System (ADS)

Weis, C. D.; Lo, C. C.; Lang, V.; George, R. E.; Tyryshkin, A. M.; Bokor, J.; Lyon, S. A.; Morton, J. J. L.; Schenkel, T.

2012-02-01

Spins of donor atoms in silicon are excellent qubit candidates. Isotope engineered substrates provide a nuclear spin free host environment, resulting in long spin coherence times [1,2]. The capability of swapping quantum information between electron and nuclear spins can enable quantum communication and gate operation via the electron spin and quantum memory via the nuclear spin [2]. Spin properties of donor qubit candidates in silicon have been studied mostly for phosphorous and antimony [1-3]. Bismuth donors in silicon exhibit a zero field splitting of 7.4 GHz and have attracted attention as potential nuclear spin memory and spin qubit candidates [4,5] that could be coupled to superconducting resonators [4,6]. We report on progress in the formation of bismuth doped 28-Si epi layers by ion implantation, electrical dopant activation and their study via pulsed electron spin resonance measurements showing narrow linewidths and good coherence times. [4pt] [1] A. M. Tyryshkin, et al. arXiv: 1105.3772 [2] J. J. L. Morton, et al. Nature (2008) [3] T. Schenkel, et al APL 2006; F. R. Bradbury, et al. PRL (2006) [4] R. E. George, et al. PRL (2010) [5] G. W. Morley, et al. Nat Mat (2010) [6] M. Hatridge, et al. PRB (2011), R. Vijay, et al. APL (2010) This work was supported by NSA (100000080295) and DOE (DE-AC02-05CH11231).

Chemical and isotopic equilibrium between CO 2 and CH 4 in fumarolic gas discharges: Generation of CH 4 in arc magmatic-hydrothermal systems

NASA Astrophysics Data System (ADS)

Fiebig, Jens; Chiodini, Giovanni; Caliro, Stefano; Rizzo, Andrea; Spangenberg, Jorge; Hunziker, Johannes C.

2004-05-01

The chemical and isotopic composition of fumarolic gases emitted from Nisyros Volcano, Greece, and of a single gas sample from Vesuvio, Italy, was investigated in order to determine the origin of methane (CH 4) within two subduction-related magmatic-hydrothermal environments. Apparent temperatures derived from carbon isotope partitioning between CH 4 and CO 2 of around 340°C for Nisyros and 470°C for Vesuvio correlate well with aquifer temperatures as measured directly and/or inferred from compositional data using the H 2O-H 2-CO 2-CO-CH 4 geothermometer. Thermodynamic modeling reveals chemical equilibrium between CH 4, CO 2 and H 2O implying that carbon isotope partitioning between CO 2 and CH 4 in both systems is controlled by aquifer temperature. N 2/ 3He and CH 4/ 3He ratios of Nisyros fumarolic gases are unusually low for subduction zone gases and correspond to those of midoceanic ridge environments. Accordingly, CH 4 may have been primarily generated through the reduction of CO 2 by H 2 in the absence of any organic matter following a Fischer-Tropsch-type reaction. However, primary occurrence of minor amounts of thermogenic CH 4 and subsequent re-equilibration with co-existing CO 2 cannot be ruled out entirely. CO 2/ 3He ratios and δ 13C CO 2 values imply that the evolved CO 2 either derives from a metasomatized mantle or is a mixture between two components, one outgassing from an unaltered mantle and the other released by thermal breakdown of marine carbonates. The latter may contain traces of organic matter possibly decomposing to CH 4 during thermometamorphism.

Dual stable isotopes of CH4 from Yellowstone hot-springs suggest hydrothermal processes involving magmatic CO2

NASA Astrophysics Data System (ADS)

Moran, James J.; Whitmore, Laura M.; Jay, Zackary J.; Jennings, Ryan deM.; Beam, Jacob P.; Kreuzer, Helen W.; Inskeep, William P.

2017-07-01

Volcanism and post-magmatism contribute significant annual methane (CH4) fluxes to the atmosphere (on par with other natural sources such as forest fire and wild animal emissions) and have been implicated in past climate-change events. The Yellowstone hot spot is one of the largest volcanic systems on Earth and is known to emit CH4 (as well as carbon dioxide (CO2) and other gases), but the ultimate sources of this CH4 flux have not been elucidated. Here we use dual stable isotope analysis (δ2H and δ13C) of CH4 sampled from ten high-temperature geothermal pools in Yellowstone National Park along with other isotopic and gas analyses to evaluate potential sources of methane. The average δ13C and δ2H values of CH4 emitted from hot springs (26.7 (± 2.4) and - 236.9 (± 12.0) ‰, respectively) are inconsistent with microbial methanogenesis but do not allow distinction between thermogenic and abiotic sources. Correlation between δ13CCH4 and δ13C of dissolved inorganic C (DIC) is consistent with DIC as the parent C source for the observed CH4, or with equilibration of CH4 and DIC. Methane formation temperatures estimated by isotopic geothermometry based on δ13CCH4 and δ13CCO2 ranged from 250-350 °C, which is just below previous temperature estimates for the hydrothermal reservoir. Further, the δ2HH2O of the thermal springs and the measured δ2HCH4 values are consistent with equilibration between the source water and the CH4 at the formation temperatures. Though the ultimate origin of the CH4 could be attributed to either abiotic of themorgenic processes with subsequent isotopic equilibration, the C1/C2 + composition of the gases is more consistent with abiotic origins for most of the samples. Thus, our data support the hypothesis that subsurface rock-water interactions are responsible for at least a significant fraction of the CH4 flux from the Yellowstone National Park volcanic system.

Effects of temperature, ultraviolet radiation and pectin methyl esterase on aerobic methane release from plant material.

PubMed

Bruhn, D; Mikkelsen, T N; Obro, J; Willats, W G T; Ambus, P

2009-11-01

This study examines the effects of different irradiance types on aerobic methane (CH(4)) efflux rates from terrestrial plant material. Furthermore, the role of the enzyme pectin methyl esterase (PME) on CH(4) efflux potential was also examined. Different types of plant tissue and purified pectin were incubated in glass vials with different combinations of irradiation and/or temperature. Purified dry pectin was incubated in solution, and with or without PME. Before and after incubation, the concentration of CH(4) was measured with a gas chromatograph. Rates of CH(4) emission were found to depend exponentially on temperature and linearly on UV-B irradiance. UV-B had a greater stimulating effect than UV-A, while visible light had no effect on emission rates. PME was found to substantially reduce the potential for aerobic CH(4) emissions upon demethylation of pectin.

Magnetic field induced anisotropy of 139La spin-lattice relaxation rates in stripe ordered La 1.875Ba 0.125CuO 4

DOE PAGES

S. -H. Baek; Gu, G. D.; Utz, Y.; ...

2015-10-26

We report 139La nuclear magnetic resonance studies performed on a La 1.875Ba 0.125CuO 4 single crystal. The data show that the structural phase transitions (high-temperature tetragonal → low-temperature orthorhombic → low-temperature tetragonal phase) are of the displacive type in this material. The 139La spin-lattice relaxation rate T –1 1 sharply upturns at the charge-ordering temperature T CO = 54 K, indicating that charge order triggers the slowing down of spin fluctuations. Detailed temperature and field dependencies of the T –1 1 below the spin-ordering temperature T SO=40 K reveal the development of enhanced spin fluctuations in the spin-ordered state formore » H ∥ [001], which are completely suppressed for large fields along the CuO 2 planes. Lastly, our results shed light on the unusual spin fluctuations in the charge and spin stripe ordered lanthanum cuprates.« less

Magnetic field induced anisotropy of 139La spin-lattice relaxation rates in stripe ordered La 1.875Ba 0.125CuO 4

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

S. -H. Baek; Gu, G. D.; Utz, Y.

We report 139La nuclear magnetic resonance studies performed on a La 1.875Ba 0.125CuO 4 single crystal. The data show that the structural phase transitions (high-temperature tetragonal → low-temperature orthorhombic → low-temperature tetragonal phase) are of the displacive type in this material. The 139La spin-lattice relaxation rate T –1 1 sharply upturns at the charge-ordering temperature T CO = 54 K, indicating that charge order triggers the slowing down of spin fluctuations. Detailed temperature and field dependencies of the T –1 1 below the spin-ordering temperature T SO=40 K reveal the development of enhanced spin fluctuations in the spin-ordered state formore » H ∥ [001], which are completely suppressed for large fields along the CuO 2 planes. Lastly, our results shed light on the unusual spin fluctuations in the charge and spin stripe ordered lanthanum cuprates.« less

Tessellated gold nanostructures from Au144(SCH2CH2Ph)60 molecular precursors and their use in organic solar cell enhancement

NASA Astrophysics Data System (ADS)

Bauld, Reg; Hesari, Mahdi; Workentin, Mark S.; Fanchini, Giovanni

2014-06-01

We report for the first time the fabrication of nanocomposite hole-blocking layers consisting of poly-3,4-ethylene-dioxythiophene:poly-styrene-sulfonate (PEDOT:PSS) thin films incorporating networks of gold nanoparticles assembled from Au144(SCH2CH2Ph)60, a molecular gold precursor. These thin films can be prepared reproducibly on indium tin oxide by spinning on it Au144(SCH2CH2Ph)60 solutions in chlorobenzene, annealing the resulting thin film at 400 °C, and subsequently spinning PEDOT:PSS on top. The use of our nanocomposite hole-blocking layers for enhancing the photoconversion efficiency of bulk heterojunction organic solar cells is demonstrated. By varying the concentration of Au144(SCH2CH2Ph)60 in the starting solution and the annealing time, different gold nanostructures were obtained ranging from individual gold nanoparticles (AuNPs) to tessellated networks of gold nanostructures (Tess-AuNPs). Improvement in organic solar cell efficiencies up to 10% relative to a reference cell is demonstrated with Tess-AuNPs embedded in PEDOT:PSS.

Theoretical survey of the reaction between osmium and acetaldehyde

NASA Astrophysics Data System (ADS)

Dai, Guo-Liang; Wang, Chuan-Feng

2012-05-01

The mechanism of the reaction of osmium atom with acetaldehyde has been investigated with a DFT approach. All the stationary points are determined at the UB3LYP/ sdd/6-311++G** level of the theory. Both ground and excited state potential energy surfaces are investigated in detail. The present results show that the title reaction start with the formation of a CH3CHO-metal complex followed by C-C, aldehyde C-H, C-O, and methyl C-H activation. These reactions can lead to four different products (HOsCH3 + CO, OsCO + CH4, OsCOCH3 + H, and OsO + C2H4). The minimum energy reaction path is found to involve the spin inversion in the initial reaction step. This potential energy curve-crossing dramatically affects reaction exothermic. The present results may be helpful in understanding the mechanism of the title reaction and further experimental investigation of the reaction.

Evidence for a temperature-induced spin-state transition of Co3+ in La2-xSrxCoO4

NASA Astrophysics Data System (ADS)

Hollmann, N.; Haverkort, M. W.; Benomar, M.; Cwik, M.; Braden, M.; Lorenz, T.

2011-05-01

We study the magnetic susceptibility of mixed-valent La2-xSrxCoO4 single crystals in the doping range of 0.5⩽x⩽0.8 for temperatures up to 1000 K. The magnetism below room temperature is described by paramagnetic Co2+ in the high-spin state and by Co3+ in the nonmagnetic low-spin state. At high temperatures, an increase in susceptibility is seen, which we attribute to a temperature-induced spin-state transition of Co3+. The susceptibility is analyzed by comparison to full-multiplet calculations for the thermal population of the high- and intermediate-spin states of Co3+.

Continuous spin detonation of poorly detonable fuel-air mixtures in annular combustors

NASA Astrophysics Data System (ADS)

Bykovskii, F. A.; Zhdan, S. A.

2017-09-01

This paper reports on the results of experimental investigations of continuous spin detonation of three fuel-air mixtures (syngas-air, CH4/H2-air, and kerosene/H2-air in a flow-type annular cylindrical combustor 503 mm in diameter. The limits of existence of continuous detonation in terms of the specific flow rates of the mixtures (minimum values) are determined. It is found that all gas mixtures, including the least detonable methane-air mixture, with addition of hydrogen can be burned in the continuous spin detonation regime.

Large-scale patterns in summer diffusive CH4 fluxes across boreal lakes, and contribution to diffusive C emissions.

PubMed

Rasilo, Terhi; Prairie, Yves T; Del Giorgio, Paul A

2015-03-01

Lakes are a major component of boreal landscapes, and whereas lake CO2 emissions are recognized as a major component of regional C budgets, there is still much uncertainty associated to lake CH4 fluxes. Here, we present a large-scale study of the magnitude and regulation of boreal lake summer diffusive CH4 fluxes, and their contribution to total lake carbon (C) emissions, based on in situ measurements of concentration and fluxes of CH4 and CO2 in 224 lakes across a wide range of lake type and environmental gradients in Québec. The diffusive CH4 flux was highly variable (mean 11.6 ± 26.4 SD mg m(-2)  d(-1) ), and it was positively correlated with temperature and lake nutrient status, and negatively correlated with lake area and colored dissolved organic matter (CDOM). The relationship between CH4 and CO2 concentrations fluxes was weak, suggesting major differences in their respective sources and/or regulation. For example, increasing water temperature leads to higher CH4 flux but does not significantly affect CO2 flux, whereas increasing CDOM concentration leads to higher CO2 flux but lower CH4 flux. CH4 contributed to 8 ± 23% to the total lake C emissions (CH4  + CO2 ), but 18 ± 25% to the total flux in terms of atmospheric warming potential, expressed as CO2 -equivalents. The incorporation of ebullition and plant-mediated CH4 fluxes would further increase the importance of lake CH4 . The average Q10 of CH4 flux was 3.7, once other covarying factors were accounted for, but this apparent Q10 varied with lake morphometry and was higher for shallow lakes. We conclude that global climate change and the resulting shifts in temperature will strongly influence lake CH4 fluxes across the boreal biome, but these climate effects may be altered by regional patterns in lake morphometry, nutrient status, and browning. © 2014 John Wiley & Sons Ltd.

Site-selective detection of vibrational modes of an iron atom in a trinuclear complex

NASA Astrophysics Data System (ADS)

Faus, Isabelle; Rackwitz, Sergej; Wolny, Juliusz A.; Banerjee, Atanu; Kelm, Harald; Krüger, Hans-Jörg; Schlage, Kai; Wille, Hans-Christian; Schünemann, Volker

2016-12-01

Nuclear inelastic scattering (NIS) experiments on the trinuclear complex [57Fe{L-N4(CH2Fc)2} (CH3CN)2](ClO4)2 have been performed. The octahedral iron ion in the complex was labelled with 57Fe and thereby exclusively the vibrational modes of this iron ion have been detected with NIS. The analysis of nuclear forward scattering (NFS) data yields a ferrous low-spin state for the 57Fe labelled iron ion. The simulation of the partial density of states (pDOS) for the octahedral low-spin iron(II) ion of the complex by density functional theory (DFT) calculations is in excellent agreement with the experimental pDOS of the complex determined from the NIS data obtained at 80 K. Thereby it was possible to assign almost each of the experimentally observed NIS bands to the corresponding molecular vibrational modes.

The effect of high dose on residual radicals in open air irradiated α-T UHMWPE resin powder

NASA Astrophysics Data System (ADS)

Mehmood, Malik S.; Shah, Jahan M.; Mishra, Sanjay R.; Walters, Benjamin M.

2013-03-01

Powder samples of UHMWPE (GUR 1020) containing 0.1 wt%. vitamin E (α-tocopherol, α-T) were irradiated at room temperature in air for doses of 30-kGy, 65-kGy or 100-kGy (60Co). After irradiation, they were stored at -78.5 °C (dry ice temperature) for 1 year and then opened to air at room temperature. Following the decay of the primary alkyl and allyl radicals (at room temperature in air), growth of the carbon-centered polyenyl R1 (-˙CH-[-CHCH-]m-, m≥3), and the oxygen-centered di- or tri-enyl R2 (-˙OCH-[-CHCH-]m-, m≤3) residual radicals were measured for 8 weeks. An X-band electron spin resonance (ESR) spectrometer was used for radical measurements. The initial relative radical concentrations (R2/R1) were found to be 10.13, 4.6 and 3.7 for the 65-kGy, 30-kGy and 100-kGy samples, respectively. R1 and R2 were both found to grow significantly in the 65-kGy sample while they grew only slightly in the 30-kGy and 100-kGy samples. In 65-kGy sample, R1 grew faster than R2 and the relative concentration R2/R1 was reduced from 10.13 to 2.9 for the 65-kGy sample while those for the 30-kGy and 100-kGy samples reduced only slightly, from 4.6 to 3.5 and 3.7 to 3.2, respectively. The behavior of the residual radicals can be explained by Raman spectroscopic data which suggest that the 65-kGy samples had a higher percentage of amorphous regions when compared to the 30-kGy or 100-kGy ones (21.7 compared to 15.7 or 17.9) and also suggest a lower percentage of interfacial regions (16.4 compared to 25.6 or 17.5) and a lower level of structural disorder (0.26 compared to 0.44 or 0.27).

Controls of Methane Dynamics and Emissions in an Arctic Warming Experiment

NASA Astrophysics Data System (ADS)

Nielsen, C. S.; Elberling, B.; Michelsen, A.; Strobel, B. W.; Wulff, K.; Banyasz, I.

2015-12-01

Climatic changes have resulted in increasing air temperatures across the Arctic. This may increase anaerobic decomposition of soil organic matter to methane (CH4) in wetlands and increase plant growth and thereby production of substrate. Little is known about how seasonal variations in dissolved CH4 in soil water, substrate availability, and the effect of warming affect arctic wetland dynamics of CH4 production and emission. In 2013 we established two experiments in a fen at Disko Island, W Greenland; one with year round warming by open-top chambers and removal of shrubs, and one with removal of the aerenchymatous sedge Carex aquatilis ssp. stans. Throughout the growing season 2014 we measured how the treatments affected CH4 emissions, dissolved CH4 in the soil water, and substrate availability. Ecosystem CH4 emissions peaked at August 5th 2014 (7.5 μmol m-2 h-1) without coinciding with time of highest concentrations of dissolved CH4 or acetate indicating a decoupling between production and emission of CH4. The peak in dissolved CH4 concentration, at ten cm depth (1368 ppm, September 18th 2014), followed the peak in concentration of acetate in the same depth (0.30 ppm, August 30th 2014) highlighting the importance of this substance as a substrate for methanogenesis. C. aquatilis ssp. stans accounted for 60% and 77% of the ecosystem CH4 emissions in areas of the fen with water table above and below soil surface showing the importance of the presence of this species to serve as a pipe for CH4 emission which is bypassing the upper soil zone and potential methane oxidation. Throughout the season, warming increased the air temperature at soil surface by on average 0.89°C and occasionally warming and shrub removal increased soil temperature in 2 and 5 cm depth, but there was no effect of the treatments on the CH4 emissions indicating that this wetland is quite resilient towards future climate change.

Non-microbial methane emissions from soils

NASA Astrophysics Data System (ADS)

Wang, Bin; Hou, Longyu; Liu, Wei; Wang, Zhiping

2013-12-01

Traditionally, methane (CH4) is anaerobically formed by methanogenic archaea. However, non-microbial CH4 can also be produced from geologic processes, biomass burning, animals, plants, and recently identified soils. Recognition of non-microbial CH4 emissions from soils remains inadequate. To better understand this phenomenon, a series of laboratory incubations were conducted to examine effects of temperature, water, and hydrogen peroxide (H2O2) on CH4 emissions under both aerobic and anaerobic conditions using autoclaved (30 min, 121 °C) soils and aggregates (>2000 μm, A1; 2000-250 μm, A2; 250-53 μm, M1; and <53 μm, M2). Results show that applying autoclaving to pre-treat soils is effective to inhibit methanogenic activity, ensuring the CH4 emitted being non-microbial. Responses of non-microbial CH4 emissions to temperature, water, and H2O2 were almost identical between aerobic and anaerobic conditions. Increasing temperature, water of proper amount, and H2O2 could significantly enhance CH4 emissions. However, the emission rates were inhibited and enhanced by anaerobic conditions without and with the existence of H2O2, respectively. As regards the aggregates, aggregate-based emission presented an order of M1 > A2 > A1 > M2 and C-based emission an order of M2 > M1 > A1 > A2, demonstrating that both organic carbon quantity and property are responsible for CH4 emissions from soils at the scale of aggregate. Whole soil-based order of A2 > A1 > M1 > M2 suggests that non-microbial CH4 release from forest soils is majorly contributed by macro-aggregates (i.e., >250 μm). The underlying mechanism is that organic matter through thermal treatment, photolysis, or reactions with free radicals produce CH4, which, in essence, is identical with mechanisms of other non-microbial sources, indicating that non-microbial CH4 production may be a widespread phenomenon in nature. This work further elucidates the importance of non-microbial CH4 formation which should be distinguished from the well-known microbial CH4 formation in order to define both roles in the atmospheric CH4 global budget.

A neutral molecular-based layered magnet [Fe(C2O4)(CH3OH)]n exhibiting magnetic ordering at TN approximately 23 K.

PubMed

Zhang, Bin; Zhang, Yan; Zhang, Jinbiao; Li, Junchao; Zhu, Daoben

2008-10-07

Solvothermal synthesis of FeCl(2).4H2O and H2C2O(4).2H2O in methanol at 120 degrees C yielded yellow plate-like crystals of [Fe(C2O4)(CH3OH)]n. Each iron atom is in a distorted octahedral environment, being bonded to four oxygen atoms from two bisbidentate oxalate anions, one O atom of a chelating oxalate anion and one O atom from a methanol molecule as an oxalate group bridging ligand in a five-coordination mode. The neutral layer of [Fe(C2O4)(CH3OH)]n with a [4,4] net along the ac plane. There is no interaction between layers. A long range magnetic ordering with spin canting at TN approximately 23 K was observed and confirmed by AC susceptibility measurements.

Effect of temperature and oxidation rate on carbon-isotope fractionation during methane oxidation by landfill cover materials.

PubMed

Chanton, Jeffrey P; Powelson, David K; Abichou, Tarek; Fields, Dana; Green, Roger

2008-11-01

The quantification of methane oxidation is one of the major uncertainties in estimating CH4 emissions from landfills. Stable isotope methods provide a useful field approach for the quantification of methane oxidation in landfill cover soils. The approach relies upon the difference between the isotopic composition of oxidized gas at the location of interest and anaerobic zone CH4 and knowledge of alpha(ox), a term that describes the isotopic fractionation of the methanotrophic bacteria in their discrimination against (13)CH4. Natural variability in alpha(0x) in different landfill soils and the effect of temperature and other environmental factors on this parameter are not well defined. Therefore, standard determinations of alpha(ox), batch incubations of landfill cover soils with CH4, were conducted to determine alpha(ox) under a variety of conditions. When these results were combined with those of previous landfill incubation studies, the average alpha(ox) at 25 degrees C was 1.022 +/- 0.0015. alpha(ox) decreased with increasing temperature (-0.00039 alpha(ox) degrees C(-1)) overthe temperature range of 3-35 degrees C. alpha(ox) was found to be higher when determined after CH4-free storage and declined following CH4 pretreatment. alpha(ox) declined nonlinearly with increasing methane oxidation rate, Vmax.

[Emission of CH4, N2O and NH3 from vegetable field applied with animal manure composts].

PubMed

Wan, He-Feng; Zhao, Chen-Yang; Zhong, Jia; Ge, Zhen; Wei, Yuan-Song; Zheng, Jia-Xi; Wu, Yu-Long; Han, Sheng-Hui; Zheng, Bo-Fu; Li, Hong-Mei

2014-03-01

Greenhouse gas (GHG) emission from vegetable land is of great concern recently because agriculture land is one of the major sources contributing to global GHG emission. In this study, an experiment of Lactuca sativa L. land applied with different animal manure composts was carried out in a greenhouse vegetable land located in the surburb of Beijing to monitor the emission of GHG (CH4 and N2O) and ammonia in situ, and to analyze the affecting factors of GHG and ammonia emission. Results showed that the emission factors (EFs) of CH4 from Treatment NRM, RM and CF were 0.2%, 0.027% and 0.004%, respectively,the EFs of N2O from these three treatments were 0.18%, 0.63% and 0.74%, respectively, and the EFs of ammonia were 2.00%, 3.98% and 2.53%, respectively. CH4 emission flux was significantly affected by soil temperature and humidity, while N2O emission flux was related to soil temperature, surface temperature and humidity. The emission fluxes of CH4, N2O and NH3 were significantly affected by soil moisture, but there was little relation between CH4, N2O and NH3 emissions and the ambient temperature in the greenhouse.

Continuous measurements of methane flux in two Japanese temperate forests based on the micrometeorological and chamber methods

NASA Astrophysics Data System (ADS)

Yoshikawa, K.; Ueyama, M.; Takagi, K.; Kominami, Y.

2015-12-01

Methane (CH4) budget in forest ecosystems have not been accurately quantified due to limited measurements and considerable spatiotemporal heterogeneity. In order to quantify CH4 fluxes at temperate forest at various spatiotemporal scales, we have continuously measured CH4 fluxes at two upland forests based on the micrometeorological hyperbolic relaxed eddy accumulation (HREA) and automated dynamic closed chamber methods.The measurements have been conducted at Teshio experimental forest (TSE) since September 2013 and Yamashiro forest meteorology research site (YMS) since November 2014. Three automated chambers were installed on each site. Our system can measure CH4 flux by the micrometeorological HREA, vertical concentration profile at four heights, and chamber measurements by a laser-based gas analyzer (FGGA-24r-EP, Los Gatos Research Inc., USA).Seasonal variations of canopy-scale CH4 fluxes were different in each site. CH4 was consumed during the summer, but was emitted during the fall and winter in TSE; consequently, the site acted as a net annual CH4 source. CH4 was steadily consumed during the winter, but CH4 fluxes fluctuated between absorption and emission during the spring and summer in YMS. YMS acted as a net annual CH4 sink. CH4 uptake at the canopy scale generally decreased with rising soil temperature and increased with drying condition for both sites. CH4 flux measured by most of chambers showed the consistent sensitivity examined for the canopy scale to the environmental variables. CH4 fluxes from a few chambers located at a wet condition were independent of variations in soil temperature and moisture at both sites. Magnitude of soil CH4 uptake was higher than the canopy-scale CH4 uptake. Our results showed that the canopy-scale CH4 fluxes were totally different with the plot-scale CH4 fluxes by chambers, suggesting the considerable spatial heterogeneity in CH4 flux at the temperate forests.

A unified equation for calculating methane vapor pressures in the CH4-H2O system with measured Raman shifts

USGS Publications Warehouse

Lu, W.; Chou, I.-Ming; Burruss, R.C.; Song, Y.

2007-01-01

A unified equation has been derived by using all available data for calculating methane vapor pressures with measured Raman shifts of C-H symmetric stretching band (??1) in the vapor phase of sample fluids near room temperature. This equation eliminates discrepancies among the existing data sets and can be applied at any Raman laboratory. Raman shifts of C-H symmetric stretching band of methane in the vapor phase of CH4-H2O mixtures prepared in a high-pressure optical cell were also measured at temperatures between room temperature and 200 ??C, and pressures up to 37 MPa. The results show that the CH4 ??1 band position shifts to higher wavenumber as temperature increases. We also demonstrated that this Raman band shift is a simple function of methane vapor density, and, therefore, when combined with equation of state of methane, methane vapor pressures in the sample fluids at elevated temperatures can be calculated from measured Raman peak positions. This method can be applied to determine the pressure of CH4-bearing systems, such as methane-rich fluid inclusions from sedimentary basins or experimental fluids in hydrothermal diamond-anvil cell or other types of optical cell. ?? 2007 Elsevier Ltd. All rights reserved.

Simultaneous Micrometeorological Flux Observations of CO2 and CH4 at a Sub-Arctic Black-Spruce Forest in Alaska

NASA Astrophysics Data System (ADS)

Harazono, Y.; Ueyama, M.; Miyata, A.

2005-12-01

Carbon dioxide (CO2) and methane (CH4) fluxes were measured at a black spruce forest over discontinuous permafrost in central Alaska since November 2002. CO2 flux was measured by open-path eddy correlation system and CH4 flux was measured by gradient method continuously. CO2 uptake was observed during daytime after DOY 60 when the forest floor was snow-covered with low temperature (<-10 °C). At the moment, CH4 flux was negative (uptake) during daytime and nearing to zero at night, which varied with surface temperature. During snow melt and following permafrost thawing periods (around DOY 110-140, 2003), nocturnal CO2 efflux was larger than daytime uptake resulted in a daily CO2 source, and CH4 flux became small positive in daytime and nearing zero at night resulted in a weak daily CH4 source. After DOY 140 in 2003, CO2 flux was strong uptake and the maximum level was 1.0 g m-2 h-1 in late July around 10:30h when 3 hr earlier than solar noon. During mid summer (DOY 180-230, 2003), daytime CH4 uptake was weak and was near zero at night resulted in a weak daily CH4 sink. 2004 was low snow fall and draught summer, the seasonal patterns of CO2 and CH4 fluxes shifted more than 3-weeks earlier than that in 2003, resulted in high CO2 and CH4 emissions in early summer. Daily amount of CH4 flux in mid summer 2003 and 2004 were 1.2 and 0.5 mg CH4 m-2 d-1, respectively. Sum of observed NEE and CO2 storage term within the canopy, NEP were -482 and -366.6 gCO2 m-2 y-1 in 2003 and 2004. However, application of u* filtering correction made NEP reduce to the ranges between -434.8 and -315.9 gCO2 m-2 y-1 (under u<0.05 ms-1 and u<0.2 ms-1) in 2003 and to -282.5 and -215.9 gCO2 m-2 y-1 in 2004. The low NEP in 2004 was caused by high temperature and low precipitation during growing season. CH4 emission was also higher in 2004. CO2 and CH4 exchanges at sub-arctic forest were quite sensitive to draught and summer temperature.

Simulated nitrogen deposition reduces CH4 uptake and increases N2O emission from a subtropical plantation forest soil in southern China.

PubMed

Wang, Yongsheng; Cheng, Shulan; Fang, Huajun; Yu, Guirui; Xu, Minjie; Dang, Xusheng; Li, Linsen; Wang, Lei

2014-01-01

To date, few studies are conducted to quantify the effects of reduced ammonium (NH4+) and oxidized nitrate (NO3-) on soil CH4 uptake and N2O emission in the subtropical forests. In this study, NH4Cl and NaNO3 fertilizers were applied at three rates: 0, 40 and 120 kg N ha(-1) yr(-1). Soil CH4 and N2O fluxes were determined twice a week using the static chamber technique and gas chromatography. Soil temperature and moisture were simultaneously measured. Soil dissolved N concentration in 0-20 cm depth was measured weekly to examine the regulation to soil CH4 and N2O fluxes. Our results showed that one year of N addition did not affect soil temperature, soil moisture, soil total dissolved N (TDN) and NH4+-N concentrations, but high levels of applied NH4Cl and NaNO3 fertilizers significantly increased soil NO3(-)-N concentration by 124% and 157%, respectively. Nitrogen addition tended to inhibit soil CH4 uptake, but significantly promoted soil N2O emission by 403% to 762%. Furthermore, NH4+-N fertilizer application had a stronger inhibition to soil CH4 uptake and a stronger promotion to soil N2O emission than NO3(-)-N application. Also, both soil CH4 and N2O fluxes were driven by soil temperature and moisture, but soil inorganic N availability was a key integrator of soil CH4 uptake and N2O emission. These results suggest that the subtropical plantation soil sensitively responses to atmospheric N deposition, and inorganic N rather than organic N is the regulator to soil CH4 uptake and N2O emission.

Hydrogen-bonded networks of [Fe(bpp)2]2+ spin crossover complexes and dicarboxylate anions: structural and photomagnetic properties.

PubMed

Jornet-Mollá, Verónica; Duan, Yan; Giménez-Saiz, Carlos; Waerenborgh, João C; Romero, Francisco M

2016-11-28

The paper reports the syntheses, crystal structures, thermal and (photo)magnetic properties of spin crossover salts of formula [Fe(bpp) 2 ](C 6 H 8 O 4 )·4H 2 O (1·4H 2 O), [Fe(bpp) 2 ](C 8 H 4 O 4 )·2CH 3 OH·H 2 O (2·2MeOH·H 2 O) and [Fe(bpp) 2 ](C 8 H 4 O 4 )·5H 2 O (2·5H 2 O) (bpp = 2,6-bis(pyrazol-3yl)pyridine; C 6 H 8 O 4 = adipate dianion; C 8 H 4 O 4 = terephthalate dianion). The salts exhibit an intricate network of hydrogen bonds between low-spin iron(ii) complexes and carboxylate dianions, with solvent molecules sitting in the voids. Desolvation is accompanied by a low-spin (LS) to high-spin (HS) transformation in the materials. The dehydrated phase 2 undergoes a two-step transition with a second step showing thermal hysteresis (T 1/2 ↑ = 139 K and T 1/2 ↓ = 118 K). 2 displays a quantitative LS to HS photomagnetic conversion, with a T(LIESST) value of 63 K.

Reactive Intermediates or Inert Graphene? Temperature- and Pressure-Determined Evolution of Carbon in the CH 4–Ni(111) System

DOE PAGES

Yuan, Kaidi; Zhong, Jian-Qiang; Sun, Shuo; ...

2017-08-15

Atomic-level identification of carbon intermediates under reaction conditions is essential for carbon-related heterogeneous catalysis. Using the in operando technique of near-ambient-pressure X-ray photoelectron spectroscopy, we have identified in this paper various carbon intermediates during the thermal decomposition of CH 4 on Ni(111), including *CH, *C 1/Ni 3C, *C n (n ≥ 2), and clock-reconstructed Ni 2C at different temperature regions (300–900 K). These “reactive” carbon precursors can either react with probing molecules such as O 2 at room temperature or be etched away by CH 4. They can also develop into graphene flakes under controlled conditions: a temperature between 800more » and 900 K and a suitable CH 4 pressure (10 –3–10 –1 mbar, depending on temperature). The growth rate of graphene is significantly restrained at higher CH 4 pressures, due to the accelerated etching of its carbon precursors. The identification of in operando carbon intermediates and the control of their evolution have great potential in designing heterogeneous catalysts for the direct conversion of methane. Finally, the observed carbon aggregation/etching equilibrium reveals an underlying mechanism in coking prevention and in the fabrication of large-area single-crystal graphene, where the suppression of seeding density and etching up of small grains are required.« less

Reactive Intermediates or Inert Graphene? Temperature- and Pressure-Determined Evolution of Carbon in the CH 4–Ni(111) System

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

Yuan, Kaidi; Zhong, Jian-Qiang; Sun, Shuo

Atomic-level identification of carbon intermediates under reaction conditions is essential for carbon-related heterogeneous catalysis. Using the in operando technique of near-ambient-pressure X-ray photoelectron spectroscopy, we have identified in this paper various carbon intermediates during the thermal decomposition of CH 4 on Ni(111), including *CH, *C 1/Ni 3C, *C n (n ≥ 2), and clock-reconstructed Ni 2C at different temperature regions (300–900 K). These “reactive” carbon precursors can either react with probing molecules such as O 2 at room temperature or be etched away by CH 4. They can also develop into graphene flakes under controlled conditions: a temperature between 800more » and 900 K and a suitable CH 4 pressure (10 –3–10 –1 mbar, depending on temperature). The growth rate of graphene is significantly restrained at higher CH 4 pressures, due to the accelerated etching of its carbon precursors. The identification of in operando carbon intermediates and the control of their evolution have great potential in designing heterogeneous catalysts for the direct conversion of methane. Finally, the observed carbon aggregation/etching equilibrium reveals an underlying mechanism in coking prevention and in the fabrication of large-area single-crystal graphene, where the suppression of seeding density and etching up of small grains are required.« less

Highly Depleted Ethane and Mildly Depleted Methanol in Comet 21P/Giacobini-Zinner: Application of a New Empirical nu(sub 2) Band Model for CH30H Near 50 K

NASA Technical Reports Server (NTRS)

DiSanti, M. A.; Bonev, B. P.; Villanueva, G. L.; Mumma, M. J.

2012-01-01

Infrared spectra of Comet 2lP/Giacobini-Zinner (hereafter 2IP/GZ) were obtained using NIRSPEC at Keck II on UT 2005 June 03, approximately one month before perihelion, that simultaneously measured H2O, C2H6, and CH3OH. For H2O, the production rate of 3.8 x 10(exp 28) molecules / S was consistent with that measured during other apparitions of 21P/GZ retrieved from optical, infrared, and mm-wavelength observations. The water analysis also provided values for rotational temperature (T(sub rot) = 55(epx +3) /-.2 K) and the abundance ratio of ortho- and para-water (3.00 +/-0.15, implying a spin temperature exceeding 50 K). Six Q-branches in the V7 band of C2H6 provided a production rate (5.27 +/- 0.90 x 10(exp 25)/S) that corresponded to an abundance ratio of 0.139 +/- 0.024 % relative to H2O, confirming the previously reported strong depletion of C2H6 from IR observations during the 1998 apparition, and in qualitative agreement with the depletion in C2 known from optical studies. For CH30H, we applied our recently published ab initia model for the v3 band to obtain a rotational temperature (48(exp + 10) / -7 K) consistent with that obtained for H2O. In addition we applied a newly developed empirical model for the CH30H v2 band, and obtained a production rate consistent with that obtained from the v3 band. Combining results from both v2 and v3 bands provided a production rate (47.5 +/- 4.4 x 10(exp 25) / S) that corresponded to an abundance ratio of 1.25 +/- 0.12 % relative to H2O in 21P/GZ. Our study provides the first measure of primary volatile production rates for any Jupiter family comet over multiple apparitions using high resolution IR spectroscopy.

Demonstration of efficient spin injection and detection in various systems using Fe{sub 3}O{sub 4} based spin injectors

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

Bhat, Shwetha G., E-mail: shwethabhat@physics.iisc.ernet.in; Anil Kumar, P. S.

2016-05-15

Half-metal based spin injector devices for spin injection and detection application have proven to be efficient owing to their enhanced injection and detection efficiency. In this study, we extend the all-electrical spin injection and detection studies into different systems like Si and GaAs using half-metal Fe{sub 3}O{sub 4} as a spin injector in the presence and absence of tunnel barrier MgO. Injection into GaAs is verified using conventional Fe/MgO/GaAs devices. Room temperature spin injection into both p-type and n-type Si is achieved and the spin injection could be observed down to 100 K. Obtained spin relaxation time for these n-typemore » and p-type Si at different temperatures agree well with the existing reports. Further, the temperature dependent spin injection and detection is also successfully achieved in Fe{sub 3}O{sub 4}/GaAs (n-type) Schottky devices, and a comparison study of the results with control experiment using Fe/MgO/GaAs (n-type) devices confirm the relaxation to be similar in the GaAs substrate, as expected. Hence, even Fe{sub 3}O{sub 4} material can be effectively used as an efficient spin injector as well as detector, making it an attractive candidate for the room temperature spintronics device applications.« less

The Structure of Titan’s N2 and CH4 Coronae

NASA Astrophysics Data System (ADS)

Jiang, Fayu; Cui, Jun; Xu, Jiyao

2017-12-01

In this study, we analyze the structures of Titan’s N2 and CH4 coronae using a large data set acquired by the Ion Neutral Mass Spectrometer (INMS) instrument on board Cassini. The N2 and CH4 densities measured from the exobase up to 2000 km imply a mean exobase temperature of 146 K and 143 K, respectively, which is lower than the mean upper atmospheric temperature by 4 and 7 K. This indicates that on average, Titan possesses a subthermal rather than suprathermal corona. A careful examination reveals that the variability in corona structure is not very likely to be solar driven. Within the framework of the collisionless kinetic model, we investigate how the CH4 energy distribution near the exobase could be constrained if strong CH4 escape occurs on Titan. Several functional forms for the CH4 energy distribution are attempted, assuming two representative CH4 escape rates of 1.2× {10}25 s-1 and 2.2× {10}27 s-1. We find that the double Maxwellian and power-law distributions can reproduce the shape of the CH4 corona structure as well as the imposed CH4 escape rate. In both cases, the escape rate is contributed by a suprathermal CH4 population on the high-energy tail, with a number fraction below 5% and a characteristic energy of 0.1-0.6 eV per suprathermal CH4 molecule. The coexistence of the subthermal CH4 corona revealed by the INMS data and substantial CH4 escape suggested by some previous works could be reconciled by a significant departure in the exobase CH4 energy distribution from ideal Maxwellian that enhances escape and causes a noticeable redistribution of the corona structure.

Probing the Impact of Solvation on Photoexcited Spin Crossover Complexes with High-Precision X-ray Transient Absorption Spectroscopy

DOE PAGES

Liu, Cunming; Zhang, Jianxin; Lawson Daku, Latevi M.; ...

2017-11-10

Investigating the photoinduced electronic and structural response of bistable molecular building blocks incorporating transition metals in solution phase constitutes a necessary stepping stone for steering their properties towards applications and perfomance optimizations. Here, this paper presents a detailed X-ray transient absorption (XTA) spectroscopy study of a prototypical spin crossover (SCO) complex [Fe II(mbpy) 3] 2+ (where mbpy=4,4’-dimethyl-2,2’-bipyridine) with a [Fe IIN 6] first coordination shell in water (H 2O) and acetonitrile (CH 3CN). The unprecedented data quality of the XTA spectra together with the direct fitting of the difference spectra in k space using a large number of scattering pathsmore » enables resolving the subtle difference in the photoexcited structures of an Fe II complex in two solvents for the first time. Also, compared to the low spin (LS) 1A 1 state, the average Fe-N bond elongations for the photoinduced high spin (HS) 5T 2 state are found to be 0.181 ± 0.003 Å in H 2O and 0.199 ± 0.003 Å in CH 3CN. This difference in structural response is attributed to ligand-solvent interactions that are stronger in H 2O than in CH 3CN for the HS excited state. Our studies demonstrate that, although the metal center of [Fe II(mbpy) 3] 2+ could have been expected to be rather shielded by the three bidentate ligands with quasi-octahedral-coordination, the ligand field strength in the HS excited state is nevertheless indirectly affected by solvation that modifies the charge distribution within the Fe-N covalent bonds. More generally, this work highlights the importance of including solvation effects in order to develop a generalized understanding of the spin-state switching at the atomic level.« less

New polynuclear manganese clusters from the use of the hydrophobic carboxylate ligand 2,2-dimethylbutyrate.

PubMed

Chakov, Nicole E; Zakharov, Lev N; Rheingold, Arnold L; Abboud, Khalil A; Christou, George

2005-06-27

The syntheses, structures, and magnetic properties are reported of [Mn12O12(O2CPe(t))16(MeOH)4] (4), [Mn6O2(O2CH2)(O2CPe(t))11(HO2CPe(t))2(O2CMe)] (5), [Mn9O6(OH)(CO3)(O2CPe(t))12(H2O)2] (6), and [Mn4O2(O2CPe(t))6(bpy)2] (7, bpy = 2,2'-bipyridine), where Pe(t) = tert-pentyl (Pe(t)CO2H = 2,2-dimethylbutyric acid). These complexes were all prepared from reactions of [Mn12O12(O2CPe(t))16(H2O)4] (3) in CH2Cl2. Complex 4 x 2MeCN crystallizes in the triclinic space group P1 and contains a central [Mn(IV)4O4] cubane core that is surrounded by a nonplanar ring of eight alternating Mn(III) and eight mu3-O(2-) ions. This is only the third Mn12 complex in which the four bound water molecules have been replaced by other ligands, in this case MeOH. Complex 5 x (1/2)CH2Cl2 crystallizes in the monoclinic space group P2(1)/c and contains two [Mn3(mu3-O)]7+ units linked at two of their apexes by two Pe(t)CO2(-) ligands and one mu4-CH2O2(2-) bridge. The complex is a new structural type in Mn chemistry, and also contains only the third example of a gem-diolate unit bridging four metal ions. Complex 6 x H2O x Pe(t)CO2H crystallizes in the orthorhombic space group Cmc2(1) and possesses a [Mn(III)9(mu3-O)6(mu-OH)(mu3-CO3)]12+ core. The molecule contains a mu3-CO3(2-) ion, the first example in a discrete Mn complex. Complex 7 x 2H2O crystallizes in the monoclinic space group P2(1)/c and contains a known [Mn(III)2Mn(II)2(mu3-O)2]6+ core that can be considered as two edge-sharing, triangular [Mn3O] units. Additionally, the synthesis and magnetic properties of a new enneanuclear cluster of formula [Mn9O7(O2CCH2Bu(t))13(THF)2] (8, THF = tetrahydrofuran) are reported. The molecule was obtained by the reaction of [Mn12O12(O2CCH2Bu(t))16(H2O)4] (2) with THF. Complexes 2 and 4 display quasireversible redox couples when examined by cyclic voltammetry in CH2Cl2; oxidations are observed at -0.07 V (2) and -0.21 V (4) vs ferrocene. The magnetic properties of complexes 4-8 have been studied by direct current (DC) and alternating current (AC) magnetic susceptibility techniques. The ground-state spin of 4 was established by magnetization measurements in the 1.80-4.00 K and 0.5-7 T ranges. Fitting of the reduced magnetization data by full matrix diagonalization, incorporating a full powder average and including only axial anisotropy, gave S = 10, g = 2.0(1), and D = -0.39(10) cm(-1). The complex exhibits two frequency-dependent out-of-phase AC susceptibility signals (chi(M)'') indicative of slow magnetization relaxation. An Arrhenius plot obtained from chi(M)'' vs T data gave an effective energy barrier to relaxation (U(eff)) of 62 and 35 K for the slower and faster relaxing species, respectively. These studies suggest that complex 4 is a single-molecule magnet (SMM). DC susceptibility studies on complexes 5-8 display overall antiferromagnetic behavior and indicate ground-state spin values of S < or = 2. AC susceptibility studies at < 10 K confirm these small values and indicate the population of low-lying excited states even at these low temperatures. This supports the small ground-state spin values to be due to spin frustration effects.

Fast Abiotic Production of Methane at Temperatures Below 100°C

NASA Astrophysics Data System (ADS)

Etiope, G.; Ionescu, A.

2015-12-01

Fischer-Tropsch Type (FTT) reactions, e.g., the Sabatier synthesis between H2 and CO2, are considered a main source of abiotic methane on Earth and likely on other planets. Several laboratory FTT experiments demonstrated abiotic CH4 production at temperatures above 200°C, by using Fe, Ni or Cr catalysts, simulating hydrothermal conditions in peridotite-hosted systems in mid-ocean ridges. Nevertheless, at least on laboratory experiment time-scale, Fe-Ni-Cr catalysts do not support CH4 generation at T<100°C, such as those of land-based serpentinization systems. We have recently reported rapid production of considerable amounts of CH4 (>800 ppmv in 155 mL bottles after 1 day) via Sabatier reaction at 90, 50 and 25°C, using small concentrations of non-pretreated ruthenium (Ru) equivalent to those occurring in chromitites in continental ultramafic rocks (Etiope & Ionescu, 2014; Geofluids, doi:10.1111/gfl.12106). We have repeated the experiments by using 13C-enriched CO2 and we confirm fast production of CH4at percentage levels. The experiments performed so far show that: 1. considerable amounts of CH4can be produced in dry conditions below 100°C with small quantities of Ru; 2. under the same experimental conditions (<100°C), Fe, Ni and Cr oxides do not produce CH4; 3. low T Sabatier reaction can produce CH4 with a large C isotope fractionation between CO2 and CH4, leading to relatively " light" (13C-depleted) CH4, resembling microbial gas; 4. the CO2-CH4isotope separation decreases over time and by increasing the temperature; 5. minor amounts of C2-C6hydrocarbons are also generated. Our laboratory data are compatible with the isotopic patterns of CH4 naturally occurring in land-based seeps and springs. Our experiments suggest that Ru-enriched chromitites could potentially generate CH4 at low T. Since Ru is reported in Martian meteorites, low T abiotic CH4 production on Mars via Sabatier reaction cannot be excluded (Etiope et al. 2013, Icarus, 224, 276-285).

Thermal effects of an ICL-based mid-infrared CH 4 sensor within a wide atmospheric temperature range

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

Ye, Weilin; Zheng, Chuantao; Sanchez, Nancy P.

Here, thermal effects of an interband cascade laser (ICL) based mid-infrared methane (CH 4) sensor that uses long-path absorption spectroscopy were studied. The sensor performance in the laboratory at a constant temperature of ~ 25°C was measured for 5 hours and its Allan deviation was ~ 2 ppbv with a 1 s averaging time. A LabVIEW-based simulation program was developed to study thermal effects on infrared absorption and a temperature compensation technique was developed to control such effects. An environmental test chamber was employed to investigate thermal effects that occur in the sensor system with variation of the test chambermore » temperature between 10 and 30°C. The thermal response of the sensor in a laboratory setting was observed using a 2.1 ppm CH 4 standard gas sample. indoor/outdoor CH 4 measurements were conducted to evaluate the sensor performance within a wide atmospheric temperature range.« less

Thermal effects of an ICL-based mid-infrared CH4 sensor within a wide atmospheric temperature range

NASA Astrophysics Data System (ADS)

Ye, Weilin; Zheng, Chuantao; Sanchez, Nancy P.; Girija, Aswathy V.; He, Qixin; Zheng, Huadan; Griffin, Robert J.; Tittel, Frank K.

2018-03-01

The thermal effects of an interband cascade laser (ICL) based mid-infrared methane (CH4) sensor that uses long-path absorption spectroscopy were studied. The sensor performance in the laboratory at a constant temperature of ∼25 °C was measured for 5 h and its Allan deviation was ∼2 ppbv with a 1 s averaging time. A LabVIEW-based simulation program was developed to study thermal effects on infrared absorption and a temperature compensation technique was developed to minimize these effects. An environmental test chamber was employed to investigate the thermal effects that occur in the sensor system with variation of the test chamber temperature between 10 and 30 °C. The thermal response of the sensor in a laboratory setting was observed using a 2.1 ppm CH4 standard gas sample. Indoor/outdoor CH4 measurements were conducted to evaluate the sensor performance within a wide atmospheric temperature range.

Thermal effects of an ICL-based mid-infrared CH 4 sensor within a wide atmospheric temperature range

DOE PAGES

Ye, Weilin; Zheng, Chuantao; Sanchez, Nancy P.; ...

2018-01-31

Here, thermal effects of an interband cascade laser (ICL) based mid-infrared methane (CH 4) sensor that uses long-path absorption spectroscopy were studied. The sensor performance in the laboratory at a constant temperature of ~ 25°C was measured for 5 hours and its Allan deviation was ~ 2 ppbv with a 1 s averaging time. A LabVIEW-based simulation program was developed to study thermal effects on infrared absorption and a temperature compensation technique was developed to control such effects. An environmental test chamber was employed to investigate thermal effects that occur in the sensor system with variation of the test chambermore » temperature between 10 and 30°C. The thermal response of the sensor in a laboratory setting was observed using a 2.1 ppm CH 4 standard gas sample. indoor/outdoor CH 4 measurements were conducted to evaluate the sensor performance within a wide atmospheric temperature range.« less

A new metal-organic framework for separation of C2H2/CH4 and CO2/CH4 at room temperature

NASA Astrophysics Data System (ADS)

Duan, Xing; Zhou, You; Lv, Ran; Yu, Ben; Chen, Haodong; Ji, Zhenguo; Cui, Yuanjing; Yang, Yu; Qian, Guodong

2018-04-01

A 3D microporous metal-organic framework with open Cu2+ sites and suitable pore space, [Cu2(L)(H2O)2]·(H2O)4(DMF)8 (ZJU-15, H4L = 5,5‧-(9H-carbazole-2,7-diyl)diisophthalic acid; DMF = N,N-dimethylformamide; ZJU = Zhejiang University), has been constructed and characterized. The activated ZJU-15a has three different types of cages and exhibits BET surface area of 1660 m2 g-1, and can separate gas mixture of C2H2/CH4 and CO2/CH4 at room temperature.

A global wetland methane emissions and uncertainty dataset for atmospheric chemical transport models (WetCHARTs version 1.0)

NASA Astrophysics Data System (ADS)

Bloom, A. Anthony; Bowman, Kevin W.; Lee, Meemong; Turner, Alexander J.; Schroeder, Ronny; Worden, John R.; Weidner, Richard; McDonald, Kyle C.; Jacob, Daniel J.

2017-06-01

Wetland emissions remain one of the principal sources of uncertainty in the global atmospheric methane (CH4) budget, largely due to poorly constrained process controls on CH4 production in waterlogged soils. Process-based estimates of global wetland CH4 emissions and their associated uncertainties can provide crucial prior information for model-based top-down CH4 emission estimates. Here we construct a global wetland CH4 emission model ensemble for use in atmospheric chemical transport models (WetCHARTs version 1.0). Our 0.5° × 0.5° resolution model ensemble is based on satellite-derived surface water extent and precipitation reanalyses, nine heterotrophic respiration simulations (eight carbon cycle models and a data-constrained terrestrial carbon cycle analysis) and three temperature dependence parameterizations for the period 2009-2010; an extended ensemble subset based solely on precipitation and the data-constrained terrestrial carbon cycle analysis is derived for the period 2001-2015. We incorporate the mean of the full and extended model ensembles into GEOS-Chem and compare the model against surface measurements of atmospheric CH4; the model performance (site-level and zonal mean anomaly residuals) compares favourably against published wetland CH4 emissions scenarios. We find that uncertainties in carbon decomposition rates and the wetland extent together account for more than 80 % of the dominant uncertainty in the timing, magnitude and seasonal variability in wetland CH4 emissions, although uncertainty in the temperature CH4 : C dependence is a significant contributor to seasonal variations in mid-latitude wetland CH4 emissions. The combination of satellite, carbon cycle models and temperature dependence parameterizations provides a physically informed structural a priori uncertainty that is critical for top-down estimates of wetland CH4 fluxes. Specifically, our ensemble can provide enhanced information on the prior CH4 emission uncertainty and the error covariance structure, as well as a means for using posterior flux estimates and their uncertainties to quantitatively constrain the biogeochemical process controls of global wetland CH4 emissions.

Low temperature studies of the removal reactions of 1CH2 with particular relevance to the atmosphere of Titan

NASA Astrophysics Data System (ADS)

Douglas, Kevin; Blitz, Mark A.; Feng, Wuhu; Heard, Dwayne E.; Plane, John M. C.; Slater, Eloise; Willacy, Karen; Seakins, Paul W.

2018-03-01

Methylene, CH2, is one of the major photolysis products of methane by Lyman-α radiation and is involved in the photochemistry of the atmospheres of Titan and the giant planets. The kinetics of the reactions of the first excited state of methylene, 1CH2, with He, N2, O2, H2 and CH4 have been measured over the temperature range 43-160 K by pulsed laser photolysis, monitoring 1CH2 removal by laser induced fluorescence. Low temperatures were obtained with either a pulsed Laval expansion (43-134 K) or a, slow flow reaction cell (160 K). The rate coefficients for the reactions with N2, O2, H2 and CH4 all showed a strong negative temperature dependence. In combination with other literature data, the rate coefficients can be parameterised as: kHe(43 < T/K < 800) = (1.90 ± 0.23) × 10-12 × (T/298)1.74±0.16 × exp((88±23)/T) kN2(43 < T / K < 800) = (2.29 ± 1.12) × 10-12 × (T/298)-2.15±1.38 × exp((-74±96)/T) + (3.91 ± 0.78) × 10-11 × exp((-469±114)/T) kO2(43 < T / K < 300) = (6.16 ± 1.09) × 10-11 × (T/298)-0.65±0.14 kH2(43 < T / K < 800) = (1.10 ± 0.04) × 10-10 × (T/298)-0.40±0.06 × exp((11.1±6.9)/T) kCH4(43 < T / K < 475) = (8.20 ± 0.46) × 10-11 × (T/298)-0.93±0.10 × exp((-20.5±12.8)/T) For the reactions of 1CH2 with H2 and CH4, the branching ratio for quenching to ground state, 3CH2, vs chemical reaction was also determined at 160 and 73 K. The values measured (H2: 0.39 ± 0.10 at 160 K, 0.78 ± 0.15 at 73 K; CH4: 0.49 ± 0.09 at 160 K, 0.64 ± 0.19 at 73 K) confirm trends of an increased proportion of reactive loss with increasing temperature determined at higher temperatures. The impacts of the new measurements for Titan's atmosphere have been ascertained using a 1D chemistry and transport model. A significant decrease (∼40%) in the mixing ratio of ethane between 800 and 1550 km is calculated due to the decrease contribution of methyl production from the reaction of 1CH2 with CH4, with smaller increases in the concentrations of ethene and acetylene. Ethene production is enhanced by more methylene being converted to methylidene, CH, and the subsequent reaction of CH with CH4 to generate ethene. Photolysis of ethene is the major route to acetylene formation.

Temperature sensitivity of methanogenesis in a thermokarst lake sediment core

NASA Astrophysics Data System (ADS)

Heslop, J. K.; Walter Anthony, K. M.; Grosse, G.; Anthony, P.; Bondurant, A.

2016-12-01

Little is known about temperature sensitivity of permafrost organic carbon (OC) mineralization over time scales of years to centuries following thaw. Due to their formation and thaw histories, taliks (thaw bulbs) beneath thermokarst lakes provide a unique natural laboratory from which to examine how permafrost thawed in saturated anaerobic conditions responds to changes in temperature following long periods of time since thaw. We anaerobically incubated samples from a 590 cm thermokarst lake sediment core near Fairbanks, Alaska at four temperatures (0, 3, 10, and 25 ºC) bracketing observed talik temperatures. We show that since initial thaw 400 yr BP CH4 production shifts from being most sensitive to at lower (0-3 ºC; Q10-EC=1.15E7) temperatures to being most sensitive at higher (10-25 ºC; Q10-EC=67) temperatures. Frozen sediments collected from beneath the talik, thawed at the commencement of the incubation, had significant (p ≤ 0.05) increases in CH4 production rates at lower temperatures but did not show significant CH4 production rate increases at higher temperatures (10-25 ºC). We hypothesize the thawing of sediments removed a major barrier to C mineralization, leading to rapid initial permafrost C mineralization and preferential mineralization of the most biolabile OC compounds. In contrast, sediments which had been thawed beneath the lake for longer periods of time did not experience statistically significant increases in CH4 production at lower temperatures (0-10 ºC), but had high temperature sensitivities at higher temperatures (10-25 ºC). We believe these rate increases are due to warmer temperatures in the experimental incubations crossing activation energy thresholds, allowing previously recalcitrant fractions of OC to be utilized, and/or the presence of different microbial communities adapted to thawed sediments. Recently-deposited sediments at shallow depths in the lake core experienced increases in CH4 production across all incubation temperatures (Q10-ST=4.4).

Spatio-temporal variability of lake CH4 fluxes and its influence on annual estimates

NASA Astrophysics Data System (ADS)

Natchimuthu, S.; Sundgren, I.; Gålfalk, M.; Klemedtsson, L.; Crill, P. M.; Danielsson, Å.; Bastviken, D.

2014-12-01

Lakes are major sources of methane (CH4) to the atmosphere and it has been shown that lakes contribute significantly to the global CH4 budget. However, the data behind these global estimates are snapshots in time and space only and they typically lack information on spatial and temporal variability of fluxes which can potentially lead to biased estimates. Recent studies have shown that diffusive flux, gas exchange velocity (k), ebullition and concentration of CH4 in the surface water can vary significantly in space within lakes. CH4 fluxes can also change at a broad range of temporal scales in response to seasons, temperature, lake mixing events, short term weather events like pressure variations, shifting winds and diel cycles. We sampled CH4 fluxes and surface water concentrations from three lakes of differing characteristics in southwest Sweden over two annual cycles, approximately every 14 days from April to October 2012 and from April to November 2013. CH4 fluxes were measured using floating chambers distributed in the lakes based on depth categories and dissolved CH4 concentrations were determined by a headspace equilibration method. We observed significant differences in CH4 concentration, diffusion, ebullition and total fluxes between and within the lakes. The fluxes increased exponentially with temperature in all three lakes and water temperature, for example, explained 53-78% of variations in total fluxes in the lakes. Based on our data which relied on improved spatial and temporal information, we demonstrate that measurements which do not take into account of the spatial variability in the lakes could substantially bias the whole lake estimates. For instance, in one of the lakes, measurements from the central parts of the lake represented only 58% of our estimates from all chambers on an average. In addition, we consider how intensive sampling in one season of the year may affect the annual estimates due to the complex interaction of temperature, air pressure and lake mixing events on CH4 fluxes. For example, samples collected when the average air temperatures during chamber deployments were above 15 °C overestimated the total fluxes by 17-157% in all lakes when compared to averages from all measurement times.

Methane emission by plant communities in an alpine meadow on the Qinghai-Tibetan Plateau: a new experimental study of alpine meadows and oat pasture.

PubMed

Wang, Shiping; Yang, Xiaoxia; Lin, Xingwu; Hu, Yigang; Luo, Caiyun; Xu, Guangping; Zhang, Zhenhua; Su, Ailing; Chang, Xiaofen; Chao, Zengguo; Duan, Jichuang

2009-08-23

Recently, plant-derived methane (CH(4)) emission has been questioned because limited evidence of the chemical mechanism has been identified to account for the process. We conducted an experiment with four treatments (i.e. winter-grazed, natural alpine meadow; naturally restored alpine meadow eight years after cultivation; oat pasture and bare soil without roots) during the growing seasons of 2007 and 2008 to examine the question of CH(4) emission by plant communities in the alpine meadow. Each treatment consumed CH(4) in closed, opaque chambers in the field, but two types of alpine meadow vegetation reduced CH(4) consumption compared with bare soil, whereas oat pasture increased consumption. This result could imply that meadow vegetation produces CH(4). However, measurements of soil temperature and water content showed significant differences between vegetated and bare soil and appeared to explain differences in CH(4) production between treatments. Our study strongly suggests that the apparent CH(4) production by vegetation, when compared with bare soil in some previous studies, might represent differences in soil temperature and water-filled pore space and not the true vegetation sources of CH(4).

The Self-Evolving Cosmos: A Phenomenological Approach to Nature's Unity-in-Diversity

NASA Astrophysics Data System (ADS)

Rosen, Steven M.

ch. 1. Introduction: individuation and the quest for unity -- ch. 2. The obstacle to unification in modern physics. 2.1. Introduction. 2.2. Does contemporary mathematical physics actually depart from the classical formulation? -- ch. 3. The phenomenological challenge to the classical formula -- ch. 4. Topological phenomenology. 4.1. Introduction. 4.2. Phenomenological intuition, topology, and the Klein bottle. 4.3. The physical significance of the Klein bottle -- ch. 5. The dimensional family of topological spinors. 5.1. Generalization of intuitive topology. 5.2. Topodimensional spin matrix -- ch. 6. Basic principles of dimensional transformation. 6.1. Synsymmetry and the self-transformation of space. 6.2. From symmetry breaking to dimensional generation. 6.3. The three basic stages of dimensional generation. 6.4. Kleinian topogeny -- ch. 7. Waves carrying waves: the co-evolution of lifeworlds -- ch. 8. The forces of nature. 8.1. The phenomenon of light. 8.2. Phenomenological Kaluza-Klein theory. 8.3. Summary comparison of conventional and topo-phenomenological approaches to Kaluza-Klein theory -- ch. 9. Cosmogony, symmetry, and phenomenological intuition. 9.1. Conventional view of the evolving cosmos. 9.2. The problem of symmetry. 9.3. A new kind of clarity -- ch. 10. The self-evolving cosmos. 10.1. Introduction to the cosmogonic matrix. 10.2. Overview of cosmic evolution. 10.3. The role of the fermions in dimensional generation. 10.4. Projective stages of cosmogony: dimensional divergence. 10.5. Proprioceptive stages of cosmogony: dimensional convergence. 10.6. Conclusion: wider horizons of cosmic evolution -- ch. 11. The psychophysics of cosmogony. 11.1. Psychical aspects of the fundamental particles. 11.2. Toward a reflexive physics. 11.3. Concretization of the self-evolving cosmos.

The effects of climate changes on soil methane oxidation in a dry Arctic tundra

NASA Astrophysics Data System (ADS)

D'Imperio, Ludovica

2014-05-01

The effects of climate changes on soil methane oxidation in a dry Arctic tundra. Ludovica D'Imperio1, Anders Michelsen1, Christian J. Jørgensen1, Bo Elberling1 1Center for Permafrost (CENPERM), Department of Geosciences and Natural Resource Management, University of Copenhagen, Denmark At Northern latitudes climatic changes are predicted to be most pronounced resulting in increasing active layer depth and changes in growing season length, vegetation cover and nutrient cycling. As a consequence of increased temperature, large stocks of carbon stored in the permafrost-affected soils could become available for microbial transformations and under anoxic conditions result in increasing methane production affecting net methane (CH4) budget. Arctic tundra soils also serves as an important sink of atmospheric CH4 by microbial oxidation under aerobic conditions. While several process studies have documented the mechanisms behind both production and emissions of CH4 in arctic ecosystems, an important knowledge gap exists with respect to the in situ dynamics of microbial-driven uptake of CH4 in arctic dry lands which may be enhanced as a consequence of global warming and thereby counterbalancing CH4 emissions from Arctic wetlands. In-situ methane measurements were made in a dry Arctic tundra in Disko Island, Western Greenland, during the summer 2013 to assess the role of seasonal and inter-annual variations in temperatures and snow cover. The experimental set-up included snow fences installed in 2012, allowed investigations of the emissions of GHGs from soil under increased winter snow deposition and ambient field conditions. The soil fluxes of CH4 and CO2 were measured using closed chambers in manipulated plots with increased summer temperatures and shrub removal with or without increased winter precipitation. At the control plots, the averaged seasonal CH4 oxidation rates ranged between -0.05 mg CH4 m-2 hr-1 (end of August) and -0.32 mg CH4 m-2 hr-1 (end of June). In the plots with increased summer temperatures the rates ranged between -0.08 mg CH4 m-2 hr-1 (end of August) and -0.40 mg CH4 m-2 hr-1 (beginning of July). Preliminary results show a significant effect of increased winter precipitation (p<0.01) over the season as well as a significant warming effect (p<0.05) during July and August. These results suggest that in a warmer climate increasing CH4 uptake rates in dry Arctic soils could become an important factor for net CH4 budget.

Dual stable isotopes of CH 4 from Yellowstone hot-springs suggest hydrothermal processes involving magmatic CO 2

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

Moran, James J.; Whitmore, Laura M.; Jay, Zackary J.

Volcanism and post-magmatism contribute both significant annual CH 4 fluxes to the atmosphere (on par with other natural sources such as forest fire and wild animal emissions) and have been implicated in past climate-change events. The Yellowstone hot spot is one of the largest volcanic systems on Earth and is known to emit methane in addition to other greenhouse gases (e.g. carbon dioxide) but the ultimate source of this methane flux has not been elucidated. Here we use dual stable isotope analysis (δ 2H and δ 13C) of CH 4(g) sampled from ten high-temperature geothermal pools in Yellowstone National Parkmore » to show that the predominant flux of CH4(g) is abiotic. The average δ 13C and δ 2H values of CH 4(g) emitted from hot springs (-26.7 (±2.4) and -236.9 (±12.0) ‰, respectively) are not consistent with biotic (microbial or thermogenic) methane sources, but are within previously reported ranges for abiotic methane production. Correlation between δ 13C CH4 and δ 13C-dissolved inorganic C (DIC) also suggests that CO 2 is a parent C source for the observed CH 4(g). Moreover, CH 4-CO 2 isotopic geothermometry was used to estimate CH 4(g) formation temperatures ranging from ~ 250 - 350°C, which is just below the temperature estimated for the hydrothermal reservoir and consistent with the hypothesis that subsurface, rock-water interactions are responsible for large methane fluxes from this volcanic system. An understanding of conditions leading to the abiotic production of methane and associated isotopic signatures are central to understanding the evolutionary history of deep carbon sources on Earth.« less

Temporal variation in methane emissions in a shallow lake at a southern mid latitude during high and low rainfall periods.

PubMed

Fusé, Victoria S; Priano, M Eugenia; Williams, Karen E; Gere, José I; Guzmán, Sergio A; Gratton, Roberto; Juliarena, M Paula

2016-10-01

The global methane (CH 4 ) emission of lakes is estimated at between 6 and 16 % of total natural CH 4 emissions. However, these values have a high uncertainty due to the wide variety of lakes with important differences in their morphological, biological, and physicochemical parameters and the relatively scarse data from southern mid-latitude lakes. For these reasons, we studied CH 4 fluxes and CH 4 dissolved in water in a typical shallow lake in the Pampean Wetland, Argentina, during four periods of consecutive years (April 2011-March 2015) preceded by different rainfall conditions. Other water physicochemical parameters were measured and meteorological data were reported. We identified three different states of the lake throughout the study as the result of the irregular alternation between high and low rainfall periods, with similar water temperature values but with important variations in dissolved oxygen, chemical oxygen demand, water turbidity, electric conductivity, and water level. As a consequence, marked seasonal and interannual variations occurred in CH 4 dissolved in water and CH 4 fluxes from the lake. These temporal variations were best reflected by water temperature and depth of the Secchi disk, as a water turbidity estimation, which had a significant double correlation with CH 4 dissolved in water. The mean CH 4 fluxes values were 0.22 and 4.09 mg/m 2 /h for periods with low and high water turbidity, respectively. This work suggests that water temperature and turbidity measurements could serve as indicator parameters of the state of the lake and, therefore, of its behavior as either a CH 4 source or sink.

Estimating regional-scale methane flux and budgets using CARVE aircraft measurements over Alaska

NASA Astrophysics Data System (ADS)

Hartery, Sean; Commane, Róisín; Lindaas, Jakob; Sweeney, Colm; Henderson, John; Mountain, Marikate; Steiner, Nicholas; McDonald, Kyle; Dinardo, Steven J.; Miller, Charles E.; Wofsy, Steven C.; Chang, Rachel Y.-W.

2018-01-01

Methane (CH4) is the second most important greenhouse gas but its emissions from northern regions are still poorly constrained. In this study, we analyze a subset of in situ CH4 aircraft observations made over Alaska during the growing seasons of 2012-2014 as part of the Carbon in Arctic Reservoirs Vulnerability Experiment (CARVE). Net surface CH4 fluxes are estimated using a Lagrangian particle dispersion model which quantitatively links surface emissions from Alaska and the western Yukon with observations of enhanced CH4 in the mixed layer. We estimate that between May and September, net CH4 emissions from the region of interest were 2.2 ± 0.5 Tg, 1.9 ± 0.4 Tg, and 2.3 ± 0.6 Tg of CH4 for 2012, 2013, and 2014, respectively. If emissions are only attributed to two biogenic eco-regions within our domain, then tundra regions were the predominant source, accounting for over half of the overall budget despite only representing 18 % of the total surface area. Boreal regions, which cover a large part of the study region, accounted for the remainder of the emissions. Simple multiple linear regression analysis revealed that, overall, CH4 fluxes were largely driven by soil temperature and elevation. In regions specifically dominated by wetlands, soil temperature and moisture at 10 cm depth were important explanatory variables while in regions that were not wetlands, soil temperature and moisture at 40 cm depth were more important, suggesting deeper methanogenesis in drier soils. Although similar environmental drivers have been found in the past to control CH4 emissions at local scales, this study shows that they can be used to generate a statistical model to estimate the regional-scale net CH4 budget.

Analysis of the heat capacity for pure CH4 and CH4/CCl4 on graphite near the melting point and calculation of the T-X phase diagram for (CH3)CCl3 + CCl4

NASA Astrophysics Data System (ADS)

Yurtseven, Hamit; Yılmaz, Aygül

2016-06-01

We study the temperature dependence of the heat capacity Cp for the pure CH4 and the coadsorbed CH4/CCl4 on graphite near the melting point. The heat capacity peaks are analyzed using the experimental data from the literature by means of the power-law formula. The critical exponents for the heat capacity are deduced below and above the melting point for CH4 (Tm = 104.8 K) and CH4/CCl4 (Tm = 99.2 K). Our exponent values are larger as compared with the predicted values of some theoretical models exhibiting second order transition. Our analyses indicate that the pure methane shows a nearly second order (weak discontinuity in the heat capacity peak), whereas the transition in coadsorbed CH4/CCl4 is of first order (apparent discontinuity in Cp). We also study the T - X phase diagram of a two-component system of CH3CCl3+CCl4 using the Landau phenomenological model. Phase lines of the R+L (rhombohedral+liquid) and FCC+L (face-centred cubic + liquid) are calculated using the observed T - X phase diagram of this binary mixture. Our results show that the Landau mean field theory describes the observed behavior of CH3CCl3+CCl4 adequately. From the calculated T - X phase diagram, critical behavior of some thermodynamic quantities can be predicted at various temperatures and concentrations (CCl4) for a binary mixture of CH3CCl3+CCl4.

Optical sensor system for time-resolved quantification of methane densities in CH4-fueled spark ignition engines.

PubMed

Golibrzuch, Kai; Digulla, Finn-Erik; Bauke, Stephan; Wackerbarth, Hainer; Thiele, Olaf; Berg, Thomas

2017-08-01

We present the development and the first application of an optical sensor system that allows single-cycle determination of methane (CH 4 ) concentration inside internal combustion (IC) engines. We use non-dispersive infrared absorption spectroscopy to detect the CH 4 density with a time resolution up to 33 μs at acquisition rates of 30 kHz. The measurement scheme takes advantage of the strong temperature dependence of the absorption band applying two detection channels for CH 4 that detect different spectral regions of the ν 3 anti-symmetric C-H-stretch absorption. The strategy allows the simultaneous determination of fuel concentration as well as gas temperature. We show the proof-of-concept by validation of the measurement strategy in static pressure cell experiments as well as its application to a methane-fueled IC engine using a modified spark plug probe. Our results clearly demonstrate that it is crucial to determine the CH 4 temperature in the probe volume. Due to thermal influences of the sensor probe, the temperature needed to calculate the desired quantities (fuel density, fuel concentration) significantly differs from the gas phase temperature in the rest of the combustion chamber and estimations from standard thermodynamic models, e.g., polytropic compression, will fail.

Cross continental increase in methane ebullition under climate change.

PubMed

Aben, Ralf C H; Barros, Nathan; van Donk, Ellen; Frenken, Thijs; Hilt, Sabine; Kazanjian, Garabet; Lamers, Leon P M; Peeters, Edwin T H M; Roelofs, Jan G M; de Senerpont Domis, Lisette N; Stephan, Susanne; Velthuis, Mandy; Van de Waal, Dedmer B; Wik, Martin; Thornton, Brett F; Wilkinson, Jeremy; DelSontro, Tonya; Kosten, Sarian

2017-11-22

Methane (CH 4 ) strongly contributes to observed global warming. As natural CH 4 emissions mainly originate from wet ecosystems, it is important to unravel how climate change may affect these emissions. This is especially true for ebullition (bubble flux from sediments), a pathway that has long been underestimated but generally dominates emissions. Here we show a remarkably strong relationship between CH 4 ebullition and temperature across a wide range of freshwater ecosystems on different continents using multi-seasonal CH 4 ebullition data from the literature. As these temperature-ebullition relationships may have been affected by seasonal variation in organic matter availability, we also conducted a controlled year-round mesocosm experiment. Here 4 °C warming led to 51% higher total annual CH 4 ebullition, while diffusion was not affected. Our combined findings suggest that global warming will strongly enhance freshwater CH 4 emissions through a disproportional increase in ebullition (6-20% per 1 °C increase), contributing to global warming.

Two-State Reactivity in Low-Valent Iron-Mediated C-H Activation and the Implications for Other First-Row Transition Metals.

PubMed

Sun, Yihua; Tang, Hao; Chen, Kejuan; Hu, Lianrui; Yao, Jiannian; Shaik, Sason; Chen, Hui

2016-03-23

C-H bond activation/functionalization promoted by low-valent iron complexes has recently emerged as a promising approach for the utilization of earth-abundant first-row transition metals to carry out this difficult transformation. Herein we use extensive density functional theory and high-level ab initio coupled cluster calculations to shed light on the mechanism of these intriguing reactions. Our key mechanistic discovery for C-H arylation reactions reveals a two-state reactivity (TSR) scenario in which the low-spin Fe(II) singlet state, which is initially an excited state, crosses over the high-spin ground state and promotes C-H bond cleavage. Subsequently, aryl transmetalation occurs, followed by oxidation of Fe(II) to Fe(III) in a single-electron transfer (SET) step in which dichloroalkane serves as an oxidant, thus promoting the final C-C coupling and finalizing the C-H functionalization. Regeneration of the Fe(II) catalyst for the next round of C-H activation involves SET oxidation of the Fe(I) species generated after the C-C bond coupling. The ligand sphere of iron is found to play a crucial role in the TSR mechanism by stabilization of the reactive low-spin state that mediates the C-H activation. This is the first time that the successful TSR concept conceived for high-valent iron chemistry is shown to successfully rationalize the reactivity for a reaction promoted by low-valent iron complexes. A comparative study involving other divalent middle and late first-row transition metals implicates iron as the optimum metal in this TSR mechanism for C-H activation. It is predicted that stabilization of low-spin Mn(II) using an appropriate ligand sphere should produce another promising candidate for efficient C-H bond activation. This new TSR scenario therefore emerges as a new strategy for using low-valent first-row transition metals for C-H activation reactions.

NH4+ transport system of a psychrophilic marine bacterium, Vibrio sp. strain ABE-1.

PubMed

Chou, M; Matsunaga, T; Takada, Y; Fukunaga, N

1999-05-01

NH4(+) transport system of a psychrophilic marine bacterium Vibrio sp. strain ABE-1 (Vibrio ABE-1) was examined by measuring the uptake of [14C]methylammonium ion (14CH3NH3+) into the intact cells. 14CH3NH3+ uptake was detected in cells grown in medium containing glutamate as the sole nitrogen source, but not in those grown in medium containing NH4Cl instead of glutamate. Vibrio ABE-1 did not utilize CH3NH3+ as a carbon or nitrogen source. NH4Cl and nonradiolabeled CH3NH3+ completely inhibited 14CH3NH3+ uptake. These results indicate that 14CH3NH3+ uptake in this bacterium is mediated via an NH4+ transport system and not by a specific carrier for CH3NH3+. The respiratory substrate succinate was required to drive 14CH3NH3+ uptake and the uptake was completely inhibited by KCN, indicating that the uptake was energy dependent. The electrochemical potentials of H+ and/or Na+ across membranes were suggested to be the driving forces for the transport system because the ionophores carbonylcyanide m-chlorophenylhydrazone and monensin strongly inhibited uptake activities at pH 6.5 and 8.5, respectively. Furthermore, KCl activated 14CH3NH3+ uptake. The 14CH3NH3+ uptake activity of Vibrio ABE-1 was markedly high at temperatures between 0 degrees and 15 degrees C, and the apparent Km value for CH3NH3+ of the uptake did not change significantly over the temperature range from 0 degrees to 25 degrees C. Thus, the NH4+ transport system of this bacterium was highly active at low temperatures.

Orthorhombic fulleride (CH3NH2)K3C60 close to Mott-Hubbard instability: Ab initio study

NASA Astrophysics Data System (ADS)

Potočnik, Anton; Manini, Nicola; Komelj, Matej; Tosatti, Erio; Arčon, Denis

2012-08-01

We study the electronic structure and magnetic interactions in methylamine-intercalated orthorhombic alkali-doped fullerene (CH3NH2)K3C60 within the density functional theory. As in the simpler ammonia intercalated compound (NH3)K3C60, the orthorhombic crystal-field anisotropy Δ lifts the t1u triple degeneracy at the Γ point and drives the system deep into the Mott-insulating phase. However, the computed Δ and conduction electron bandwidth W cannot alone account for the abnormally low experimental Néel temperature, TN=11 K, of the methylamine compound, compared to the much higher value TN=40 K of the ammonia one. Significant interactions between CH3NH2 and C603- are responsible for the stabilization of particular fullerene-cage distortions and the ensuing low-spin S=1/2 state. These interactions also seem to affect the magnetic properties, as interfullerene exchange interactions depend on the relative orientation of deformations of neighboring C603- molecules. For the ferro-orientational order of CH3NH2-K+ groups we find an apparent reduced dimensionality in magnetic exchange interactions, which may explain the suppressed Néel temperature. The disorder in exchange interactions caused by orientational disorder of CH3NH2-K+ groups could further contribute to this suppression.

Searching for trans ethyl methyl ether in Orion KL⋆

NASA Astrophysics Data System (ADS)

Tercero, B.; Cernicharo, J.; López, A.; Brouillet, N.; Kolesniková, L.; Motiyenko, R. A.; Margulès, L.; Alonso, J. L.; Guillemin, J.-C.

2015-10-01

We report on the tentative detection of trans ethyl methyl ether (tEME), t-CH3CH2OCH3, through the identification of a large number of rotational lines from each one of the spin states of the molecule towards Orion KL. We also search for gauche-trans-n-propanol, Gt-n-CH3CH2CH2OH, an isomer of tEME in the same source. We have identified lines of both species in the IRAM 30 m line survey and in the ALMA Science Verification data. We have obtained ALMA maps to establish the spatial distribution of these species. Whereas tEME mainly arises from the compact ridge component of Orion, Gt-n-propanol appears at the emission peak of ethanol (south hot core). The derived column densities of these species at the location of their emission peaks are ≤(4.0 ± 0.8) × 1015 cm-2 and ≤(1.0 ± 0.2) × 1015 cm-2 for tEME and Gt-n-propanol, respectively. The rotational temperature is ~100 K for both molecules. We also provide maps of CH3OCOH, CH3CH2OCOH, CH3OCH3, CH3OH, and CH3CH2OH to compare the distribution of these organic saturated O-bearing species containing methyl and ethyl groups in this region. Abundance ratios of related species and upper limits to the abundances of non-detected ethers are provided. We derive an abundance ratio N(CH3OCH3)/N(tEME) ≥ 150 in the compact ridge of Orion. This paper makes use of the following ALMA data: ADS/JAO.ALMA#2011.0.00009.SV. ALMA is a partnership of ESO (representing its member states), NSF (USA), and NINS (Japan) with NRC (Canada), NSC, and ASIAA (Taiwan), and KASI (Republic of Korea), in cooperation with the Republic of Chile. The Joint ALMA Observatory is operated by ESO, AUI/NRAO, and NAOJ. This work was also based on observations carried out with the IRAM 30-m telescope. IRAM is supported by INSU/CNRS (France), MPG (Germany), and IGN (Spain).Appendix A is available in electronic form at http://www.aanda.org

Temperature and burning history affect emissions of greenhouse gases and aerosol particles from tropical peatland fire

NASA Astrophysics Data System (ADS)

Kuwata, Mikinori; Kai, Fuu Ming; Yang, Liudongqing; Itoh, Masayuki; Gunawan, Haris; Harvey, Charles F.

2017-01-01

Tropical peatland burning in Asia has been intensifying over the last decades, emitting huge amounts of gas species and aerosol particles. Both laboratory and field studies have been conducted to investigate emission from peat burning, yet a significant variability in data still exists. We conducted a series of experiments to characterize the gas and particulate matter emitted during burning of a peat sample from Sumatra in Indonesia. Heating temperature of peat was found to regulate the ratio of CH4 to CO2 in emissions (ΔCH4/ΔCO2) as well as the chemical composition of particulate matter. The ΔCH4/ΔCO2 ratio was larger for higher temperatures, meaning that CH4 emission is more pronounced at these conditions. Mass spectrometric analysis of organic components indicated that aerosol particles emitted at higher temperatures had more unsaturated bonds and ring structures than that emitted from cooler fires. The result was consistently confirmed by nuclear magnetic resonance analysis. In addition, CH4 emitted by burning charcoal, which is derived from previously burned peat, was lower by at least an order of magnitude than that from fresh peat. These results highlight the importance of both fire history and heating temperature for the composition of tropical peat-fire emissions. They suggest that remote sensing technologies that map fire histories and temperatures could provide improved estimates of emissions.

Enhanced simulations of CH4 and CO2 production in permafrost-affected soils address soil moisture controls on anaerobic decomposition

NASA Astrophysics Data System (ADS)

Graham, D. E.; Zheng, J.; Moon, J. W.; Painter, S. L.; Thornton, P. E.; Gu, B.; Wullschleger, S. D.

2017-12-01

Rapid warming of Arctic ecosystems exposes soil organic carbon (SOC) to accelerated microbial decomposition, leading to increased emissions of carbon dioxide (CO2) and methane (CH4) that have a positive feedback on global warming. The magnitude, timing, and form of carbon release will depend not only on changes in temperature, but also on biogeochemical and hydrological properties of soils. In this synthesis study, we assessed the decomposability of thawed organic carbon from active layer soils and permafrost from the Barrow Environmental Observatory across different microtopographic positions under anoxic conditions. The main objectives of this study were to (i) examine environmental conditions and soil properties that control anaerobic carbon decomposition and carbon release (as both CO2 and CH4); (ii) develop a common set of parameters to simulate anaerobic CO2 and CH4 production; and (iii) evaluate uncertainties generated from representations of pH and temperature effects in the current model framework. A newly developed anaerobic carbon decomposition framework simulated incubation experiment results across a range of soil water contents. Anaerobic CO2 and CH4 production have different temperature and pH sensitivities, which are not well represented in current biogeochemical models. Distinct dynamics of CH4 production at -2° C suggest methanogen biomass and growth rate limit activity in these near-frozen soils, compared to warmer temperatures. Anaerobic CO2 production is well constrained by the model using data-informed labile carbon pool and fermentation rate initialization to accurately simulate its temperature sensitivity. On the other hand, CH4 production is controlled by water content, methanogenesis biomass, and the presence of alternative electron acceptors, producing a high temperature sensitivity with large uncertainties for methanogenesis. This set of environmental constraints to methanogenesis is likely to undergo drastic changes due to permafrost thawing, and extrapolation of methanogenesis rates into a future warmer climate remains challenging.

Environmental and physical controls on northern terrestrial methane emissions across permafrost zones

USGS Publications Warehouse

Olefeldt, David; Turetsky, Merritt R.; Crill, Patrick M.; McGuire, A. David

2013-01-01

Methane (CH4) emissions from the northern high-latitude region represent potentially significant biogeochemical feedbacks to the climate system. We compiled a database of growing-season CH4 emissions from terrestrial ecosystems located across permafrost zones, including 303 sites described in 65 studies. Data on environmental and physical variables, including permafrost conditions, were used to assess controls on CH4 emissions. Water table position, soil temperature, and vegetation composition strongly influenced emissions and had interacting effects. Sites with a dense sedge cover had higher emissions than other sites at comparable water table positions, and this was an effect that was more pronounced at low soil temperatures. Sensitivity analysis suggested that CH4 emissions from ecosystems where the water table on average is at or above the soil surface (wet tundra, fen underlain by permafrost, and littoral ecosystems) are more sensitive to variability in soil temperature than drier ecosystems (palsa dry tundra, bog, and fen), whereas the latter ecosystems conversely are relatively more sensitive to changes of the water table position. Sites with near-surface permafrost had lower CH4 fluxes than sites without permafrost at comparable water table positions, a difference that was explained by lower soil temperatures. Neither the active layer depth nor the organic soil layer depth was related to CH4 emissions. Permafrost thaw in lowland regions is often associated with increased soil moisture, higher soil temperatures, and increased sedge cover. In our database, lowland thermokarst sites generally had higher emissions than adjacent sites with intact permafrost, but emissions from thermokarst sites were not statistically higher than emissions from permafrost-free sites with comparable environmental conditions. Overall, these results suggest that future changes to terrestrial high-latitude CH4 emissions will be more proximately related to changes in moisture, soil temperature, and vegetation composition than to increased availability of organic matter following permafrost thaw.

An alternative NMR method to determine nuclear shielding anisotropies for molecules in liquid-crystalline solutions with (13)C shielding anisotropy of methyl iodide as an example.

PubMed

Tallavaara, Pekka; Jokisaari, Jukka

2008-03-28

An alternative NMR method for determining nuclear shielding anisotropies in molecules is proposed. The method is quite simple, linear and particularly applicable for heteronuclear spin systems. In the technique, molecules of interest are dissolved in a thermotropic liquid crystal (LC) which is confined in a mesoporous material, such as controlled pore glass (CPG) used in this study. CPG materials consist of roughly spherical particles with a randomly oriented and connected pore network inside. LC Merck Phase 4 was confined in the pores of average diameter from 81 to 375 A and LC Merck ZLI 1115 in the pores of average diameter 81 A. In order to demonstrate the functionality of the method, the (13)C shielding anisotropy of (13)C-enriched methyl iodide, (13)CH(3)I, was determined as a function of temperature using one dimensional (13)C NMR spectroscopy. Methane gas, (13)CH(4), was used as an internal chemical shift reference. It appeared that methyl iodide molecules experience on average an isotropic environment in LCs inside the smallest pores within the whole temperature range studied, ranging from bulk solid to isotropic phase. In contrast, in the spaces in between the particles, whose diameter is approximately 150 microm, LCs behave as in the bulk. Consequently, isotropic values of the shielding tensor can be determined from spectra arising from molecules inside the pores at exactly the same temperature as the anisotropic ones from molecules outside the pores. Thus, for the first time in the solution state, shielding anisotropies can easily be determined as a function of temperature. The effects of pore size as well as of different LC media on the shielding anisotropy are examined and discussed.

New Radiative Transfer Capability in the EPIC Atmospheric Model with Application to Saturn and Uranus

NASA Astrophysics Data System (ADS)

Dowling, Timothy Edward; Greathouse, T. K.; Sussman, M. G.; Chanover, N. J.

2010-10-01

We have adapted radiative transfer (RT) schemes from the gas-giant seasonal models of Greathouse et al. (EGU 2010) and Sussman et al. (AGU 2009) into the EPIC atmospheric model, and applied them to Saturn and Uranus. These additions give EPIC a hierarchy of RT options to account for solar heating via CH4 absorption from 5 microns to the UV, and radiative cooling due to thermal emission of CH4, C2H2, C2H6, and collision-induced opacity between 0 and 1600 cm-1. We have written an IDL tool to calculate radiative-equilibrium T(p) profiles for model initialization. We have ported the versatile DISORT RT model (Stamnes et al. 1988) from Fortran to C, and are incorporating it into an IDL post-processing tool to allow us to create synthetic spectra from EPIC output that accounts for thermal emission, reflected solar light, and aerosol and Rayleigh scattering. We give an update of applications to simulations of middle-atmosphere temperatures for Saturn and zonal-wind spin-up experiments for Uranus. This research is supported by NASA Planetary Atmospheres grant NNX08AE64G and NSF Planetary Astronomy grant AST-0807989.

Fabrication of a Highly Sensitive Single Aligned TiO2 and Gold Nanoparticle Embedded TiO2 Nano-Fiber Gas Sensor.

PubMed

Nikfarjam, Alireza; Hosseini, Seyedsina; Salehifar, Nahideh

2017-05-10

In this research, a single-aligned nanofiber of pure TiO 2 and gold nanoparticle (GNP)-TiO 2 were fabricated using a novel electro-spinning procedure equipped with secondary electrostatic fields on highly sharp triangular and rectangular electrodes provided for gas sensing applications. The sol used for spinning nanofiber consisted of titanium tetraisopropoxide (C 12 H 28 O 4 Ti), acetic acid (CH 3 COOH), ethanol (C 2 H 5 OH), polyvinylpyrrolidone (PVP), and gold nanoparticle solution. FE-SEM, TEM, and XRD were used to characterize the single nanofiber. In triangular electrodes, the electrostatic voltage for aligning single nanofiber between electrodes depends on the angle tip of the electrode, which was around 1.4-2.1, 2-2.9, and 3.2-4.1 kV for 30°, 45°, and 60°, respectively. However, by changing the shape of the electrodes to rectangular samples and by increasing distance between electrodes from 100 to 200 μm, electro-spinning applied voltage decreased. Response of pure TiO 2 single nanofiber sensor was measured for 30-200 ppb carbon monoxide gas. The triangular sample revealed better response and lower threshold than the rectangular sample. Adding appropriate amounts of GNP decreased the operating temperature and increased the responses. CO concentration threshold for the pure TiO 2 and GNP-TiO 2 triangular samples was about 5 ppb and 700 ppt, respectively.

Methane flux from Minnesota Peatlands

NASA Astrophysics Data System (ADS)

Crill, P. M.; Bartlett, K. B.; Harriss, R. C.; Gorham, E.; Verry, E. S.; Sebacher, D. I.; Madzar, L.; Sanner, W.

1988-12-01

Northern (>40°N) wetlands have been suggested as the largest natural source of methane (CH4) to the troposphere. To refine our estimates of source strengths from this region and to investigate climatic controls on the process, fluxes were measured from a variety of Minnesota peatlands during May, June, and August 1986. Sites included forested and unforested ombrotrophic bogs and minerotrophic fens in and near the U.S. Department of Agriculture Marcell Experimental Forest and the Red Lake peatlands. Late spring and summer fluxes ranged from 11 to 866 mg CH4 m-2 d-1, averaging 207 mg CH4 m-2 d-1 overall. At Marcell Forest, forested bogs and fen sites had lower fluxes (averages of 77 ± 21 mg CH4 m-2 d-1 and 142 ± 19 mg CH4 m-2 d-1) than open bogs (average of 294 ± 30 mg CH4 m-2 d-1). In the Red Lake peatland, circumneutral fens, with standing water above the peat surface, produced more methane than acid bog sites in which the water table was beneath the moss surface (325 ± 31 and 102 ± 13 mg CH4 m-2 d-1, respectively). Peat temperature was an important control. Methane flux increased in response to increasing soil temperature. For example, the open bog in the Marcell Forest with the highest CH4 flux exhibited a 74-fold increase in flux over a three-fold increase in temperature. We estimate that the methane flux from all peatlands north of 40° may be on the order of 70 to 90 Tg/yr though estimates of this sort are plagued by uncertainties in the areal extent of peatlands, length of the CH4 producing season, and the spatial and temporal variability of the flux.

Effects of animal activity and air temperature on methane and ammonia emissions from a naturally ventilated building for dairy cows

NASA Astrophysics Data System (ADS)

Ngwabie, N. M.; Jeppsson, K.-H.; Gustafsson, G.; Nimmermark, S.

2011-12-01

Knowledge of how different factors affect gas emissions from animal buildings can be useful for emission prediction purposes and for the improvement of emission abatement techniques. In this study, the effects of dairy cow activity and indoor air temperature on gas emissions were examined. The concentrations of CH 4, NH 3, CO 2 and N 2O inside and outside a dairy cow building were measured continuously between February and May together with animal activity and air temperature. The building was naturally ventilated and had a solid concrete floor which sloped towards a central urine gutter. Manure was scraped from the floor once every hour in the daytime and once every second hour at night into a partly covered indoor pit which was emptied daily at 6 a.m. and at 5 p.m. Gas emissions were calculated from the measured gas concentrations and ventilation rates estimated by the CO 2 balance method. The animal activity and emission rates of CH 4 and NH 3 showed significant diurnal variations with two peaks which were probably related to the feeding routine. On an average day, CH 4 emissions ranged from 7 to 15 g LU -1 h -1 and NH 3 emissions ranged from 0.4 to 1.5 g LU -1 h -1 (1 LU = 500 kg animal weight). Mean emissions of CH 4 and NH 3 were 10.8 g LU -1 h -1 and 0.81 g LU -1 h -1, respectively. The NH 3 emissions were comparable to emissions from tied stall buildings and represented a 4% loss in manure nitrogen. At moderate levels, temperature seems to affect the behaviour of dairy cows and in this study where the daily indoor air temperature ranged from about 5 up to about 20 °C, the daily activity of the cows decreased with increasing indoor air temperature ( r = -0.78). Results suggest that enteric fermentation is the main source of CH 4 emissions from systems of the type in this study, while NH 3 is mainly emitted from the manure. Daily CH 4 emissions increased significantly with the activity of the cows ( r = 0.61) while daily NH 3 emissions increased significantly with the indoor air temperatures ( r = 0.66). Daily CH 4 emissions were negatively correlated to the indoor air temperature ( r = -0.84). This suggests that increased daily indoor air temperatures due to seasonal changes may bring about decreased animal activity which may decrease the release of CH 4 from dairy cows. Finally, changes in daily NH 3 emissions were influenced more by the indoor air temperature than by the activity of the cows.

Magnetic tunnel spin injectors for spintronics

NASA Astrophysics Data System (ADS)

Wang, Roger

Research in spin-based electronics, or "spintronics", has a universal goal to develop applications for electron spin in a broad range of electronics and strives to produce low power nanoscale devices. Spin injection into semiconductors is an important initial step in the development of spintronic devices, with the goal to create a highly spin polarized population of electrons inside a semiconductor at room temperature for study, characterization, and manipulation. This dissertation investigates magnetic tunnel spin injectors that aim to meet the spin injection requirements needed for potential spintronic devices. Magnetism and spin are inherently related, and chapter 1 provides an introduction on magnetic tunneling and spintronics. Chapter 2 then describes the fabrication of the spin injector structures studied in this dissertation, and also illustrates the optical spin detection technique that correlates the measured electroluminescence polarization from quantum wells to the electron spin polarization inside the semiconductor. Chapter 3 reports the spin injection from the magnetic tunnel transistor (MTT) spin injector, which is capable of producing highly spin polarized tunneling currents by spin selective scattering in its multilayer structure. The MTT achieves ˜10% lower bound injected spin polarization in GaAs at 1.4 K. Chapter 4 reports the spin injection from CoFe-MgO(100) tunnel spin injectors, where spin dependent tunneling through MgO(100) produces highly spin polarized tunneling currents. These structures achieve lower bound spin polarizations exceeding 50% at 100 K and 30% in GaAs at 290 K. The CoFe-MgO spin injectors also demonstrate excellent thermal stability, maintaining high injection efficiencies even after exposure to temperatures of up to 400 C. Bias voltage and temperature dependent studies on these structures indicate a significant dependence of the electroluminescence polarization on the spin and carrier recombination lifetimes inside the semiconductor. Chapter 5 investigates these spin and carrier lifetime effects on the electroluminescence polarization using time resolved optical techniques. These studies suggest that a peak in the carrier lifetime with temperature is responsible for the nonmonotonic temperature dependence observed in the electroluminescence polarization, and that the initially injected spin polarization from CoFe-MgO spin injectors is a nearly temperature independent ˜70% from 10 K up to room temperature.

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

NASA Technical Reports Server (NTRS)

Smith, Gregory P.; Huestis, David L.

2002-01-01

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

Nuclear spin polarized H and D by means of spin-exchange optical pumping

NASA Astrophysics Data System (ADS)

Stenger, Jörn; Grosshauser, Carsten; Kilian, Wolfgang; Nagengast, Wolfgang; Ranzenberger, Bernd; Rith, Klaus; Schmidt, Frank

1998-01-01

Optically pumped spin-exchange sources for polarized hydrogen and deuterium atoms have been demonstrated to yield high atomic flow and high electron spin polarization. For maximum nuclear polarization the source has to be operated in spin temperature equilibrium, which has already been demonstrated for hydrogen. In spin temperature equilibrium the nuclear spin polarization PI equals the electron spin polarization PS for hydrogen and is even larger than PS for deuterium. We discuss the general properties of spin temperature equilibrium for a sample of deuterium atoms. One result are the equations PI=4PS/(3+PS2) and Pzz=PSṡPI, where Pzz is the nuclear tensor polarization. Furthermore we demonstrate that the deuterium atoms from our source are in spin temperature equilibrium within the experimental accuracy.

Reflected shock tube studies of high-temperature rate constants for OH + CH4 --> CH3 + H2O and CH3 + NO2 --> CH3O + NO.

PubMed

Srinivasan, N K; Su, M-C; Sutherland, J W; Michael, J V

2005-03-10

The reflected shock tube technique with multipass absorption spectrometric detection of OH radicals at 308 nm has been used to study the reactions OH + CH(4) --> CH(3) + H(2)O and CH(3) + NO(2) --> CH(3)O + NO. Over the temperature range 840-2025 K, the rate constants for the first reaction can be represented by the Arrhenius expression k = (9.52 +/- 1.62) x 10(-11) exp[(-4134 +/- 222 K)/T] cm(3) molecule(-1) s(-1). Since this reaction is important in both combustion and atmospheric chemistry, there have been many prior investigations with a variety of techniques. The present results extend the temperature range by 500 K and have been combined with the most accurate earlier studies to derive an evaluation over the extended temperature range 195-2025 K. A three-parameter expression describes the rate behavior over this temperature range, k = (1.66 x 10(-18))T(2.182) exp[(-1231 K)/T] cm(3) molecule(-1) s(-1). Previous theoretical studies are discussed, and the present evaluation is compared to earlier theoretical estimates. Since CH(3) radicals are a product of the reaction and could cause secondary perturbations in rate constant determinations, the second reaction was studied by OH radical production from the fast reactions CH(3)O --> CH(2)O + H and H + NO(2) --> OH + NO. The measured rate constant is 2.26 x 10(-11) cm(3) molecule(-1) s(-1) and is not dependent on temperature from 233 to 1700 K within experimental error.

Monitoring a simple hydrolysis process in an organic solid by observing methyl group rotation.

PubMed

Beckmann, Peter A; Bohen, Joseph M; Ford, Jamie; Malachowski, William P; Mallory, Clelia W; Mallory, Frank B; McGhie, Andrew R; Rheingold, Arnold L; Sloan, Gilbert J; Szewczyk, Steven T; Wang, Xianlong; Wheeler, Kraig A

2017-09-01

We report a variety of experiments and calculations and their interpretations regarding methyl group (CH 3 ) rotation in samples of pure 3-methylglutaric anhydride (1), pure 3-methylglutaric acid (2), and samples where the anhydride is slowly absorbing water from the air and converting to the acid [C 6 H 8 O 3 (1) + H 2 O → C 6 H 10 O 4 (2)]. The techniques are solid state 1 H nuclear magnetic resonance (NMR) spin-lattice relaxation, single-crystal X-ray diffraction, electronic structure calculations in both isolated molecules and in clusters of molecules that mimic the crystal structure, field emission scanning electron microscopy, differential scanning calorimetry, and high resolution 1 H NMR spectroscopy. The solid state 1 H spin-lattice relaxation experiments allow us to observe the temperature dependence of the parameters that characterize methyl group rotation in both compounds and in mixtures of the two compounds. In the mixtures, both types of methyl groups (that is, molecules of 1 and 2) can be observed independently and simultaneously at low temperatures because the solid state 1 H spin-lattice relaxation is appropriately described by a double exponential. We have followed the conversion 1 → 2 over periods of two years. The solid state 1 H spin-lattice relaxation experiments in pure samples of 1 and 2 indicate that there is a distribution of NMR activation energies for methyl group rotation in 1 but not in 2 and we are able to explain this in terms of the particle sizes seen in the field emission scanning electron microscopy images. Copyright © 2017 Elsevier Inc. All rights reserved.

Room temperature spin diffusion in (110) GaAs/AlGaAs quantum wells

PubMed Central

2011-01-01

Transient spin grating experiments are used to investigate the electron spin diffusion in intrinsic (110) GaAs/AlGaAs multiple quantum well at room temperature. The measured spin diffusion length of optically excited electrons is about 4 μm at low spin density. Increasing the carrier density yields both a decrease of the spin relaxation time and the spin diffusion coefficient Ds. PMID:21711662

Synthesis and Characterization of Methylammonium Borohydride

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

Graham, Kathryn R.; Bowden, Mark E.; Kemmitt, Tim

2011-01-06

A new borohydride, [CH3NH3]+[BH4]-, has been synthesised by the metathesis of CH3NH3X and MBH4 in methylamine in order to determine its behaviour in comparison to ammonium borohydride [NH4]+[BH4]-. The introduction of methyl groups is expected to disrupt the hydrogen bonding network of [NH4]+[BH4]- and in turn alter the hydrogen release properties. Room temperature X-ray diffraction studies have shown that [CH3NH3]+[BH4]- adopts a tetragonal unit cell with lattice parameters of a = 4.9486 Å and b = 8.9083 Å. The room temperature structure shows considerable hydrogen mobility similar to that observed in NH3BH3. The kinetics and thermodynamics of these reactions havemore » been investigated and show hydrogen release follows a similar pathway to that of [NH4]+[BH4]-. Both compounds decompose slowly at room temperature and rapidly at ca. 40 °C to form the diammoniate of diborane or the methylated analogue [BH2(CH3NH2)2]+BH4-. The first stage of decomposition has been further investigated by means on in-situ X-ray diffraction and solid state 11B NMR spectroscopy, and appears to occur in the absence of any detectable intermediates to form crystalline [BH2(CH3NH2)2]+BH4-. [(CH3)2NH2]+[BH4]- and [BH2{(CH3)2NH}2]+BH4- have also been synthesised by analogous routes, indicating a more general applicability of the synthetic method.« less

Nuclearity controlled cyanide-bridged bimetallic CrIII-MnII compounds: synthesis, crystal structures, magnetic properties and theoretical calculations.

PubMed

Toma, Luminita; Lescouëzec, Rodrigue; Vaissermann, Jacqueline; Delgado, Fernando S; Ruiz-Pérez, Catalina; Carrasco, Rosa; Cano, Juan; Lloret, Francesc; Julve, Miguel

2004-11-19

The preparation, X-ray crystallography and magnetic investigation of the compounds PPh4[Cr(bipy)(CN)4].2 CH3CN.H2O (1) (mononuclear), [[Cr(bipy)(CN)4]2Mn-(H2O)4].4H2O (2) (trinuclear), [[Cr(bipy)(CN)4]2Mn(H2O)2] (3) (chain) and [[Cr(bipy)(CN)4]2Mn(H2O)].H2O.CH3CN (4) (double chain) [bipy=2,2'-bipyridine; PPh4 (+)=tetraphenylphosphonium] are described herein. The [Cr(bipy)(CN)4]- unit act either as a monodentate (2) or bis-monodentate (3) ligand toward the manganese atom through one (2) or two (3) of its four cyanide groups. The manganese atom is six-coordinate with two (2) or four (3) cyanide nitrogens and four (2) or two (3) water molecules building a distorted octahedral environment. In 4, two chains of 3 are pillared through interchain Mn-N-C-Cr links which replace one of the two trans-coordinated water molecules at the manganese atom to afford a double chain structure where bis- and tris-monodenate coordination modes of [Cr(bipy)(CN)4]- coexist. The magnetic properties of 1-4 were investigated in the temperature range 1.9-300 K. A Curie law behaviour for a magnetically isolated spin quartet is observed for 1. A significant antiferromagnetic interaction between CrIII and MnII through the single cyanide bridge [J=-6.2 cm(-1), the Hamiltonian being defined as H=-J(SCr1.SMn+SCr2.SMn] occurs in 2 leading to a low-lying spin doublet which is fully populated at T <5 K. A metamagnetic behaviour is observed for 3 and 4 [the values of the critical field Hc being ca. 3000 (3) and 1500 Oe (4)] which is associated to the occurrence of weak interchain antiferromagnetic interactions between ferrimagnetic Cr2III MnII chains. The analysis of the exchange pathways in 2-4 through DFT type calculations together with the magnetic bevaviour simulation using the quantum Monte Carlo methodology provided a good understanding of their magnetic properties.

Estimation of Methane Emissions from Slurry Pits below Pig and Cattle Confinements

PubMed Central

Petersen, Søren O.; Olsen, Anne B.; Elsgaard, Lars; Triolo, Jin Mi; Sommer, Sven G.

2016-01-01

Quantifying in-house emissions of methane (CH4) from liquid manure (slurry) is difficult due to high background emissions from enteric processes, yet of great importance for correct estimation of CH4 emissions from manure management and effects of treatment technologies such as anaerobic digestion. In this study CH4 production rates were determined in 20 pig slurry and 11 cattle slurry samples collected beneath slatted floors on six representative farms; rates were determined within 24 h at temperatures close to the temperature in slurry pits at the time of collection. Methane production rates in pig and cattle slurry differed significantly at 0.030 and 0.011 kg CH4 kg-1 VS (volatile solids). Current estimates of CH4 emissions from pig and cattle manure management correspond to 0.032 and 0.015 kg CH4 kg-1, respectively, indicating that slurry pits under animal confinements are a significant source. Fractions of degradable volatile solids (VSd, kg kg-1 VS) were estimated using an aerobic biodegradability assay and total organic C analyses. The VSd in pig and cattle slurry averaged 0.51 and 0.33 kg kg-1 VS, and it was estimated that on average 43 and 28% of VSd in fresh excreta from pigs and cattle, respectively, had been lost at the time of sampling. An empirical model of CH4 emissions from slurry was reparameterised based on experimental results. A sensitivity analysis indicated that predicted CH4 emissions were highly sensitive to uncertainties in the value of lnA of the Arrhenius equation, but much less sensitive to uncertainties in VSd or slurry temperature. A model application indicated that losses of carbon in VS as CO2 may be much greater than losses as CH4. Implications of these results for the correct estimation of CH4 emissions from manure management, and for the mitigation potential of treatments such as anaerobic digestion, are discussed. PMID:27529692

Isotopic insights into methane production, oxidation, and emissions in Arctic polygon tundra.

PubMed

Vaughn, Lydia J S; Conrad, Mark E; Bill, Markus; Torn, Margaret S

2016-10-01

Arctic wetlands are currently net sources of atmospheric CH4 . Due to their complex biogeochemical controls and high spatial and temporal variability, current net CH4 emissions and gross CH4 processes have been difficult to quantify, and their predicted responses to climate change remain uncertain. We investigated CH4 production, oxidation, and surface emissions in Arctic polygon tundra, across a wet-to-dry permafrost degradation gradient from low-centered (intact) to flat- and high-centered (degraded) polygons. From 3 microtopographic positions (polygon centers, rims, and troughs) along the permafrost degradation gradient, we measured surface CH4 and CO2 fluxes, concentrations and stable isotope compositions of CH4 and DIC at three depths in the soil, and soil moisture and temperature. More degraded sites had lower CH4 emissions, a different primary methanogenic pathway, and greater CH4 oxidation than did intact permafrost sites, to a greater degree than soil moisture or temperature could explain. Surface CH4 flux decreased from 64 nmol m(-2)  s(-1) in intact polygons to 7 nmol m(-2)  s(-1) in degraded polygons, and stable isotope signatures of CH4 and DIC showed that acetate cleavage dominated CH4 production in low-centered polygons, while CO2 reduction was the primary pathway in degraded polygons. We see evidence that differences in water flow and vegetation between intact and degraded polygons contributed to these observations. In contrast to many previous studies, these findings document a mechanism whereby permafrost degradation can lead to local decreases in tundra CH4 emissions. © 2016 John Wiley & Sons Ltd.

Interannual variation in methane emissions from tropical wetlands triggered by repeated El Niño Southern Oscillation

USGS Publications Warehouse

Zhu, Qiuan; Peng, Changhui; Ciais, Philippe; Jiang, Hong; Liu, Jinxun; Bousquet, Philippe; Li, Shiqin; Chang, Jie; Fang, Xiuqin; Zhou, Xiaolu; Chen, Huai; Liu, Shirong; Lin, Guanghui; Gong, Peng; Wang, Meng; Wang, Han; Xiang, Wenhua; Chen, Jing

2017-01-01

Methane (CH4) emissions from tropical wetlands contribute 60%–80% of global natural wetland CH4 emissions. Decreased wetland CH4 emissions can act as a negative feedback mechanism for future climate warming and vice versa. The impact of the El Niño–Southern Oscillation (ENSO) on CH4 emissions from wetlands remains poorly quantified at both regional and global scales, and El Niño events are expected to become more severe based on climate models’ projections. We use a process-based model of global wetland CH4 emissions to investigate the impacts of the ENSO on CH4 emissions in tropical wetlands for the period from 1950 to 2012. The results show that CH4 emissions from tropical wetlands respond strongly to repeated ENSO events, with negative anomalies occurring during El Niño periods and with positive anomalies occurring during La Niña periods. An approximately 8-month time lag was detected between tropical wetland CH4 emissions and ENSO events, which was caused by the combined time lag effects of ENSO events on precipitation and temperature over tropical wetlands. The ENSO can explain 49% of interannual variations for tropical wetland CH4 emissions. Furthermore, relative to neutral years, changes in temperature have much stronger effects on tropical wetland CH4 emissions than the changes in precipitation during ENSO periods. The occurrence of several El Niño events contributed to a lower decadal mean growth rate in atmospheric CH4 concentrations throughout the 1980s and 1990s and to stable atmospheric CH4 concentrations from 1999 to 2006, resulting in negative feedback to global warming.

Interannual variation in methane emissions from tropical wetlands triggered by repeated El Niño Southern Oscillation.

PubMed

Zhu, Qiuan; Peng, Changhui; Ciais, Philippe; Jiang, Hong; Liu, Jinxun; Bousquet, Philippe; Li, Shiqin; Chang, Jie; Fang, Xiuqin; Zhou, Xiaolu; Chen, Huai; Liu, Shirong; Lin, Guanghui; Gong, Peng; Wang, Meng; Wang, Han; Xiang, Wenhua; Chen, Jing

2017-11-01

Methane (CH 4 ) emissions from tropical wetlands contribute 60%-80% of global natural wetland CH 4 emissions. Decreased wetland CH 4 emissions can act as a negative feedback mechanism for future climate warming and vice versa. The impact of the El Niño-Southern Oscillation (ENSO) on CH 4 emissions from wetlands remains poorly quantified at both regional and global scales, and El Niño events are expected to become more severe based on climate models' projections. We use a process-based model of global wetland CH 4 emissions to investigate the impacts of the ENSO on CH 4 emissions in tropical wetlands for the period from 1950 to 2012. The results show that CH 4 emissions from tropical wetlands respond strongly to repeated ENSO events, with negative anomalies occurring during El Niño periods and with positive anomalies occurring during La Niña periods. An approximately 8-month time lag was detected between tropical wetland CH 4 emissions and ENSO events, which was caused by the combined time lag effects of ENSO events on precipitation and temperature over tropical wetlands. The ENSO can explain 49% of interannual variations for tropical wetland CH 4 emissions. Furthermore, relative to neutral years, changes in temperature have much stronger effects on tropical wetland CH 4 emissions than the changes in precipitation during ENSO periods. The occurrence of several El Niño events contributed to a lower decadal mean growth rate in atmospheric CH 4 concentrations throughout the 1980s and 1990s and to stable atmospheric CH 4 concentrations from 1999 to 2006, resulting in negative feedback to global warming. © 2017 John Wiley & Sons Ltd.

Emerging role of wetland methane emissions in driving 21st century climate change.

PubMed

Zhang, Zhen; Zimmermann, Niklaus E; Stenke, Andrea; Li, Xin; Hodson, Elke L; Zhu, Gaofeng; Huang, Chunlin; Poulter, Benjamin

2017-09-05

Wetland methane (CH 4 ) emissions are the largest natural source in the global CH 4 budget, contributing to roughly one third of total natural and anthropogenic emissions. As the second most important anthropogenic greenhouse gas in the atmosphere after CO 2 , CH 4 is strongly associated with climate feedbacks. However, due to the paucity of data, wetland CH 4 feedbacks were not fully assessed in the Intergovernmental Panel on Climate Change Fifth Assessment Report. The degree to which future expansion of wetlands and CH 4 emissions will evolve and consequently drive climate feedbacks is thus a question of major concern. Here we present an ensemble estimate of wetland CH 4 emissions driven by 38 general circulation models for the 21st century. We find that climate change-induced increases in boreal wetland extent and temperature-driven increases in tropical CH 4 emissions will dominate anthropogenic CH 4 emissions by 38 to 56% toward the end of the 21st century under the Representative Concentration Pathway (RCP2.6). Depending on scenarios, wetland CH 4 feedbacks translate to an increase in additional global mean radiative forcing of 0.04 W·m -2 to 0.19 W·m -2 by the end of the 21st century. Under the "worst-case" RCP8.5 scenario, with no climate mitigation, boreal CH 4 emissions are enhanced by 18.05 Tg to 41.69 Tg, due to thawing of inundated areas during the cold season (December to May) and rising temperature, while tropical CH 4 emissions accelerate with a total increment of 48.36 Tg to 87.37 Tg by 2099. Our results suggest that climate mitigation policies must consider mitigation of wetland CH 4 feedbacks to maintain average global warming below 2 °C.

Emerging role of wetland methane emissions in driving 21st century climate change

PubMed Central

Zimmermann, Niklaus E.; Stenke, Andrea; Li, Xin; Hodson, Elke L.; Zhu, Gaofeng; Huang, Chunlin; Poulter, Benjamin

2017-01-01

Wetland methane (CH4) emissions are the largest natural source in the global CH4 budget, contributing to roughly one third of total natural and anthropogenic emissions. As the second most important anthropogenic greenhouse gas in the atmosphere after CO2, CH4 is strongly associated with climate feedbacks. However, due to the paucity of data, wetland CH4 feedbacks were not fully assessed in the Intergovernmental Panel on Climate Change Fifth Assessment Report. The degree to which future expansion of wetlands and CH4 emissions will evolve and consequently drive climate feedbacks is thus a question of major concern. Here we present an ensemble estimate of wetland CH4 emissions driven by 38 general circulation models for the 21st century. We find that climate change-induced increases in boreal wetland extent and temperature-driven increases in tropical CH4 emissions will dominate anthropogenic CH4 emissions by 38 to 56% toward the end of the 21st century under the Representative Concentration Pathway (RCP2.6). Depending on scenarios, wetland CH4 feedbacks translate to an increase in additional global mean radiative forcing of 0.04 W·m−2 to 0.19 W·m−2 by the end of the 21st century. Under the “worst-case” RCP8.5 scenario, with no climate mitigation, boreal CH4 emissions are enhanced by 18.05 Tg to 41.69 Tg, due to thawing of inundated areas during the cold season (December to May) and rising temperature, while tropical CH4 emissions accelerate with a total increment of 48.36 Tg to 87.37 Tg by 2099. Our results suggest that climate mitigation policies must consider mitigation of wetland CH4 feedbacks to maintain average global warming below 2 °C. PMID:28827347

Illuminating Geochemical Controls of Methane Oxidation Along a Gradient of Permafrost Thaw

NASA Astrophysics Data System (ADS)

Perryman, C. R.; Kashi, N.; McCalley, C. K.; Malhotra, A.; Giesler, R.; Varner, R.

2017-12-01

Increases in annual mean temperature in the subarctic have accelerated the thaw of organic-rich permafrost peatlands, exacerbating methane (CH4) production from microbial decomposition of peat deposits and subsequent CH4 emissions. Methanotrophic bacteria may oxidize/consume upwards of 90% of produced CH4 in some settings, pending substrate availability and environmental conditions. Redox chemistry may also control the rate of CH4 oxidation in thawing permafrost areas, particularly redox potential (Eh) and the availability of oxygen (O2) and other terminal electron receptors. We investigated potential CH4 oxidation rates across a permafrost thaw gradient in Stordalen Mire (68°21'N,18°49'E) near Abisko, Sweden. Methane oxidation rates for sites from thawing and collapsed palsa, semi-wet Sphagnum, and open-water sedge sites were determined through laboratory incubations. Peat cores were extracted from two depths at each site and incubated at in situ temperatures and CH4 concentrations. Headspace samples were collected over a 48-hour period and analyzed for CH4 concentration using flame ionization detection gas chromatography (GC-FID). Dissolved O2, Eh, and dissolved CH4 were measured in sites with porewater. Oxidation rates ranged from <0.1 to 19 μg of CH4 per gram of dry biomass per day. Eh remained positive (41.6 to 316.8 mV) with available dissolved O2 (0.3 - 5.2 mg/L) in all measurement locations down to 20cm, indicating in situ aerobic CH4 oxidation is viable across these environments. Potential CH4 oxidation rates increased with increasing dissolved CH4 concentration. Highest potential CH4 oxidation rates were found in open-water sedge sites. Eh and dissolved O2 were lowest at these sites, suggesting that methanotrophs with low-O2 demand may populate sedge areas. Furthermore, potential CH4 oxidation rates were higher at depth than at the surface in thawing palsa, suggesting CH4 oxidation may mitigate CH4 production triggered by warming in these actively thawing environments. Forthcoming elemental analyses of peat and pore water will further elucidate trends and geochemical controls of CH4 oxidation rates in thawing permafrost areas.

The origin of transverse anisotropy in axially symmetric single molecule magnets.

PubMed

Barra, Anne-Laure; Caneschi, Andrea; Cornia, Andrea; Gatteschi, Dante; Gorini, Lapo; Heiniger, Leo-Philipp; Sessoli, Roberta; Sorace, Lorenzo

2007-09-05

Single-crystal high-frequency electron paramagnetic resonance spectroscopy has been employed on a truly axial single molecule magnet of formula [Mn(12)O(12)(tBu-CH(2)CO(2))16(CH(3)OH)4].CH(3)OH to investigate the origin of the transverse magnetic anisotropy, a crucial parameter that rules the quantum tunneling of the magnetization. The crystal structure, including the absolute structure of the crystal used for EPR experiments, has been fully determined and found to belong to I4 tetragonal space group. The angular dependence of the resonance fields in the crystallographic ab plane shows the presence of high-order tetragonal anisotropy and strong dependence on the MS sublevels with the second-highest-field transition being angular independent. This was rationalized including competing fourth- and sixth-order transverse parameters in a giant spin Hamiltonian which describes the magnetic anisotropy in the ground S = 10 spin state of the cluster. To establish the origin of these anisotropy terms, the experimental results have been further analyzed using a simplified multispin Hamiltonian which takes into account the exchange interactions and the single ion magnetic anisotropy of the Mn(III) centers. It has been possible to establish magnetostructural correlations with spin Hamiltonian parameters up to the sixth order. Transverse anisotropy in axial single molecule magnets was found to originate from the multispin nature of the system and from the breakdown of the strong exchange approximation. The tilting of the single-ion easy axes of magnetization with respect to the 4-fold molecular axis of the cluster plays the major role in determining the transverse anisotropy. Counterintuitively, the projections of the single ion easy axes on the ab plane correspond to hard axes of magnetization.

Emission of greenhouse gases from controlled incineration of cattle manure.

PubMed

Oshita, Kazuyuki; Sun, Xiucui; Taniguchi, Miki; Takaoka, Masaki; Matsukawa, Kazutsugu; Fujiwara, Taku

2012-01-01

Greenhouse gas emission is a potential limiting factor in livestock farming development. While incineration is one approach to minimize livestock manure, there are concerns about significant levels of nitrogen and organic compounds in manure as potential sources of greenhouse gas emissions (N2O and CH4). In this study, the effects of various incineration conditions, such as the furnace temperature and air ratio on N2O and CH4 formation behaviour, of cattle manure (as a representative livestock manure) were investigated in a pilot rotary kiln furnace. The results revealed that N2O emissions decreased with increasing temperature and decreasing air ratio. In addition, CH4 emissions tended to be high above 800 degrees C at a low air ratio. The emission factors for N2O and CH4 under the general conditions (combustion temperature of 800-850 degrees C and air ratio of 1.4) were determined to be 1.9-6.0% g-N2O-N/g-N and 0.0046-0.26% g-CH4/g-burning object, respectively. The emission factor for CH4 differed slightly from the published values between 0.16 and 0.38% g-CH4/g-burning object. However, the emission factor for N2O was much higher than the currently accepted value of 0.7% g-N2O-N/g-N and, therefore, it is necessary to revise the N2O emission factor for the incineration of livestock manure.

Effect of Different CH3NH3PbI3 Morphologies on Photovoltaic Properties of Perovskite Solar Cells

NASA Astrophysics Data System (ADS)

Chen, Lung-Chien; Lee, Kuan-Lin; Wu, Wen-Ti; Hsu, Chien-Feng; Tseng, Zong-Liang; Sun, Xiao Hong; Kao, Yu-Ting

2018-05-01

In this study, the perovskite layers were prepared by two-step wet process with different CH3NH3I (MAI) concentrations. The cell structure was glass/FTO/TiO2-mesoporous/CH3NH3PbI3 (MAPbI3)/spiro-OMeTAD/Ag. The MAPbI3 perovskite films were prepared using high and low MAI concentrations in a two-step process. The perovskite films were optimized at different spin coating speed and different annealing temperatures to enhance the power conversion efficiency (PCE) of perovskite solar cells. The PCE of the resulting device based on the different perovskite morphologies was discussed. The PCE of the best cell was up to 17.42%, open circuit voltage of 0.97 V, short current density of 24.06 mA/cm2, and fill factor of 0.747.

Effect of Different CH3NH3PbI3 Morphologies on Photovoltaic Properties of Perovskite Solar Cells.

PubMed

Chen, Lung-Chien; Lee, Kuan-Lin; Wu, Wen-Ti; Hsu, Chien-Feng; Tseng, Zong-Liang; Sun, Xiao Hong; Kao, Yu-Ting

2018-05-08

In this study, the perovskite layers were prepared by two-step wet process with different CH 3 NH 3 I (MAI) concentrations. The cell structure was glass/FTO/TiO 2 -mesoporous/CH 3 NH 3 PbI 3 (MAPbI 3 )/spiro-OMeTAD/Ag. The MAPbI 3 perovskite films were prepared using high and low MAI concentrations in a two-step process. The perovskite films were optimized at different spin coating speed and different annealing temperatures to enhance the power conversion efficiency (PCE) of perovskite solar cells. The PCE of the resulting device based on the different perovskite morphologies was discussed. The PCE of the best cell was up to 17.42%, open circuit voltage of 0.97 V, short current density of 24.06 mA/cm 2 , and fill factor of 0.747.

Optimization of a horizontal-flow biofilm reactor for the removal of methane at low temperatures.

PubMed

Clifford, E; Kennelly, C; Walsh, R; Gerrity, S; Reilly, E O; Collins, G

2012-10-01

Three pilot-scale, horizontal-flow biofilm reactors (HFBRs 1-3) were used to treat methane (CH4)-contaminated air to assess the potential of this technology to manage emissions from agricultural activities, waste and wastewater treatment facilities, and landfills. The study was conducted over two phases (Phase 1, lasting 90 days and Phase 2, lasting 45 days). The reactors were operated at 10 degrees C (typical of ambient air and wastewater temperatures in northern Europe), and were simultaneously dosed with CH4-contaminated air and a synthetic wastewater (SWW). The influent loading rates to the reactors were 8.6 g CH4/m3/hr (4.3 g CH4/m2 TPSA/hr; where TPSA is top plan surface area). Despite the low operating temperatures, an overall average removal of 4.63 g CH4/m3/day was observed during Phase 2. The maximum removal efficiency (RE) for the trial was 88%. Potential (maximum) rates of methane oxidation were measured and indicated that biofilm samples taken from various regions in the HFBRs had mostly equal CH4 removal potential. In situ activity rates were dependent on which part of the reactor samples were obtained. The results indicate the potential of the HFBR, a simple and robust technology, to biologically treat CH4 emissions. The results of this study indicate that the HFBR technology could be effectively applied to the reduction of greenhouse gas emissions from wastewater treatment plants and agricultural facilities at lower temperatures common to northern Europe. This could reduce the carbon footprint of waste treatment and agricultural livestock facilities. Activity tests indicate that methanotrophic communities can be supported at these temperatures. Furthermore, these data can lead to improved reactor design and optimization by allowing conditions to be engineered to allow for improved removal rates, particularly at lower temperatures. The technology is simple to construct and operate, and with some optimization of the liquid phase to improve mass transfer, the HFBR represents a viable, cost-effective solution for these emissions.

Methanol Formation via Oxygen Insertion Chemistry in Ices

NASA Astrophysics Data System (ADS)

Bergner, Jennifer B.; Öberg, Karin I.; Rajappan, Mahesh

2017-08-01

We present experimental constraints on the insertion of oxygen atoms into methane to form methanol in astrophysical ice analogs. In gas-phase and theoretical studies this process has previously been demonstrated to have a very low or nonexistent energy barrier, but the energetics and mechanisms have not yet been characterized in the solid state. We use a deuterium UV lamp filtered by a sapphire window to selectively dissociate O2 within a mixture of O2:CH4 and observe efficient production of CH3OH via O(1D) insertion. CH3OH growth curves are fit with a kinetic model, and we observe no temperature dependence of the reaction rate constant at temperatures below the oxygen desorption temperature of 25 K. Through an analysis of side products we determine the branching ratio of ice-phase oxygen insertion into CH4: ˜65% of insertions lead to CH3OH, with the remainder leading instead to H2CO formation. There is no evidence for CH3 or OH radical formation, indicating that the fragmentation is not an important channel and that insertions typically lead to increased chemical complexity. CH3OH formation from O2 and CH4 diluted in a CO-dominated ice similarly shows no temperature dependence, consistent with expectations that insertion proceeds with a small or nonexistent barrier. Oxygen insertion chemistry in ices should therefore be efficient under low-temperature ISM-like conditions and could provide an important channel to complex organic molecule formation on grain surfaces in cold interstellar regions such as cloud cores and protoplanetary disk midplanes.

Monometallic Ni(0) and Heterobimetallic Ni(0) /Au(I) Complexes of Tripodal Phosphine Ligands: Characterization in Solution and in the Solid State and Catalysis.

PubMed

Cluff, Kyle J; Bhuvanesh, Nattamai; Blümel, Janet

2015-07-06

The tridentate chelate nickel complexes [(CO)Ni{(PPh2 CH2 )3 CMe}] (2), [(CO)Ni{(PPh2 CH2 CH2 )3 SiMe}] (6), and [Ph3 PNi{(PPh2 CH2 CH2 )3 SiMe}] (7), as well as the bidentate complex [(CO)2 Ni{(PPh2 CH2 )2 CMeCH2 PPh2 }] (3) and the heterobimetallic complex [(CO)2 Ni{(PPh2 CH2 )2 CMeCH2 Ph2 PAuCl}] (4), have been synthesized and fully characterized in solution. All (1) H and (13) C NMR signal assignments are based on 2D-NMR methods. Single crystal X-ray structures have been obtained for all complexes. Their (31) P CP/MAS (cross polarization with magic angle spinning) NMR spectra have been recorded and the isotropic lines identified. The signals were assigned with the help of their chemical shift anisotropy (CSA) data. All complexes have been tested regarding their catalytic activity for the cyclotrimerization of phenylacetylene. Whereas complexes 2-4 display low catalytic activity, complex 7 leads to quantitative conversion of the substrate within four hours and is highly selective throughout the catalytic reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Decadal changes in CH4 and CO2 emissions on the Alaskan North Slope

NASA Astrophysics Data System (ADS)

Sweeney, C.; Commane, R.; Wofsy, S.; Dlugokencky, E. J.; Karion, A.; Stone, R. S.; Chang, R.; Tans, P. P.; Wolter, S.

2016-12-01

Large changes in surface air temperature, sea ice cover and permafrost in the Arctic Boreal Ecosystems (ABE) are significantly impacting the critical ecosystem services and human societies that are dependent on the ABE. In order to predict the outcome of continued change in the climate system of the ABE, it is necessary to look at how past changes in climate have affected the ABE. We look at 30 years of CH4 and 42 years of CO2 observations from the NOAA Global Greenhouse Gas Reference Network site in Barrow, Alaska. By eliminating background trends and only looking at data collected when winds are blowing off the North Slope we find very little change in CH4 enhancements, but significant changes in the CO2 enhancements coming off the tundra. The bulk of both CO2 and CH4 emissions appear to be emitted well after the first snow fall on the North Slope. CO2 emissions are a strongly correlation with summer surface temperatures, while CH4 emissions appear insensitive to the large temperature changes that occurred over the measurement period. These results suggest that CO2, and not CH4 emissions, are a likely pathway for the degradation of permafrost carbon.

Theory of long-lived nuclear spin states in methyl groups and quantum-rotor induced polarisation.

PubMed

Dumez, Jean-Nicolas; Håkansson, Pär; Mamone, Salvatore; Meier, Benno; Stevanato, Gabriele; Hill-Cousins, Joseph T; Roy, Soumya Singha; Brown, Richard C D; Pileio, Giuseppe; Levitt, Malcolm H

2015-01-28

Long-lived nuclear spin states have a relaxation time much longer than the longitudinal relaxation time T1. Long-lived states extend significantly the time scales that may be probed with magnetic resonance, with possible applications to transport and binding studies, and to hyperpolarised imaging. Rapidly rotating methyl groups in solution may support a long-lived state, consisting of a population imbalance between states of different spin exchange symmetries. Here, we expand the formalism for describing the behaviour of long-lived nuclear spin states in methyl groups, with special attention to the hyperpolarisation effects observed in (13)CH3 groups upon rapidly converting a material with low-barrier methyl rotation from the cryogenic solid state to a room-temperature solution [M. Icker and S. Berger, J. Magn. Reson. 219, 1 (2012)]. We analyse the relaxation properties of methyl long-lived states using semi-classical relaxation theory. Numerical simulations are supplemented with a spherical-tensor analysis, which captures the essential properties of methyl long-lived states.

Hydrogen and Methane Generation in Serpentinizing Systems: An Experimental Perspective

NASA Astrophysics Data System (ADS)

McCollom, T. M.; Klein, F.

2018-05-01

Experimental studies indicate rates of serpentinization as well as H2 and CH4 production are very sluggish at low temperatures. Temperatures >200–300 C or prolonged reaction times may be required to produce significant H2 and CH4 within icy worlds.

Controllable Growth of Perovskite Films by Room-Temperature Air Exposure for Efficient Planar Heterojunction Photovoltaic Cells

DOE PAGES

Yang, Bin; Dyck, Ondrej; Poplawsky, Jonathan; ...

2015-12-01

A two-step-solution-processing approach has been established to grow void-free perovskite films for low-cost and high-performance planar heterojunction photovoltaic devices. We generally applied a high-temperature thermal annealing treatment in order to drive the diffusion of CH 3NH 3I precursor molecules into the compact PbI 2 layer to form perovskite films. But, thermal annealing for extended periods would lead to degraded device performance due to the defects generated by decomposition of perovskite into PbI 2. In this work, we explored a controllable layer-by-layer spin-coating method to grow bilayer CH 3NH 3I/PbI 2 films, and then drive the interdiffusion between PbI 2 andmore » CH 3NH 3I layers by a simple room-temperature-air-exposure for making well-oriented, highly-crystalline perovskite films without thermal annealing. This high degree of crystallinity resulted in a carrier diffusion length of ~ 800 nm and high device efficiency of 15.6%, which is comparable to the reported values from thermally-annealed perovskite films based counterparts. Finally, the simplicity and high device performance of this processing approach is highly promising for direct integration into industrial-scale device manufacture.« less

Temperature dependence of greenhouse gas emissions from three hydromorphic soils at different groundwater levels.

PubMed

Vicca, S; Janssens, I A; Flessa, H; Fiedler, S; Jungkunst, H F

2009-09-01

Wetlands contribute considerably to the global greenhouse gas (GHG) balance. In these ecosystems, groundwater level (GWL) and temperature, two factors likely to be altered by climate change, exert important control over CO(2), CH(4) and N(2)O fluxes. However, little is known about the temperature sensitivity (Q(10)) of the combined GHG emissions from hydromorphic soils and how this Q(10) varies with GWL. We performed a greenhouse experiment in which three different (plant-free) hydromorphic soils from a temperate spruce forest were exposed to two GWLs (an intermediate GWL of -20 cm and a high GWL of -5 cm). Net CO(2), CH(4) and N(2)O fluxes were measured continuously. Here, we discuss how these fluxes responded to synoptic temperature fluctuations. Across all soils and GWLs, CO(2) emissions responded similarly to temperature and Q(10) was close to 2. The Q(10) of the CH(4) and N(2)O fluxes also was similar across soil types. GWL, on the other hand, significantly affected the Q(10) of both CH(4) and N(2)O emissions. The Q(10) of the net CH(4) fluxes increased from about 1 at GWL = -20 cm to 3 at GWL = -5 cm. For the N(2)O emissions, Q(10) varied around 2 for GWL = -20 cm and around 4 for GWL = -5 cm. This substantial GWL-effect on the Q(10) of CH(4) and N(2)O emissions was, however, hardly reflected in the Q(10) of the total GHG emissions (which varied around 2), because the contribution of these gases was relatively small compared to that of CO(2).

Low Temperature Studies of the Removal Reactions of 1CH2 with Relevance to the Atmosphere of Titan

NASA Astrophysics Data System (ADS)

Douglas, Kevin; Slater, Eloise; Feng, Wuhu; Blitz, Mark; Plane, John; Heard, Dwayne; Seakins, Paul

2017-04-01

The photolysis of methane by UV photons is the primary source of hydrocarbon radicals in the atmosphere of Titan and the giant planets. Although there is still significant uncertainty in the branching ratios of products, the production of the first singlet excited state of methylene, 1CH2, is thought to be a significant channel. Reactions of 1CH2 with methane (R1a) and hydrogen (R2a) are a significant source of methyl radicals, the recombination of which is the primary route to ethane on Titan (R3). The reaction of 1CH2 with acetylene is also a source of propargyl, C3H3, the recombination of which is the primary route to benzene on Titan. However, in addition to these reactions of 1CH2 leading to chemical products, there is also competition between inelastic electronic relaxation to form ground triplet state methylene, 3CH2 (R1b and R2b). Triplet methylene is much less reactive, and cannot undergo the complex insertion elimination reactions of singlet methylene. The main reaction of 3CH2 occurs with other radical species such as H (R4). 1CH2 + CH4 → CH3 + H2 (R1a) 1CH2 + CH4 → 3CH2 + CH4 (R1b) 1CH2 + H2 → CH3 + H (R2a) 1CH2 + H2 → 3CH2 + H2 (R2a) CH3 + CH3 (+M) → C2H6 (R3) 3CH2 + H → CH + H2 (R4) Using pulsed laser photolysis laser-induced fluorescence, we have studied the reaction kinetics for the removal of 1CH2 with N2, H2, CH4, C2H6, C2H4, C2H6, and O2 as a function of temperature. Low temperatures between 43 and 135 K were obtained using a pulsed Laval nozzle apparatus, while data at 160 K was obtained using a low flow reaction cell with cryogenic cooling. In addition to measuring total removal rates, the fraction of 1CH2 removed via electronic relaxation versus chemical reaction to products has also been investigated for H2 and CH4 at 160 and 73 K. Results show that that removal of 1CH2 by electronic relaxation increases with decreasing temperature. These experimental results indicate that the majority of 1CH2 formed in Titan's atmosphere will be rapidly relaxed to its ground state via collisions with both reactive and non-reactive species, and thus is likely to play a less significant role in the formation of larger hydrocarbons than previously thought. However, for a full understanding of the implications of these results, the new measurements have been included in a 1D model of Titan's atmosphere. The model results show a significant reduction in ethane concentrations (10 - 50 %), due to reduction in CH3 production via reactions R1a and R1b. In addition we also observe an increase in ethylene concentrations, the result of increased amounts of 3CH2 reacting with H radicals to form CH (R4), which primarily react with methane to form ethylene. Additional work is also underway to determine branching ratios between reaction and relaxation of 1CH2 with ethane, ethylene, and acetylene. Model results have shown that if a similar trend to reactions with H2 and CH4 is observed, there would be significant reductions in benzene production on Titan.

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

Measurements of argon-, helium-, hydrogen-, and nitrogen-broadened widths of methane lines near 9000 per cm

NASA Technical Reports Server (NTRS)

Fox, Kenneth; Jennings, Donald E.; Stern, Elizabeth A.; Hubbard, Rob

1988-01-01

Pressure-broadened widths of rotational-vibrational lines in CH4 have been measured at very high spectral resolution in the R-branch of the 3nu3 overtone. The broadening gases were Ar, He, H2, and N2. Results are presented as averages for J-multiplets at ambient temperature. The overall values (per cm per atm) for these R-branch lines are 0.0651 (CH4-Ar), 0.0508 (CH4-He), 0.0728 (CH4-H2), and 0.0715 (CH4-N2).

Intramolecular electron-transfer rates in mixed-valence triarylamines: measurement by variable-temperature ESR spectroscopy and comparison with optical data.

PubMed

Lancaster, Kelly; Odom, Susan A; Jones, Simon C; Thayumanavan, S; Marder, Seth R; Brédas, Jean-Luc; Coropceanu, Veaceslav; Barlow, Stephen

2009-02-11

The electron spin resonance spectra of the radical cations of 4,4'-bis[di(4-methoxyphenyl)amino]tolane, E-4,4'-bis[di(4-methoxyphenyl)amino]stilbene, and E,E-1,4-bis{4-[di(4-methoxyphenyl)amino]styryl}benzene in dichloromethane exhibit five lines over a wide temperature range due to equivalent coupling to two 14N nuclei, indicating either delocalization between both nitrogen atoms or rapid intramolecular electron transfer on the electron spin resonance time scale. In contrast, those of the radical cations of 1,4-bis{4-[di(4-methoxyphenyl)amino]phenylethynyl}benzene and E,E-1,4-bis{4-[di(4-n-butoxyphenyl)amino]styryl}-2,5-dicyanobenzene exhibit line shapes that vary strongly with temperature, displaying five lines at room temperature and only three lines at ca. 190 K, indicative of slow electron transfer on the electron spin resonance time scale at low temperatures. The rates of intramolecular electron transfer in the latter compounds were obtained by simulation of the electron spin resonance spectra and display an Arrhenius temperature dependence. The activation barriers obtained from Arrhenius plots are significantly less than anticipated from Hush analyses of the intervalence bands when the diabatic electron-transfer distance, R, is equated to the N[symbol: see text]N distance. Comparison of optical and electron spin resonance data suggests that R is in fact only ca. 40% of the N[symbol: see text]N distance, while the Arrhenius prefactor indicates that the electron transfer falls in the adiabatic regime.

Gyroscope-Like Complexes Based on Dibridgehead Diphosphine Cages That Are Accessed by Three-Fold Intramolecular Ring Closing Metatheses and Encase Fe(CO)3, Fe(CO)2(NO)(+), and Fe(CO)3(H)(+) Rotators.

PubMed

Lang, Georgette M; Shima, Takanori; Wang, Leyong; Cluff, Kyle J; Skopek, Katrin; Hampel, Frank; Blümel, Janet; Gladysz, John A

2016-06-22

Reactions of trans-Fe(CO)3(P((CH2)mCH═CH2)3)2 (m = a/4; b/5, c/6, e/8) and Grubbs' catalyst (12-24 mol %, CH2Cl2, reflux) give the cage-like trienes trans- Fe(CO)3(P((CH2)mCH═CH(CH2)m)3 P) (3a-c,e, 60-81%). Hydrogenations (ClRh(PPh3)3, 60-80 °C) yield the title compounds trans- Fe(CO)3(P((CH2)n)3 P) (4a-c,e, 74-86%; n = 2m + 2), which have idealized D3h symmetry. A crystal structure of 4c suggests enough van der Waals clearance for the Fe(CO)3 moiety to rotate within the three P(CH2)14P linkages; structures of E,E,E-3a show rotation to be blocked by the shorter P(CH2)4CH═CH(CH2)4P linkages. Additions of NO(+)BF4(-) give the isoelectronic and isosteric cations [ Fe(CO)2(NO)(P((CH2)n)3 P)](+)BF4(-) (5a-c(+)BF4(-); 81-98%). Additions of [H(OEt2)2](+)BArf(-) (BArf = B(3,5-C6H3(CF3)2)4) afford the metal hydride complexes mer,trans-[ Fe(CO)3(H)(P((CH2)n)3 P)](+)BArf(-) (6a-c,e(+)BArf(-); 98-99%). The behavior of the rotators in the preceding complexes is probed by VT NMR. At ambient temperature in solution, 5a,b(+)BF4(-) and 6a(+)BArf(-) show two sets of P(CH2)n/2 (13)C NMR signals (2:1), whereas 5c(+)BF4(-) and 6b,c(+)BArf(-) show only one. At higher temperatures, the signals of 5b(+)BF4(-) coalesce; at lower temperatures, those of 5c(+)BF4(-) and 6b(+)BArf(-) decoalesce. These data give ΔH(⧧)/ΔS(⧧) values (kcal/mol and eu) of 8.3/-28.4 and 9.5/-6.5 for Fe(CO)2(NO)(+) rotation (5b,c(+)) and 6.1/-23.5 for Fe(CO)3(H)(+) rotation (6b(+)). (13)C CP/MAS NMR spectra show that the Fe(CO)3 moiety in polycrystalline 4c (but not 4a) undergoes rapid rotation between -60 and 95 °C. Approaches to minimizing these barriers and developing molecular gyroscopes are discussed.

A multi-year estimate of methane fluxes in Alaska from CARVE atmospheric observations

PubMed Central

Miller, Scot M.; Miller, Charles E.; Commane, Roisin; Chang, Rachel Y.-W.; Dinardo, Steven J.; Henderson, John M.; Karion, Anna; Lindaas, Jakob; Melton, Joe R.; Miller, John B.; Sweeney, Colm; Wofsy, Steven C.; Michalak, Anna M.

2016-01-01

Methane (CH4) fluxes from Alaska and other arctic regions may be sensitive to thawing permafrost and future climate change, but estimates of both current and future fluxes from the region are uncertain. This study estimates CH4 fluxes across Alaska for 2012–2014 using aircraft observations from the Carbon in Arctic Reservoirs Vulnerability Experiment (CARVE) and a geostatistical inverse model (GIM). We find that a simple flux model based on a daily soil temperature map and a static map of wetland extent reproduces the atmospheric CH4 observations at the state-wide, multi-year scale more effectively than global-scale, state-of-the-art process-based models. This result points to a simple and effective way of representing CH4 flux patterns across Alaska. It further suggests that contemporary process-based models can improve their representation of key processes that control fluxes at regional scales, and that more complex processes included in these models cannot be evaluated given the information content of available atmospheric CH4 observations. In addition, we find that CH4 emissions from the North Slope of Alaska account for 24% of the total statewide flux of 1.74 ± 0.44 Tg CH4 (for May–Oct.). Contemporary global-scale process models only attribute an average of 3% of the total flux to this region. This mismatch occurs for two reasons: process models likely underestimate wetland area in regions without visible surface water, and these models prematurely shut down CH4 fluxes at soil temperatures near 0°C. As a consequence, wetlands covered by vegetation and wetlands with persistently cold soils could be larger contributors to natural CH4 fluxes than in process estimates. Lastly, we find that the seasonality of CH4 fluxes varied during 2012–2014, but that total emissions did not differ significantly among years, despite substantial differences in soil temperature and precipitation; year-to-year variability in these environmental conditions did not affect obvious changes in total CH4 fluxes from the state. PMID:28066129

A multi-year estimate of methane fluxes in Alaska from CARVE atmospheric observations.

PubMed

Miller, Scot M; Miller, Charles E; Commane, Roisin; Chang, Rachel Y-W; Dinardo, Steven J; Henderson, John M; Karion, Anna; Lindaas, Jakob; Melton, Joe R; Miller, John B; Sweeney, Colm; Wofsy, Steven C; Michalak, Anna M

2016-10-01

Methane (CH 4 ) fluxes from Alaska and other arctic regions may be sensitive to thawing permafrost and future climate change, but estimates of both current and future fluxes from the region are uncertain. This study estimates CH 4 fluxes across Alaska for 2012-2014 using aircraft observations from the Carbon in Arctic Reservoirs Vulnerability Experiment (CARVE) and a geostatistical inverse model (GIM). We find that a simple flux model based on a daily soil temperature map and a static map of wetland extent reproduces the atmospheric CH 4 observations at the state-wide, multi-year scale more effectively than global-scale, state-of-the-art process-based models. This result points to a simple and effective way of representing CH 4 flux patterns across Alaska. It further suggests that contemporary process-based models can improve their representation of key processes that control fluxes at regional scales, and that more complex processes included in these models cannot be evaluated given the information content of available atmospheric CH 4 observations. In addition, we find that CH 4 emissions from the North Slope of Alaska account for 24% of the total statewide flux of 1.74 ± 0.44 Tg CH 4 ( for May-Oct.). Contemporary global-scale process models only attribute an average of 3% of the total flux to this region. This mismatch occurs for two reasons: process models likely underestimate wetland area in regions without visible surface water, and these models prematurely shut down CH 4 fluxes at soil temperatures near 0°C. As a consequence, wetlands covered by vegetation and wetlands with persistently cold soils could be larger contributors to natural CH 4 fluxes than in process estimates. Lastly, we find that the seasonality of CH 4 fluxes varied during 2012-2014, but that total emissions did not differ significantly among years, despite substantial differences in soil temperature and precipitation; year-to-year variability in these environmental conditions did not affect obvious changes in total CH 4 fluxes from the state.

Thermal generation of spin current in epitaxial CoFe{sub 2}O{sub 4} thin films

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

Guo, Er-Jia, E-mail: ejguophysics@gmail.com, E-mail: klaeui@uni-mainz.de; Quantum Condensed Matter Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830; Herklotz, Andreas

2016-01-11

The longitudinal spin Seebeck effect (LSSE) has been investigated in high-quality epitaxial CoFe{sub 2}O{sub 4} (CFO) thin films. The thermally excited spin currents in the CFO films are electrically detected in adjacent Pt layers due to the inverse spin Hall effect. The LSSE signal exhibits a linear increase with increasing temperature gradient, yielding a LSSE coefficient of ∼100 nV/K at room temperature. The temperature dependence of the LSSE is investigated from room temperature down to 30 K, showing a significant reduction at low temperatures, revealing that the total amount of thermally generated magnons decreases. Furthermore, we demonstrate that the spin Seebeck effectmore » is an effective tool to study the magnetic anisotropy induced by epitaxial strain, especially in ultrathin films with low magnetic moments.« less

Temperature dependence of current polarization in Ni80Fe20 by spin wave Doppler measurements

NASA Astrophysics Data System (ADS)

Zhu, Meng; Dennis, Cindi; McMichael, Robert

2010-03-01

The temperature dependence of current polarization in ferromagnetic metals will be important for operation of spin-torque switched memories and domain wall devices in a wide temperature range. Here, we use the spin wave Doppler technique[1] to measure the temperature dependence of both the magnetization drift velocity v(T) and the current polarization P(T) in Ni80Fe20. We obtain these values from current-dependent shifts of the spin wave transmission resonance frequency for fixed-wavelength spin waves in current-carrying wires. For current densities of 10^11 A/m^2, we obtain v(T) decreasing from 4.8 ±0.3 m/s to 4.1 ±0.1 m/s and P(T) dropping from 0.75±0.05 to 0.58±0.02 over a temperature range from 80 K to 340 K. [1] V. Vlaminck et al. Science 322, 410 (2008);

Methane emissions from an alpine wetland on the Tibetan Plateau: Neglected but vital contribution of the nongrowing season

NASA Astrophysics Data System (ADS)

Song, Weimin; Wang, Hao; Wang, Guangshuai; Chen, Litong; Jin, Zhenong; Zhuang, Qianlai; He, Jin-Sheng

2015-08-01

The vast wetlands on the Tibetan Plateau are expected to be an important natural source of methane (CH4) to the atmosphere. The magnitude, patterns and environmental controls of CH4 emissions on different timescales, especially during the nongrowing season, remain poorly understood, because of technical limitations and the harsh environments. We conducted the first study on year-round CH4 fluxes in an alpine wetland using the newly developed LI-COR LI-7700 open-path gas analyzer. We found that the total annual CH4 emissions were 26.4 and 33.8 g CH4 m-2 in 2012 and 2013, respectively, and the nongrowing season CH4 emissions accounted for 43.2-46.1% of the annual emissions, highlighting an indispensable contribution that was often overlooked by previous studies. A two-peak seasonal variation in CH4 fluxes was observed, with a small peak in the spring thawing period and a large one in the peak growing season. We detected a significant difference in the diurnal variation of CH4 fluxes between the two seasons, with two peaks in the growing season and one peak in the nongrowing season. We found that the CH4 fluxes during the growing season were well correlated with soil temperature, water table depth and gross primary production, whereas the CH4 fluxes during the nongrowing season were highly correlated with soil temperature. Our results suggested that the CH4 emission during the nongrowing season cannot be ignored and the vast wetlands on the Tibetan plateau will have the potential to exert a positive feedback on climate considering the increasing warming, particularly in the nongrowing season in this region.

Long-lived nuclear spin states in rapidly rotating CH2D groups

NASA Astrophysics Data System (ADS)

Elliott, Stuart J.; Brown, Lynda J.; Dumez, Jean-Nicolas; Levitt, Malcolm H.

2016-11-01

Although monodeuterated methyl groups support proton long-lived states, hindering of the methyl rotation limits the singlet relaxation time. We demonstrate an experimental case in which the rapid rotation of the CH2D group extends the singlet lifetime but does not quench the chemical shift difference between the CH2D protons, induced by the chiral environment. Proton singlet order is accessed using Spin-Lock Induced Crossing (SLIC) experiments, showing that the singlet relaxation time TS is over 2 min, exceeding the longitudinal relaxation time T1 by a factor of more than 10. This result shows that proton singlet states may be accessible and long-lived in rapidly rotating CH2D groups.

Thermal decomposition of ethanol. 4. Ab initio chemical kinetics for reactions of H atoms with CH3CH2O and CH3CHOH radicals.

PubMed

Xu, Z F; Xu, Kun; Lin, M C

2011-04-21

The potential energy surfaces of H-atom reactions with CH(3)CH(2)O and CH(3)CHOH, two major radicals in the decomposition and oxidation of ethanol, have been studied at the CCSD(T)/6-311+G(3df,2p) level of theory with geometric optimization carried out at the BH&HLYP/6-311+G(3df,2p) level. The direct hydrogen abstraction channels and the indirect association/decomposition channels from the chemically activated ethanol molecule have been considered for both reactions. The rate constants for both reactions have been calculated at 100-3000 K and 10(-4) Torr to 10(3) atm Ar pressure by microcanonical VTST/RRKM theory with master equation solution for all accessible product channels. The results show that the major product channel of the CH(3)CH(2)O + H reaction is CH(3) + CH(2)OH under atmospheric pressure conditions. Only at high pressure and low temperature, the rate constant for CH(3)CH(2)OH formation by collisonal deactivation becomes dominant. For CH(3)CHOH + H, there are three major product channels; at high temperatures, CH(3)+CH(2)OH production predominates at low pressures (P < 100 Torr), while the formation of CH(3)CH(2)OH by collisional deactivation becomes competitive at high pressures and low temperatures (T < 500 K). At high temperatures, the direct hydrogen abstraction reaction producing CH(2)CHOH + H(2) becomes dominant. Rate constants for all accessible product channels in both systems have been predicted and tabulated for modeling applications. The predicted value for CH(3)CHOH + H at 295 K and 1 Torr pressure agrees closely with available experimental data. For practical modeling applications, the rate constants for the thermal unimolecular decomposition of ethanol giving key accessible products have been predicted; those for the two major product channels taking place by dehydration and C-C breaking agree closely with available literature data.

Methane Cycling in a Warming Wetland

NASA Astrophysics Data System (ADS)

Noyce, G. L.; Megonigal, P.; Rich, R.; Kirwan, M. L.; Herbert, E. R.

2017-12-01

Coastal wetlands are global hotspots of carbon (C) storage, but the future of these systems is uncertain. In June 2016, we initiated an in-situ, active, whole-ecosystem warming experiment in the Smithsonian's Global Change Research Wetland to quantify how warming and elevated CO2 affect the stability of coastal wetland soil C pools and contemporary rates of C sequestration. Transects are located in two plant communities, dominated by C3 sedges or C4 grasses. The experiment has a gradient design with air and soil warming treatments ranging from ambient to +5.1 °C and heated plots consistently maintain their target temperature year-round. In April 2017, an elevated CO2 treatment was crossed with temperature in the C3community. Ongoing measurements include soil elevation, C fluxes, porewater chemistry and redox potential, and above- and below-ground growth and biomass. In both years, warming increased methane (CH4) emissions (measured at 3-4 week intervals) from spring through fall at the C3 site, but had little effect on emissions from the C4 site. Winter (Dec-Mar) emissions showed no treatment effect. Stable isotope analysis of dissolved CH4 and DIC also indicated that warming had differing effects on CH4 pathways in the two vegetation communities. To better understand temperature effects on rates of CH4 production and oxidation, 1 m soil cores were collected from control areas of the marsh in summer 2017 and incubated at temperatures ranging from 4 °C to 35 °C. Warming increased CH4 production and oxidation rates in surface samples and oxidation rates in the rooting zone samples from both sites, but temperature responses in deep (1 m) soil samples were minimal. In the surface and rooting zone samples, production rates were also consistently higher in C3 soils compared to C4 soils, but, contrary to our expectations, the temperature response was stronger in the C4 soils. However, oxidation in C3 rooting zone samples did have a strong temperature response. The ratio of CO2:CH4 decreased with increasing temperature in surface samples from both sites, indicating that anaerobic respiration in surface soil may become increasingly methanogenic with warming. In contrast, the rooting zone and deep soil samples showed the opposite trend, again suggesting that the soil profile will not respond consistently to warming.

Anaerobic co-digestion of sewage sludge and food waste using temperature-phased anaerobic digestion process.

PubMed

Kim, H W; Han, S K; Shin, H S

2004-01-01

This study was performed to overcome the low efficiency of anaerobic digestion of sewage sludge and food waste by combining temperature-phased digestion, sequencing batch operation, and co-digestion technology. It was demonstrated that the temperature-phased anaerobic sequencing batch reactor (TPASBR) system for the co-digestion of sewage sludge and food waste resulted in enhanced volatile solids (VS) reduction and methane production rate. At the organic loading rate (OLR) of 2.7 g VS/l/d, the TPASBR system showed the higher VS reduction (61.3%), CH4 yield (0.28 l/g VS(added)) and CH4 production rate (0.41 l CH4/l/d) than those (0.29 l CH4/l/d) of the mesophilic two-stage ASBR (MTSASBR). In the specific methanogenic activity (SMA) tests on thermophilic biomass of the TPASBR system, the average SMA of acetate (93 ml CH4/gVSS/d) was much higher than those of propionate (46 ml CH4/g VSS/d) and butyrate (76 ml CH4/g VSS/d). Also, higher specific hydrolytic activity (SHA, 217 mg COD/g VSS/d) of the biomass supported fast hydrolysis under thermophilic conditions. The track study revealed that the most active period of the 24 h cycle was between 6 and 12 h. The enhanced performance of the TPASBR system could be attributed to longer solids retention time, fast hydrolysis, higher CH4 conversion rate, and balanced nutrient condition of co-substrate. It was verified that this combination could be a promising and practical alternative for the simultaneous recycling of two types of organic fraction of municipal solid waste (OFMSW) with high stability.

How does whole ecosystem warming of a peatland affect methane production and consumption?

NASA Astrophysics Data System (ADS)

Hopple, A.; Brunik, K.; Keller, J.; Pfeifer-Meister, L.; Woerndle, G.; Zalman, C.; Hanson, P.; Bridgham, S. D.

2017-12-01

Peatlands are among Earth's most important terrestrial ecosystems due to their massive soil carbon (C) stores and significant release of methane (CH4) into the atmosphere. Methane has a sustained-flux global warming potential 45-times greater than carbon dioxide (CO2), and the accuracy of Earth system model projections relies on our mechanistic understanding of peatland CH4 cycling in the context of environmental change. The objective of this study was to determine, under in situ conditions, how heating of the peat profile affects ecosystem-level anaerobic C cycling. We assessed the response of CO2 and CH4 production, as well as the anaerobic oxidation of CH4 (AOM), in a boreal peatland following 13 months of deep peat heating (DPH) and 16 months of subsequent whole-ecosystem warming (surface and deep heating; WEW) as part of the Spruce and Peatland Responses Under Changing Environments (SPRUCE) project in northern Minnesota, USA. The study uses a regression-based experimental design including 5 temperature treatments that warmed the entire 2 m peat profile from 0 to +9 °C above ambient temperature. Soil cores were collected at multiple depths (25-200 cm) from each experimental chamber at the SPRUCE site and anaerobically incubated at in situ temperatures for 1-2 weeks. Methane and CO2 production in surface peat were positively correlated with elevated temperature, but no consistent temperature response was found at depth (75-200 cm) following DPH. However, during WEW, we observed significant increases in both surface and deep peat methanogenesis with increasing temperature. Surface peat had greater CH4 production rates than deeper peat, implying that the increased CH4 emissions observed in the field were largely driven by surface peat warming. The CO2:CH4 ratio was inversely correlated with temperature across all depths following 16 months of WEW, indicating that the entire peat profile is becoming more methanogenic with warming. We also observed AOM throughout the whole peat profile, with the highest rates observed at the surface and initial data suggesting a positive correlation with increasing temperature. While SPRUCE will continue for many years, our initial results suggest that the vast C stores at depth in peatlands are minimally responsive to warming and any response will be driven largely by surface peat.

Influence of processing parameters on the characteristics of surface layers of low temperature plasma nitrocarburized AISI 630 martensitic stainless steel

NASA Astrophysics Data System (ADS)

Lee, Insup

2017-11-01

Plasma nitrocarburizing was performed on solution-treated AISI 630 martensitic precipitation hardening stainless steel samples with a gas mixture of H2, N2, and CH4 with changing temperature, discharge voltage and amount of CH4. When nitrocarburized with increasing temperature from 380 °C to 430 °C at fixed 25% N2 and 6% CH4, the thickness of expanded martensite (α'N) layer and surface hardness increased up to 10 μm and 1323 HV0.05, respectively but the corrosion resistance decreased. Though the increase of discharge voltage from 400 V to 600 V increased α'N layer thickness and surface hardness (up to 13 μm and 1491 HV0.05, respectively), the treated samples still showed very poor corrosion behavior. Thus, to further improve the corrosion resistance, the influence of variation of the amount of CH4 in the nitrocarburizing process was investigated. Increasing the CH4 percentage aided higher corrosion resistance, although it decreased the α'N layer thickness. The most appropriate conditions for moderate α'N layer thickness, high surface hardness and better corrosion resistance than the solution-treated bare sample were established, which is plasma nitrocarburizing at 400 °C with 400 V discharge voltage and containing 25% N2 and 4% CH4.

Deep peat warming increases surface methane and carbon dioxide emissions in a black spruce-dominated ombrotrophic bog.

PubMed

Gill, Allison L; Giasson, Marc-André; Yu, Rieka; Finzi, Adrien C

2017-12-01

Boreal peatlands contain approximately 500 Pg carbon (C) in the soil, emit globally significant quantities of methane (CH 4 ), and are highly sensitive to climate change. Warming associated with global climate change is likely to increase the rate of the temperature-sensitive processes that decompose stored organic carbon and release carbon dioxide (CO 2 ) and CH 4 . Variation in the temperature sensitivity of CO 2 and CH 4 production and increased peat aerobicity due to enhanced growing-season evapotranspiration may alter the nature of peatland trace gas emission. As CH 4 is a powerful greenhouse gas with 34 times the warming potential of CO 2 , it is critical to understand how factors associated with global change will influence surface CO 2 and CH 4 fluxes. Here, we leverage the Spruce and Peatland Responses Under Changing Environments (SPRUCE) climate change manipulation experiment to understand the impact of a 0-9°C gradient in deep belowground warming ("Deep Peat Heat", DPH) on peat surface CO 2 and CH 4 fluxes. We find that DPH treatments increased both CO 2 and CH 4 emission. Methane production was more sensitive to warming than CO 2 production, decreasing the C-CO 2 :C-CH 4 of the respired carbon. Methane production is dominated by hydrogenotrophic methanogenesis but deep peat warming increased the δ 13 C of CH 4 suggesting an increasing contribution of acetoclastic methanogenesis to total CH 4 production with warming. Although the total quantity of C emitted from the SPRUCE Bog as CH 4 is <2%, CH 4 represents >50% of seasonal C emissions in the highest-warming treatments when adjusted for CO 2 equivalents on a 100-year timescale. These results suggest that warming in boreal regions may increase CH 4 emissions from peatlands and result in a positive feedback to ongoing warming. © 2017 John Wiley & Sons Ltd.

The Application Of Biofilter System For Reduction Of Methane Emissions From Modern Sanitary Landfills

NASA Astrophysics Data System (ADS)

Sung, K.; Park, S.

2007-12-01

Increased atmospheric concentrations of greenhouse gases (GHG) caused by anthropogenic activities has been related to global climate change. Methane, the second most important GHG after CO2, is 21 times more effective at trapping heat than CO2. Therefore, methane emission control is of utmost importance for global warming reduction. To minimize leachate production and protect groundwater resources, modern sanitary landfills are equipped with composite covers and gas collection systems. Methane from modern sanitary landfills is vented directly to the atmosphere, except for some of the largest landfills where it is recovered as energy and burned at the site. However, the efficiency of energy recovery systems in larger landfills is reduced as the amount of CH4 generated from landfill begins to decrease. In this study, the performance of a lab-scale model biofilter system was investigated to treat CH4 gas emitted from modern sanitary landfills by conducting batch and column experiments using landfill cover soil amended with earthworm cast as the filter bed medium. From the batch experiments to measure the influence of moisture content and temperature of the filter medium on CH4 removal capacity of a biofilter system, the optimum moisture content and temperature were found to be 10-15% by weight and 25-35°C, respectively. The column experiment was conducted to measure the influence of inlet CH4 concentration and CH4 loading rate on CH4 removal capacity of a biofilter system. As the inlet CH4 concentration decreased, the percentage of CH4 oxidized increased. Up to a CH4 loading rate of 2785 g CH4 m3 h- 1 (EBRT = 7.7 min), the CH4 removal efficiency of the biofilter was able to reach 100%. Based on the results of the study, the installation of a properly managed biofilter system should be capable of achieving a reduction in atmospheric CH4 emissions from modern sanitary landfills at low CH4 generation stage.

Spin-crossover in [Fe(3-bpp)2][BF4]2 in different solvents--a dramatic stabilisation of the low-spin state in water.

PubMed

Barrett, Simon A; Kilner, Colin A; Halcrow, Malcolm A

2011-12-07

The temperature of spin-crossover in [Fe(3-bpp)(2)][BF(4)](2) (3-bpp = 2,6-di{pyrazol-3-yl}pyridine) tends to increase in associating solvents. In particular, T(½) shifts to 60-70 K higher temperature in water compared to organic solvents.

Diffusion and reactivity of ground-state nitrogen atoms N(4S) between 3 and 15 K: application to the hydrogen abstraction reaction from methane under non-energetic conditions

NASA Astrophysics Data System (ADS)

Nourry, Sendres; Krim, Lahouari

2015-07-01

We have characterized the CH4 + N(4S) reaction in solid phase, at very low temperature, under non-energetic conditions and where the CH4 and N reactants are in their ground states. A microwave-driven atomic source has been used to generate ground-state nitrogen atoms N(4S), and experiments have been carried out at temperatures as low as 3 K to reduce the mobility of the trapped species in solid phase and hence to freeze the first step of the CH4 + N reaction pathway. Leaving the formed solid sample in the dark for a while allows all trapped reactants to relax to the ground state, specifically radicals and excited species streaming from the plasma discharge. Such a method could be the only possibility of proving that the CH4 + N reaction occurs between CH4 and N reactants in their ground states without any additional energy to initiate the chemical process. The appearance of the CH3 reaction product, just by inducing the mobility of N atoms between 3 and 11 K, translates that a hydrogen abstraction reaction from methane, under non-energetic conditions, will start occurring at very low temperature. The formation of methyl radical, under these experimental conditions, is due to recombination processes N(4S)-N(4S) of ground-state nitrogen atoms without any contribution of cosmic ray particles or high-energy photons.

Synergy between nutrients and warming enhances methane ebullition from experimental lakes

NASA Astrophysics Data System (ADS)

Davidson, Thomas A.; Audet, Joachim; Jeppesen, Erik; Landkildehus, Frank; Lauridsen, Torben L.; Søndergaard, Martin; Syväranta, Jari

2018-01-01

Lakes and ponds are important natural sources of the potent greenhouse gas methane (CH4), with small shallow waters identified as particular hotspots1,2. Ebullition (bubbles) of CH4 makes up a large proportion of total CH4 flux3,4. However, difficulty measuring such episodic events5 makes prediction of how ebullition responds to nutrient enrichment and rising temperatures challenging. Here, the world's longest running, mesocosm-based, shallow lake climate change experiment was used to investigate how the combination of warming and eutrophication (that is, nutrient enrichment) affects CH4 ebullition. Eutrophication without heating increased the relative contribution of ebullition from 51% to 75%. More strikingly the combination of nutrient enrichment and experimental warming treatments of +2-3 °C and +4-5 °C had a synergistic effect, increasing mean annual ebullition by at least 1900 mg CH4-C m-2 yr-1. In contrast, diffusive flux showed no response to eutrophication and only a small increase at higher temperatures (average 63 mg CH4-C m-2 yr-1). As shallow lakes are the most common lake type globally, abundant in highly climate sensitive regions6 and most vulnerable to eutrophication, these results suggest their current and future contributions to atmospheric CH4 concentrations may be significantly underestimated.

[Impacts of meteorological factors on atmospheric methane mole fractions in the background area of Yangtze River delta].

PubMed

Pu, Jing-Jiao; Xu, Hong-Hui; Gu, Jun-Qiang; Ma, Qian-Li; Fang, Shuang-Xi; Zhou, Ling-Xi

2013-03-01

Impacts of surface wind direction, surface wind speed, surface air temperature and sunshine hours on the CH4 concentration at Lin'an regional atmospheric background station were studied based on the results from Jan. 2009 to Dec. 2011. The results revealed that the diurnal variation of atmospheric CH4 concentration presented a single-peak curve at Lin'an regional background station. The diurnal amplitude varied from 19.0 x 10(-9) to 74.7 x 10(-9), with the lowest value observed in the afternoon and the highest at dawn. The monthly mean CH4 concentrations varied from 1955.7 x 10(-9) to 2036.2 x 10(-9), with the highest concentration observed in autumn and the lowest in spring. The wind directions NE-SSE could induce higher CH4 concentrations while SW-NNW wind directions had negative effects on the observed results. The CH4 concentration turned out to be lower with higher surface wind speed. With the increase of surface air temperature or sunshine hours, the CH4 concentration went up first till reaching a peak, and then decreased.

Evaluation of seasonal changes in methane flux in a wetland ecosystem using the Closed Geosphere Experiment Facility

NASA Astrophysics Data System (ADS)

Suzuki, S.; Inubushi, K.; Yokozawa, M.; Hara, T.; Nishidate, K.; Tsuga, S.; Tako, Y.; Nakamura, Y.

2009-04-01

To estimate CH4 emission from a wetland ecosystem to the atmosphere, seasonal change in CH4 flux was measured continuously in the Closed Geosphere Experiment Facility (CGEF). Plant-mediated transport is one of the important pathways for CH4 emission from Phragmites australis-dominated vegetation because most CH4 emission occurs through P. australis plant. The CGEF is equipped with a Geosphere Module (GM) and a Geosphere Material Circulation (GMC) system. The size of the GM is 5.8 m Ã- 8.7 m in ground area with an average height of 11.9 m, including the soil depth of 3.1 m. A wetland ecosystem dominated by P. australis was introduced into the GM. The CGEF can control air temperature and CO2 concentration in the GM automatically. Hourly CH4 flux from the wetland ecosystem can be calculated easily by measuring continuously the changes in CH4 concentration in air, air temperature and pressure in the GM. The method showed that monthly CH4 flux varied from 0.39 to 1.11 g C m-2 month-1 from April to November and the CH4 emission for the plant growing season (eight months) was 5.64 g C m-2. The CGEF has an advantage in studying total CH4 emission from soil to the atmosphere through plant-mediated transport, diffusion and ebullition because of the large size of the GM.

Effect of ammonia and methane adsorption on the electronic structure of undoped and Fe-doped 2D silica: a first-principles calculation

NASA Astrophysics Data System (ADS)

Chibisov, A. N.; Chibisova, M. A.

2018-05-01

Two-dimensional silicon oxide (2D SiO2) is a unique surface phase with interesting optical, structural and electronic properties. In this study, important novel results on the effect of Fe on the structural and electronic properties of 2D SiO2 during adsorption of CH4 and NH3 molecules are presented. Density functional theory calculations are used to investigate the interaction of CH4 and NH3 molecules with silica. The electronic structure and molecules adsorption energy are studied in detail for undoped and Fe-doped surfaces. The results show that adsorption of CH4 and NH3 molecules on the surface decreases the spin polarization of Fe/SiO2. The results are relevant to understanding the adsorption physics of 2D SiO2 for practical usage in modern nanoelectronic sensors for nanotechnology and optoelectronics.

Liquid and gas phase NMR spectra of 13CH313CHO acetaldehyde

NASA Astrophysics Data System (ADS)

Makulski, Włodzimierz; Wikieł, Agata J.

2018-01-01

The gas phase NMR experiments perform a vital role in establishing the magnetic shielding and spin-spin coupling constants which are free from intermolecular interactions, equivalent to the parameter of isolated molecules. This work is concerned with an acetaldehyde molecule. Small amounts of acetaldehyde 13CH313CHO in gaseous matrices of CO2 and Xe were studied using high-precision 1H and 13C NMR measurements. Results were extrapolated to the zero-density limit permitting the determinations of the 1H and 13C absolute nuclear magnetic shielding of an isolated acetaldehyde molecule. The difference between the experimental and recent theoretical DFT results is discussed. Several samples of 13CH313CHO dissolved in popular organic and inorganic solvents were also investigated. Gas-to-solution shifts show the influence of the association process when acetaldehyde is transferred from gas to liquid state. Several spin-spin coupling constants in the gas phase and in different solvents were precisely measured.

Does shortwave absorption by methane influence its effectiveness?

NASA Astrophysics Data System (ADS)

Modak, Angshuman; Bala, Govindasamy; Caldeira, Ken; Cao, Long

2018-01-01

In this study, using idealized step-forcing simulations, we examine the effective radiative forcing of CH4 relative to that of CO2 and compare the effects of CH4 and CO2 forcing on the climate system. A tenfold increase in CH4 concentration in the NCAR CAM5 climate model produces similar long term global mean surface warming ( 1.7 K) as a one-third increase in CO2 concentration. However, the radiative forcing estimated for CO2 using the prescribed-SST method is 81% that of CH4, indicating that the efficacy of CH4 forcing is 0.81. This estimate is nearly unchanged when the CO2 physiological effect is included in our simulations. Further, for the same long-term global mean surface warming, we simulate a smaller precipitation increase in the CH4 case compared to the CO2 case. This is because of the fast adjustment processes—precipitation reduction in the CH4 case is larger than that of the CO2 case. This is associated with a relatively more stable atmosphere and larger atmospheric radiative forcing in the CH4 case which occurs because of near-infrared absorption by CH4 in the upper troposphere and lower stratosphere. Within a month after an increase in CH4, this shortwave heating results in a temperature increase of 0.8 K in the lower stratosphere and upper troposphere. In contrast, within a month after a CO2 increase, longwave cooling results in a temperature decrease of 3 K in the stratosphere and a small change in the upper troposphere. These fast adjustments in the lower stratospheric and upper tropospheric temperature, along with the adjustments in clouds in the troposphere, influence the effective radiative forcing and the fast precipitation response. These differences in fast climate adjustments also produce differences in the climate states from which the slow response begins to evolve and hence they are likely associated with differing feedbacks. We also find that the tropics and subtropics are relatively warmer in the CH4 case for the same global mean surface warming because of a larger longwave clear-sky and shortwave cloud forcing over these regions in the CH4 case. Further investigation using a multi-model intercomparison framework would permit an assessment of the robustness of our results.

Observations and modeling of methane flux in northern wetlands

NASA Astrophysics Data System (ADS)

Futakuchi, Y.; Ueyama, M.; Matsumoto, Y.; Yazaki, T.; Hirano, T.; Kominami, Y.; Harazono, Y.; Igarashi, Y.

2016-12-01

Methane (CH4) budgets in northern wetlands vary greatly with high spatio-temporal heterogeneity. Owing to limited available data, yet, it is difficult to constrain the CH4 emission from northern wetlands. In this context, we continuously measured CH4 fluxes at two northern wetlands. Measured fluxes were used for constraining the new model that empirically partitioned net CH4 fluxes into the processes of production, oxidation, and transport associated with ebullition, diffusion, and plant, based on the optimization technique. This study reveal the important processes related to the seasonal variations in CH4 emission with the continuous observations and inverse model analysis. The measurements have been conducted at a Sphagnum-dominated cool temperate bog (BBY) since April 2015 using the open-path eddy covariance method and a sub-arctic forested bog on permafrost in University of Alaska Fairbanks (UAF) since May 2016 using three automated chambers by a laser-based gas analyzer (FGGA-24r-EP, Los Gatos Research Inc., USA). In BBY, daily CH4 fluxes ranged from 1.9 nmol m-2 s-1 in early spring to 97.9 nmol m-2 s-1 in mid-summer. Growing-season total CH4 flux was 13 g m-2 yr-1 in 2015. In contrast, CH4 flux at the UAF site was small (0.2 to 1.0 nmol m-2 s-1), and hardly increased since start of the observation. This difference could be caused by the difference in the climate and soil conditions; mean air and soil temperature, and presence of permafrost. For BBY, the seasonal variation of CH4 emission was mostly explained by soil temperature, suggesting that the production was the important controlling process. In mid-summer when soil temperature was high, however, decrease in atmospheric pressure and increase in vegetation greenness stimulated CH4 emission probably through plant-mediated transport and form of bubble, suggesting that the transport processes were important. Based on a preliminary results by the model optimization in BBY site, CH4 fluxes were strongly influenced by the processes associated with production, ebullition, and plant-mediated transports rather than the processes associated with oxidation and diffusion. In this presentation, we will show that the new data-model fusion that we developed is the effective tool for evaluating CH4 fluxes and controlling processes at northern wetlands.

Investigating electron spin resonance spectroscopy of a spin-½ compound in a home-built spectrometer

NASA Astrophysics Data System (ADS)

Sarkar, Jit; Roy, Subhadip; Singh, Jitendra Kumar; Singh, Sourabh; Chakraborty, Tanmoy; Mitra, Chiranjib

2018-05-01

In this work we report electron spin resonance (ESR) measurements performed on NH4CuPO4.H2O, a Heisenberg spin ½ dimer compound. We carried out the experiments both at room temperature and at 78 K, which are well above the antiferromagnetic ordering temperature of the system where the paramagnetic spins have a dominant role in determining its magnetic behavior. We performed the measurements in a home built custom designed continuous wave electron spin resonance (CW-ESR) spectrometer. By analyzing the experimental data, we were able to quantify the Landé g-factor and the ESR line-width of the sample.

A computational study of the addition of ReO3L (L = Cl(-), CH3, OCH3 and Cp) to ethenone.

PubMed

Aniagyei, Albert; Tia, Richard; Adei, Evans

2016-01-01

The periselectivity and chemoselectivity of the addition of transition metal oxides of the type ReO3L (L = Cl, CH3, OCH3 and Cp) to ethenone have been explored at the MO6 and B3LYP/LACVP* levels of theory. The activation barriers and reaction energies for the stepwise and concerted addition pathways involving multiple spin states have been computed. In the reaction of ReO3L (L = Cl(-), OCH3, CH3 and Cp) with ethenone, the concerted [2 + 2] addition of the metal oxide across the C=C and C=O double bond to form either metalla-2-oxetane-3-one or metalla-2,4-dioxolane is the most kinetically favored over the formation of metalla-2,5-dioxolane-3-one from the direct [3 + 2] addition pathway. The trends in activation and reaction energies for the formation of metalla-2-oxetane-3-one and metalla-2,4-dioxolane are Cp < Cl(-) < OCH3 < CH3 and Cp < OCH3 < CH3 < Cl(-) and for the reaction energies are Cp < OCH3 < Cl(-) < CH3 and Cp < CH3 < OCH3 < Cl CH3. The concerted [3 + 2] addition of the metal oxide across the C=C double of the ethenone to form species metalla-2,5-dioxolane-3-one is thermodynamically the most favored for the ligand L = Cp. The direct [2 + 2] addition pathways leading to the formations of metalla-2-oxetane-3-one and metalla-2,4-dioxolane is thermodynamically the most favored for the ligands L = OCH3 and Cl(-). The difference between the calculated [2 + 2] activation barriers for the addition of the metal oxide LReO3 across the C=C and C=O functionalities of ethenone are small except for the case of L = Cl(-) and OCH3. The rearrangement of the metalla-2-oxetane-3-one-metalla-2,5-dioxolane-3-one even though feasible, are unfavorable due to high activation energies of their rate-determining steps. For the rearrangement of the metalla-2-oxetane-3-one to metalla-2,5-dioxolane-3-one, the trends in activation barriers is found to follow the order OCH3 < Cl(-) < CH3 < Cp. The trends in the activation energies for the most favorable [2 + 2] addition pathways for the LReO3-ethenone system is CH3 > CH3O(-) > Cl(-) > Cp. For the analogous ethylene-LReO3 system, the trends in activation and reaction energies for the most favorable [3 + 2] addition pathway is CH3 > CH3O(-) > Cl(-) > Cp [10]. Even though the most favored pathway in the ethylene-LReO3 system is the [3 + 2] addition pathway and that on the LReO3-ethenone is the [2 + 2] addition pathway, the trends in the activation energies for both pathways are the same, i.e. CH3 > CH3O(-) > Cl(-) > Cp. However, the trends in reaction energies are quite different due to different product stabilities. The formation of the acetic acid precursor through the direct addition pathways was unsuccessful for all the ligands studied. The formation of the acetic acid precursor through the cyclization of the metalla-2-oxetane-3-one is only possible for the ligands L = Cl(-), CH3 whiles for the cyclization of metalla-2-oxetane-4-one to the acetic acid precursor is only possible for the ligand L = CH3. Although there are spin-crossover reaction observed for the ligands L = Cl(-), CH3 and CH3O(-), the reactions occurring on the single surfaces have been found to occur with lower energies than their spin-crossover counterparts.

Diminished CAGE Effect in {p}-H2: Infrared Spectra of CH3S Observed from Photolysis of CH3SH, CH3SCH3, and CH3SSCH3 Isolated in {p}-H2

NASA Astrophysics Data System (ADS)

Lee, Yuan-Pern; Bahou, Mohammed

2010-06-01

We report infrared absorption spectrum of the methylthio (or thiomethoxy) radical, CH3S, isolated in solid {p}-H2. CH3S was produced by in situ UV photodissociation of three precursors: CH3SH, CH3SH3, and CH3SSCH3 isolated in solid {p}-H2. New absorption features commonly observed with similar intensity ratios in experiments using these precursors are assigned as absorption of CH3S. In Addition to the previously assigned transitions of ν 3 (a1) at 727.1 cm-1, fundamental transitions ν 6 (a1) at 771.1, ν 6 (e) at 1056.6, ν 5 (a1) at 1400.0, and &nu 4 (a1) at 2898.0 cm-1 were observed. The wavenumbers of these features agree satisfactorily with those predicted with a spin-vibronic Hamiltonian accounting for the anharmonic effects and the Jahn-Teller effects to the qu rtic term; the corresponding wavenumbers predicted from theory are ν 6 (a1) at 793, ν 6 (e) at 1105, ν 5 (a1) at 1436, and ν 4 (a1) at 2938 cm-1, with deviations of 14-4.6 % from experiments. Previous attempts of UV photolysis of CH3SCH3 and CH3SSCH3 isolated in an Ar matrix failed to produce CH3S. These results serve as an excellent example that the diminished cae effect of solid {p}-H2 makes production of free radicals via photolysis in situ feasible. If time permits, other examples will be discussed. A. V. Marenich and J. E. Boggs, J. Chem. Theory Comput., 1, 1162 (2005).

Development of new oganic-based magments for spintronics

NASA Astrophysics Data System (ADS)

Lu, Yu

Organic-based magnets are an emerging research area. The chemical tailorability, all benefits of organic materials as well as potential use in organic spintronics make them an important supplement to traditional metal/metal oxide magnets. This dissertation focused on development of new organic-based magnets, which is composed of three parts. In the first part, a new high Curie temperature (Tc ˜ 145 K) organic-based magnet with composition of vanadium ethyl tricyanoethlyenecarboxylate (V[ETCEC]1.3•0.3 CH2Cl2) is prepared via a reaction of V(CO)6 and ETCEC in CH2Cl2. Temperature-, field-, and frequency-dependent measurements of the magnetization reveal complex magnetic behavior with a magnetic transition into a more disordered state. Since ethyl tricyanoethlyenecarboxylate (ETCEC) holds the structure similarity with tetracyanoethylene (TCNE) and methyl tricyanoethylenecarboxylate (MeTCEC), the comparison is made among these materials, which indicates the effects of steric hindrance and electron negativity on magnetic properties. Application of the random anisotropy model (RMA) shows that this disordered state is different from the correlated spin glass (CSG) phase observed in analogous organic-based magnets V[MeTCEC]x and V[TCNE]x synthesized in CH2Cl2. This suggests that V[ETCEC]x is less disordered than its analogues, which can be attributed to the slower reaction rate. In the second part, I will present the first successful attempt at ligand modification in chemical vapor deposition (CVD) prepared thin film by replacing a single cyano group on TCNE with an ester on ETCEC and MeTCEC. The resulting films have magnetic ordering temperature of ˜175 K and ˜300 K respectively, providing the first viable complement to V[TCNE]2 and opening the door to an entire class of all-organic magnetic heterostructures. These heterostructures will retain the central benefits demonstrated in other areas of organic electronics such as low cost, low deposition temperature and conformal deposition, while incorporating key magnetic based functionality such as non-volatile memory, magnetic sensing and applications in high frequency magnetoelectronics. The structures, magnetic and electronic properties of these materials are characterized by a combination of various instruments. The last part of this dissertation will focus on the progress that have been made during my PhD study toward the application of organic-based magnets, including encapsulation of these materials to protect them from degradation, optimization of growth conditions to achieve high quality films with super-narrow ferromagentic resonance (FMR) signal (˜1 G) and application of thin film V[TCNE]x as a spin injector/detector in spin-valves.

Suggestion for search of ethylene oxide (c-C2H4O) in a cosmic object

NASA Astrophysics Data System (ADS)

Sharma, M. K.; Sharma, M.; Chandra, S.

2018-05-01

Ethylene oxide (c-C2H4O) and its isomer acetaldehyde (CH3CHO) are important organic molecules because of their potential role in the formation of amino acids. The c-C2H4O molecule is a b-type asymmetric top molecule and owing to half-spin of each of the four hydrogen atoms, it has two distinct ortho (nuclear spin one) and para (nuclear spin zero and two) species. It has been detected in the Sgr B2N. Using the rotational and centrifugal distortion constants along with the electric dipole moment, we have calculated energies of 100 rotational levels of each of the ortho and para species of c-C2H4O molecule and the Einstein A-coefficients for radiative transitions between the levels. The values of Einstein A-coefficients along with the scaled values for the collisional rate coefficients are used for solving a set of statistical equilibrium equations coupled with the equations of radiative transfer. Brightness-temperatures of five rotational transitions of each of the ortho and para species of c-C2H4O molecule are investigated. Out of these ten transitions, three transitions are found to show the anomalous absorption and rest seven are found to show the emission feature. We have also investigated seven transitions observed unblended in the Sgr B2(N). We have found that the transitions 3_{3 0} - 3_{2 1} (23.134 GHz), 2_{2 0} - 2_{1 1} (15.603 GHz), 3_{3 1} - 3_{2 2} (39.680 GHz) and 1_{1 1} - 0_{0 0} (39.582 GHz) may play important role for the identification of ethylene oxide in a cosmic object.

Methanol Formation via Oxygen Insertion Chemistry in Ices

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

Bergner, Jennifer B.; Öberg, Karin I.; Rajappan, Mahesh

We present experimental constraints on the insertion of oxygen atoms into methane to form methanol in astrophysical ice analogs. In gas-phase and theoretical studies this process has previously been demonstrated to have a very low or nonexistent energy barrier, but the energetics and mechanisms have not yet been characterized in the solid state. We use a deuterium UV lamp filtered by a sapphire window to selectively dissociate O{sub 2} within a mixture of O{sub 2}:CH{sub 4} and observe efficient production of CH{sub 3}OH via O({sup 1}D) insertion. CH{sub 3}OH growth curves are fit with a kinetic model, and we observemore » no temperature dependence of the reaction rate constant at temperatures below the oxygen desorption temperature of 25 K. Through an analysis of side products we determine the branching ratio of ice-phase oxygen insertion into CH{sub 4}: ∼65% of insertions lead to CH{sub 3}OH, with the remainder leading instead to H{sub 2}CO formation. There is no evidence for CH{sub 3} or OH radical formation, indicating that the fragmentation is not an important channel and that insertions typically lead to increased chemical complexity. CH{sub 3}OH formation from O{sub 2} and CH{sub 4} diluted in a CO-dominated ice similarly shows no temperature dependence, consistent with expectations that insertion proceeds with a small or nonexistent barrier. Oxygen insertion chemistry in ices should therefore be efficient under low-temperature ISM-like conditions and could provide an important channel to complex organic molecule formation on grain surfaces in cold interstellar regions such as cloud cores and protoplanetary disk midplanes.« less

Silicotungstate, a Potential Electron Transporting Layer for Low-Temperature Perovskite Solar Cells.

PubMed

Choi, Yoon Ho; Kim, Hyun Bin; Yang, In Seok; Sung, Sang Do; Choi, Young Sik; Kim, Jeongho; Lee, Wan In

2017-08-02

Thin films of a heteropolytungstate, lithium silicotungstate (Li 4 SiW 12 O 40 , termed Li-ST), prepared by a solution process at low temperature, were successfully applied as electron transporting layer (ETL) of planar-type perovskite solar cells (PSCs). Dense and uniform Li-ST films were prepared on FTO glass by depositing a thin Li-ST buffer layer, followed by coating of a main Li-ST layer. The film thickness was controlled by varying the number of coating cycles, consisting of spin-coating and thermal treatment at 150 °C. In particular, by employing 60 nm-thick Li-ST layer obtained by two cycles of coating, the fabricated CH 3 NH 3 PbI 3 PSC device demonstrates the photovoltaic conversion efficiency (PCE) of 14.26% with J SC of 22.16 mA cm -2 , V OC of 0.993 mV and FF of 64.81%. The obtained PCE is significantly higher than that of the PSC employing a TiO 2 layer processed at the same temperature (PCE = 12.27%). Spectroscopic analyses by time-resolved photoluminescence and pulsed light-induced transient measurement of photocurrent indicate that the Li-ST layer collects electrons from CH 3 NH 3 PbI 3 more efficiently and also exhibits longer electron lifetime than the TiO 2 layer thermally treated at 150 °C. Thus, Li-ST is considered to be a promising ETL material that can be applied for the fabrication of flexible PSC devices.

High-pressure oxidation of ethane

DOE PAGES

Hashemi, Hamid; Jacobsen, Jon G.; Rasmussen, Christian T.; ...

2017-05-02

Here, ethane oxidation at intermediate temperatures and high pressures has been investigated in both a laminar flow reactor and a rapid compression machine (RCM). The flow-reactor measurements at 600–900 K and 20–100 bar showed an onset temperature for oxidation of ethane between 700 and 825 K, depending on pressure, stoichiometry, and residence time. Measured ignition delay times in the RCM at pressures of 10–80 bar and temperatures of 900–1025 K decreased with increasing pressure and/or temperature. A detailed chemical kinetic model was developed with particular attention to the peroxide chemistry. Rate constants for reactions on the C 2H 5O 2more » potential energy surface were adopted from the recent theoretical work of Klippenstein. In the present work, the internal H-abstraction in CH 3CH 2OO to form CH 2CH 2OOH was treated in detail. Modeling predictions were in good agreement with data from the present work as well as results at elevated pressure from literature. The experimental results and the modeling predictions do not support occurrence of NTC behavior in ethane oxidation. Even at the high-pressure conditions of the present work where the C 2H 5 + O 2 reaction yields ethylperoxyl rather than C 2H 4 + HO 2, the chain branching sequence CH 3CH 2OO → CH 2CH 2OOH → +O2 OOCH 2CH 2OOH → branching is not competitive, because the internal H-atom transfer in CH 3CH 2OO to CH 2CH 2OOH is too slow compared to thermal dissociation to C 2H 4 and HO 2.« less

Patterns in CH4 and CO2 concentrations across boreal rivers: Major drivers and implications for fluvial greenhouse emissions under climate change scenarios.

PubMed

Campeau, Audrey; Del Giorgio, Paul A

2014-04-01

It is now widely accepted that boreal rivers and streams are regionally significant sources of carbon dioxide (CO2), yet their role as methane (CH4) emitters, as well as the sensitivity of these greenhouse gas (GHG) emissions to climate change, are still largely undefined. In this study, we explore the large-scale patterns of fluvial CO2 and CH4 partial pressure (pCO2 , pCH4) and gas exchange (k) relative to a set of key, climate-sensitive river variables across 46 streams and rivers in two distinct boreal landscapes of Northern Québec. We use the resulting models to determine the direction and magnitude of C-gas emissions from these boreal fluvial networks under scenarios of climate change. River pCO2 and pCH4 were positively correlated, although the latter was two orders of magnitude more variable. We provide evidence that in-stream metabolism strongly influences the dynamics of surface water pCO2 and pCH4 , but whereas pCO2 is not influenced by temperature in the surveyed streams and rivers, pCH4 appears to be strongly temperature-dependent. The major predictors of ambient gas concentrations and exchange were water temperature, velocity, and DOC, and the resulting models indicate that total GHG emissions (C-CO2 equivalent) from the entire network may increase between by 13 to 68% under plausible scenarios of climate change over the next 50 years. These predicted increases in fluvial GHG emissions are mostly driven by a steep increase in the contribution of CH4 (from 36 to over 50% of total CO2 -equivalents). The current role of boreal fluvial networks as major landscape sources of C is thus likely to expand, mainly driven by large increases in fluvial CH4 emissions. © 2013 John Wiley & Sons Ltd.

Rotation Dynamics Do Not Determine the Unexpected Isotropy of Methyl Radical EPR Spectra.

PubMed

Benetis, Nikolas P; Dmitriev, Yurij; Mocci, Francesca; Laaksonen, Aatto

2015-09-03

A simple first-principles electronic structure computation, further qc (quantum chemistry) computation, of the methyl radical gives three equal hf (hyperfine) couplings for the three protons with the unpaired electron. The corresponding dipolar tensors were notably rhombic and had different orientations and regular magnitude components, as they should, but what the overall A-tensor was seen by the electron spin is a different story! The final g = (2.002993, 2.002993, 2.002231) tensor and the hf coupling results obtained in vacuum, at the B3LYP/EPRIII level of theory clearly indicate that in particular the above A = (-65.19, -65.19, 62.54) MHz tensor was axial to a first approximation without considering any rotational dynamics for the CH3. This approximation was not applicable, however, for the trifluoromethyl CF3 radical, a heavier and nonplanar rotor with very anisotropic hf coupling, used here for comparison. Finally, a derivation is presented explaining why there is actually no need for the CH3 radicals to consider additional rotational dynamics in order for the electron to obtain an axially symmetric hf (hyperfine) tensor by considering the simultaneous dipolar couplings of the three protons. An additional consequence is an almost isotropic A-tensor for the electron spin of the CH3 radical. To the best of our knowledge, this point has not been discussed in the literature before. The unexpected isotropy of the EPR parameters of CH3 was solely attributed to the rotational dynamics and was not clearly separated from the overall symmetry of the species. The present theoretical results allowed a first explanation of the "forbidden" satellite lines in the CH3 EPR spectrum. The satellites are a fingerprint of the radical rotation, helping thus in distinguishing the CH3 reorientation from quantum rotation at very low temperatures.

Optical magnetometry of superconductors using nitrogen - vacancy centers in diamond films

NASA Astrophysics Data System (ADS)

Joshi, K. R.; Nusran, N. M.; Cho, Kyuil; Tanatar, M. A.; Bud'Ko, S. L.; Canfield, P. C.; Prozorov, R.

Spin-dependent fluorescence of nitrogen - vacancy (NV) centers in diamond has emerged as a promising tool for non-invasive sensitive magnetometry with excellent sensitivity. In this work, we employ ensembles of NV centers implanted at the surface of a diamond film to study magnetic induction as the function of position, magnetic field and temperature in superconductors after different cooling/heating protocols and magnetic history. One of the motivations of our work is to study the structure of the Meissner expulsion upon field cooling, where we observe significant deviations from the simple, textbook example. Another is to determine the lower superconducting critical field, Hc1. Conventional Nb is compared with borocarbides (LuNi2B2C) and iron-pnictides(CaKFe4As4). Supported by the USDOE/Office of Science BES Materials Science and Engineering Division under contract DE-AC02-07CH11358.

Increased importance of methane reduction for a 1.5 degree target

NASA Astrophysics Data System (ADS)

Collins, William J.; Webber, Christopher P.; Cox, Peter M.; Huntingford, Chris; Lowe, Jason; Sitch, Stephen; Chadburn, Sarah E.; Comyn-Platt, Edward; Harper, Anna B.; Hayman, Garry; Powell, Tom

2018-04-01

To understand the importance of methane on the levels of carbon emission reductions required to achieve temperature goals, a processed-based approach is necessary rather than reliance on the transient climate response to emissions. We show that plausible levels of methane (CH4) mitigation can make a substantial difference to the feasibility of achieving the Paris climate targets through increasing the allowable carbon emissions. This benefit is enhanced by the indirect effects of CH4 on ozone (O3). Here the differing effects of CH4 and CO2 on land carbon storage, including the effects of surface O3, lead to an additional increase in the allowable carbon emissions with CH4 mitigation. We find a simple robust relationship between the change in the 2100 CH4 concentration and the extra allowable cumulative carbon emissions between now and 2100 (0.27 ± 0.05 GtC per ppb CH4). This relationship is independent of modelled climate sensitivity and precise temperature target, although later mitigation of CH4 reduces its value and thus methane reduction effectiveness. Up to 12% of this increase in allowable emissions is due to the effect of surface ozone. We conclude early mitigation of CH4 emissions would significantly increase the feasibility of stabilising global warming below 1.5 °C, alongside having co-benefits for human and ecosystem health.

Rotational Mode Specificity in the F(-) + CH3Y [Y = F and Cl] SN2 Reactions.

PubMed

Szabó, István; Czakó, Gábor

2015-12-17

More than 12 million quasiclassical trajectories are computed for the F(-) + CH3Y(v = 0, JK) [Y = F and Cl] SN2 reactions using full-dimensional ab initio analytical potential energy surfaces. The initial (J, K = 0) and (J, K = J) [J = 0, 2, 4, 6, 8] rotational state specific cross sections are obtained at different collision energies (Ecoll) in the 1-20 kcal mol(-1) range, and the scattering angle and initial attack angle distributions as well as the mechanism-specific opacity functions are reported at Ecoll = 10 kcal mol(-1). The tumbling rotation (K = 0) inhibits the F(-) + CH3F reaction by a factor of 3 for J = 8 at Ecoll = 10 kcal mol(-1). This tumbling rotational effect becomes smaller at low and high Ecoll, and the tumbling motion affects the cross sections of F(-) + CH3Cl by only a few percent. The spinning rotation (K = J) hinders both reactions by factors in the 1.3-1.7 range for J = 8 at low Ecoll, whereas slight promotion is found as the Ecoll increases. The tumbling rotation may counteract the attractive ion-dipole forces, and the spinning motion hinders the complex formation, thereby decreasing the reactivity.

High-temperature heat capacity of Co3O4 spinel: thermally induced spin unpairing transition

USGS Publications Warehouse

Mocala, K.; Navrotsky, A.; Sherman, David M.

1992-01-01

A strong anomaly was found in the heat capacity of Co3O4 between 1000 K and the decomposition temperature. This anomaly is not related to the decomposition of Co3O4 to CoO. The measured entropy of transition, ??S=46??4 J mol-1 K-1 of Co3O4, supports the interpretation that this anomaly reflects a spin unpairing transition in octahedrally coordinated Co3+ cations. Experimental values of heat capacity, heat content and entropy of Co3O4 in the high temperature region are provided. The enthalpy of the spin unpairing transition is 53??4 kJ mol-1 of Co3O4. ?? 1992 Springer-Verlag.

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

Kuang, Xingya; Shankar, T.J.; Bi, X.T.

Wood pellets emit CO, CO2, CH4 and other volatiles during storage. Increased concentration of these gases in a sealed storage causes depletion of concentration of oxygen. The storage environment becomes toxic to those who operate in and around these storages. The objective of this study was to investigate the effects of temperature, moisture and storage headspace on emissions from wood pellets in an enclosed space. Twelve 10-liter plastic containers were used to study the effects of headspace ratio (25%, 50%, and 75% of container volume) and temperatures (10-50oC). Another eight containers were set in uncontrolled storage relative humidity and temperature.more » Concentrations of CO2, CO and CH4 were measured by a gas chromatography (GC). The results showed that emissions of CO2, CO and CH4 from stored wood pellets are most sensitive to storage temperature. Higher peak emission factors are associated with higher temperatures. Increased headspace volume ratio increases peak off-gas emissions because of the availability of oxygen for pellet decomposition. Increased relative humidity in the enclosed container increases the rate of off-gas emissions of CO2, CO and CH4 and oxygen depletion.« less

Sunlight stimulates methane uptake and nitrous oxide emission from the High Arctic tundra.

PubMed

Li, Fangfang; Zhu, Renbin; Bao, Tao; Wang, Qing; Xu, Hua

2016-12-01

Many environmental factors affecting methane (CH 4 ) and nitrous oxide (N 2 O) fluxes have been investigated during the processes of carbon and nitrogen transformation in the boreal tundra. However, effects of sunlight on CH 4 and N 2 O fluxes and their budgets were neglected in the boreal tundra. Here, summertime CH 4 and N 2 O fluxes in the presence and total absence of sunlight were investigated at the six tundra sites (DM1-DM6) on Ny-Ålesund in the High Arctic. The mean CH 4 fluxes at the tundra sites ranged from -4.7 to -158.6μg CH 4 m -2 h -1 in the presence of light, indicating that a large CH 4 sink occurred in the tundra soils. However, enhanced CH 4 emission in total absence of light occurred at all the tundra sites. The mean N 2 O fluxes ranged from 7.4 to 14.6μg N 2 O m -2 h -1 in the presence of light, whereas in the absence of light all the tundra sites generally released less N 2 O, and even significant N 2 O uptake occurred there. Soil temperature, chamber temperature and soil moisture showed no significant correlations with tundra CH 4 and N 2 O flux. The presence of sunlight increased tundra CH 4 uptake by 114.2μg CH 4 m -2 h -1 and N 2 O emission by 10.9μg N 2 O m -2 h -1 compared with total absence of light. Overall our results showed that tundra ecosystem switched from CH 4 sink and N 2 O emission source in the presence of light to CH 4 emission source and N 2 O sink in the absence of light. Therefore sunlight had an important effect on CH 4 and N 2 O budgets in the High Arctic tundra. The exclusion of sunlight might overestimate CH 4 budgets, but underestimate N 2 O budgets in the Arctic tundra ecosystem. Copyright © 2016 Elsevier B.V. All rights reserved.

Research Update: Relativistic origin of slow electron-hole recombination in hybrid halide perovskite solar cells

NASA Astrophysics Data System (ADS)

Azarhoosh, Pooya; McKechnie, Scott; Frost, Jarvist M.; Walsh, Aron; van Schilfgaarde, Mark

2016-09-01

The hybrid perovskite CH3NH3PbI3 (MAPI) exhibits long minority-carrier lifetimes and diffusion lengths. We show that slow recombination originates from a spin-split indirect-gap. Large internal electric fields act on spin-orbit-coupled band extrema, shifting band-edges to inequivalent wavevectors, making the fundamental gap indirect. From a description of photoluminescence within the quasiparticle self-consistent GW approximation for MAPI, CdTe, and GaAs, we predict carrier lifetime as a function of light intensity and temperature. At operating conditions we find radiative recombination in MAPI is reduced by a factor of more than 350 compared to direct gap behavior. The indirect gap is retained with dynamic disorder.

Carbon isotope exchange in the system CO 2-CH 4 at elevated temperatures

NASA Astrophysics Data System (ADS)

Horita, Juske

2001-06-01

Carbon isotope exchange was investigated for the system CO 2-CH 4 at 150 to 600°C in the presence of several potential catalysts by use of isotopically normal or 13C-enriched gases. Silica gel, graphite, molecular sieve Linde 4A, magnetite, and hematite oxidized small amounts of CH 4 in starting CO 2-CH 4 mixtures to CO and CO 2 but failed to enhance the net rate of carbon isotope exchange between CO 2 and CH 4, even after 169 to 1833 h at 400 to 500°C. In contrast, several commercial transition-metal catalysts (Ni, Pd, Rh, and Pt) promoted reactions significantly toward chemical and isotopic equilibrium. With the Ni catalyst, the attainment of carbon isotopic equilibrium between CO 2 and CH 4 was demonstrated for the first time at temperatures from 200 to 600°C by complete isotopic reversal from opposite directions. The experimentally determined carbon isotope fractionation factors between CO 2 and CH 4 (10 3lnα) were similar to, but slightly greater than (0.7-1.1‰, 0.89‰ on average), those of statistical-mechanical calculations by Richet et al. (1977). The experimental results can be described by the following equation between 200 and 600°C only: 10 3lnα(CO 2-CH 4) = 26.70 - 49.137(10 3/T) + 40.828(10 6/T 2) - 7.512(10 9/T 3) (T = 473.15-873.15 K, 1σ = ±0.14‰, n = 44). Alternatively, an equation generated by fitting Richet et al. (1977) data in the temperature range from 0 to 1300°C can be modified by adding +0.89‰ to its constant; 10 3lnα(CO 2-CH 4) = 0.16 + 11.754(10 6/T 2) - 2.3655(10 9/T 3) + 0.2054(10 12/T 4) (T = 273-1573 K, 1σ = ±0.21‰, n = 44). This and other recent experimental studies in the literature demonstrate that transition metals, which are widespread in many natural materials, can catalyze reactions among natural gases at relatively low temperatures (≤200°C). The role of natural catalysts, "geocatalysts," in the abiogenic formation of methane, hydrocarbons, and simple organic compounds has important implications, ranging from the exploration of hydrocarbon resources to prebiotic organic synthesis.

Spin-Glass Ground State in a Triangular-Lattice Compound YbZnGaO4

NASA Astrophysics Data System (ADS)

Ma, Zhen; Wang, Jinghui; Dong, Zhao-Yang; Zhang, Jun; Li, Shichao; Zheng, Shu-Han; Yu, Yunjie; Wang, Wei; Che, Liqiang; Ran, Kejing; Bao, Song; Cai, Zhengwei; Čermák, P.; Schneidewind, A.; Yano, S.; Gardner, J. S.; Lu, Xin; Yu, Shun-Li; Liu, Jun-Ming; Li, Shiyan; Li, Jian-Xin; Wen, Jinsheng

2018-02-01

We report on comprehensive results identifying the ground state of a triangular-lattice structured YbZnGaO4 as a spin glass, including no long-range magnetic order, prominent broad excitation continua, and the absence of magnetic thermal conductivity. More crucially, from the ultralow-temperature ac susceptibility measurements, we unambiguously observe frequency-dependent peaks around 0.1 K, indicating the spin-glass ground state. We suggest this conclusion holds also for its sister compound YbMgGaO4 , which is confirmed by the observation of spin freezing at low temperatures. We consider disorder and frustration to be the main driving force for the spin-glass phase.

Temperature, productivity and sediment characteristics as drivers of seasonal and spatial variations of dissolved methane in the near-shore coastal areas (Belgian coastal zone, North Sea)

NASA Astrophysics Data System (ADS)

Borges, Alberto V.; Speeckaert, Gaëlle; Champenois, Willy; Scranton, Mary I.; Gypens, Nathalie

2017-04-01

The open ocean is a modest source of CH4 to the atmosphere compared to other natural and anthropogenic CH4 emissions. Coastal regions are more intense sources of CH4 to the atmosphere than open oceanic waters, in particular estuarine zones. The CH4 emission to the atmosphere from coastal areas is sustained by riverine inputs and methanogenesis in the sediments due to high organic matter (OM) deposition. Additionally, natural gas seeps are sources of CH4 to bottom waters leading to high dissolved CH4 concentrations in bottom waters (from tenths of nmol L-1 up to several µmol L-1). We report a data set of dissolved CH4 concentrations obtained at nine fixed stations in the Belgian coastal zone (Southern North Sea), during one yearly cycle, with a bi-monthly frequency in spring, and a monthly frequency during the rest of the year. This is a coastal area with multiple possible sources of CH4 such as from rivers and gassy sediments, and where intense phytoplankton blooms are dominated by the high dimethylsulfoniopropionate (DMSP) producing micro-algae Phaeocystis globosa, leading to DMSP and dimethylsulfide (DMS) concentrations. Furthermore, the BCZ is a site of important OM sedimentation and accumulation unlike the rest of the North Sea. Spatial variations of dissolved CH4 concentrations were very marked with a minimum yearly average of 9 nmol L-1 in one of the most off-shore stations and maximum yearly average of 139 nmol L-1 at one of the most near-shore stations. The spatial variations of dissolved CH4 concentrations were related to the organic matter (OM) content of sediments, although the highest concentrations seemed to also be related to inputs of CH4 from gassy sediments associated to submerged peat. In the near-shore stations with fine sand or muddy sediments with a high OM content, the seasonal cycle of dissolved CH4 concentration closely followed the seasonal cycle of water temperature, suggesting the control of methanogenesis by temperature in these OM replete sediments. In the off-shore stations with permeable sediments with a low OM content, the seasonal cycle of dissolved CH4 concentration showed a yearly peak following the chlorophyll-a spring peak. This suggests that in these OM poor sediments, methanogenesis depended on the delivery to the sediments of freshly produced OM. In both types of sediments, the seasonal cycle of dissolved CH4 concentrations was unrelated the seasonal cycles of DMS, and DMSP, despite the fact that these quantities were very high during the spring Phaeocystis globosa bloom. This suggests that in this shallow coastal environment CH4 production is overwhelmingly related to benthic processes and unrelated to DMS(P) transformations in the water column as recently suggested in several open ocean regions. The annual average CH4 emission was 41 mmol m-2 yr-1 in the most near-shore stations ( 4 km from the coast) and 10 mmol m-2 yr-1 in the most off-shore stations ( 23 km from the coast), 410-100 times higher than the average value in the open ocean (0.1 mmol m-2 yr-1). The strong control of CH4 concentrations by sediment OM content and by temperature suggests that marine coastal CH4 emissions, in particular shallow coastal areas, should respond in future to eutrophication and warming of climate. This is confirmed by the comparison of CH4 concentrations at five stations obtained in March in years 1990 and 2016, showing a decreasing trend consistent with alleviation of eutrophication in the area.

Greenhouse gas emissions from oilfield-produced water in Shengli Oilfield, Eastern China.

PubMed

Yang, Shuang; Yang, Wei; Chen, Guojun; Fang, Xuan; Lv, Chengfu; Zhong, Jiaai; Xue, Lianhua

2016-08-01

Greenhouse gas (GHG) emissions from oil and gas systems are an important component of the GHG emission inventory. To assess the carbon emissions from oilfield-produced water under atmospheric conditions correctly, in situ detection and simulation experiments were developed to study the natural release of GHG into the atmosphere in the Shengli Oilfield, the second largest oilfield in China. The results showed that methane (CH4) and carbon dioxide (CO2) were the primary gases released naturally from the oilfield-produced water. The atmospheric temperature and release time played important roles in determining the CH4 and CO2 emissions under atmospheric conditions. Higher temperatures enhanced the carbon emissions. The emissions of both CH4 and CO2 from oilfield-produced water were highest at 27°C and lowest at 3°C. The bulk of CH4 and CO2 was released from the oilfield-produced water during the first release period, 0-2hr, for each temperature, with a maximum average emission rate of 0.415gCH4/(m(3)·hr) and 3.934gCO2/(m(3)·hr), respectively. Then the carbon emissions at other time periods gradually decreased with the extension of time. The higher solubility of CO2 in water than CH4 results in a higher emission rate of CH4 than CO2 over the same release duration. The simulation proved that oilfield-produced water is one of the potential emission sources that should be given great attention in oil and gas systems. Copyright © 2016. Published by Elsevier B.V.

Formation of interstellar methanol ice prior to the heavy CO freeze-out stage

NASA Astrophysics Data System (ADS)

Qasim, D.; Chuang, K.-J.; Fedoseev, G.; Ioppolo, S.; Boogert, A. C. A.; Linnartz, H.

2018-04-01

Context. The formation of methanol (CH3OH) on icy grain mantles during the star formation cycle is mainly associated with the CO freeze-out stage. Yet there are reasons to believe that CH3OH also can form at an earlier period of interstellar ice evolution in CO-poor and H2O-rich ices. Aims: This work focuses on CH3OH formation in a H2O-rich interstellar ice environment following the OH-mediated H-abstraction in the reaction, CH4 + OH. Experimental conditions are systematically varied to constrain the CH3OH formation yield at astronomically relevant temperatures. Methods: CH4, O2, and hydrogen atoms are co-deposited in an ultrahigh vacuum chamber at 10-20 K. OH radicals are generated by the H + O2 surface reaction. Temperature programmed desorption - quadrupole mass spectrometry (TPD-QMS) is used to characterize CH3OH formation, and is complemented with reflection absorption infrared spectroscopy (RAIRS) for CH3OH characterization and quantitation. Results: CH3OH formation is shown to be possible by the sequential surface reaction chain, CH4 + OH → CH3 + H2O and CH3 + OH → CH3OH at 10-20 K. This reaction is enhanced by tunneling, as noted in a recent theoretical investigation Lamberts et al. (2017, A&A, 599, A132). The CH3OH formation yield via the CH4 + OH route versus the CO + H route is approximately 20 times smaller for the laboratory settings studied. The astronomical relevance of the new formation channel investigated here is discussed.

Methane efflux measured by eddy covariance in Alaskan upland tundra undergoing permafrost degradation

NASA Astrophysics Data System (ADS)

Taylor, M.; Celis, G.; Ledman, J.; Bracho, R. G.; Schuur, E.

2017-12-01

Permafrost thaw can increase landscape heterogeneity, leading to wetter and drier soil conditions that affect the magnitude and form (carbon dioxide - CO2 and methane - CH4) of carbon produced via microbial decomposition. Environmental controls on CH4 emissions, especially in drier upland tundra systems, are not well understood. In degrading upland tundra permafrost, cold season CH4 fluxes may contribute significantly to annual emissions from CH4 production within unfrozen layers deep in the soil profile. Eight Mile Lake (EML), located in Interior Alaska near Denali National Park, is a moist acidic tussock tundra ecosystem undergoing permafrost degradation. Perennially frozen soils have warmed between 1985 and 2016 from -1.2 to -0.75˚C resulting in a deeper active layer depth from 61 to 70 cm between 2004-2016. Depth from the soil/moss surface to the water table perched on the permafrost surface has decreased from 30 to 20 cm over the same interval. Here we present the first year of continuous CH4 flux measurements made at EML (May 2016 - May 2017). The site was a net source of low-level CH4 emissions throughout the year. Annual CH4 emissions (1.3 g C yr-1) made up 8.8% of total annual C emissions (14.7 g m-2yr-1). Methane flux is related with soil temperatures during both summer and non-summer seasons. Emissions increased throughout the summer season as thaw depth and soil temperatures increased. In contrast with wetland sites where water table is at or above the soil surface for much of the growing season, EML is relatively dry and there was no relationship between soil moisture and emissions. Non-summer season CH4 emissions are related to increases in atmospheric and shallow soil temperatures. Winter season emissions account for 37% of the annual CH4 budget, the bulk of which occurred between October and January when deep soils remained thawed. Non-summer season CH4 and CO2 pulses appear to be coupled, suggesting a similar mechanism for release. We hypothesize that this relationship is the result of surface soils warming and cracking, allowing for the escape of microbially produced gases at depth. While annual CH4 emissions made up 8.8% of total annual C emissions at this site, taking into account the greenhouse warming potential of CH4 relative to CO2, the climate impact of CH4 is 15.6 g m-2yr-1, or 69% of the C budget.

Low temperature rate coefficients for the reactions of 1CH2 with reactive and non-reactive species, and the implications for Titan's atmosphere

NASA Astrophysics Data System (ADS)

Douglas, Kevin; Slater, Eloise; Blitz, Mark; Plane, John; Heard, Dwayne; Seakins, Paul

2016-04-01

The Cassini-Huygens mission to Titan revealed unexpectedly large amounts of benzene in the troposphere, and confirmed the absence of a global ethane ocean as predicted by photochemical models of methane conversion over the lifetime of the solar system. An important chemical intermediate in both the production and loss of benzene and ethane is the first electronically excited state of methylene, 1CH2. For example, at room temperature an important reaction of 1CH2 is with acetylene (R1a), leading to the formation of propargyl (C3H3)[1]. The subsequent recombination of propargyl radicals is the major suggested route to benzene in Titan's atmosphere (R2)[2]. In addition to reaction of 1CH2 leading to products, there is also competition between inelastic electronic relaxation to form the ground triplet state 3CH2 (R1b). This ground state 3CH2 has a markedly different reactivity to the singlet, reacting primarily with methyl radicals (CH3) to form ethene (R3). As methyl radical recombination is the primary route to ethane (R4)[3], reactions of 1CH2 will also heavily influence the ethane budget on Titan. 1CH2 + C2H2 → C3H3 + H (R1a) 1CH2 + C2H2 → 3CH2 + C2H2 (R1b) C3H3 + C3H3 → C6H6 (R2) 3CH2 + CH3 → C2H4 + H (R3) CH3 + CH3 (+ M) → C2H6 (R4) Thus this competition between chemical reaction and electronic relaxation in the reactions of 1CH2 with H2, CH4, C2H4, and C2H6 will play an important role in determining the benzene and ethane budgets on Titan. Despite this there are no measurements of any rate constants for 1CH2 at temperatures relevant to Titan's atmosphere (60 - 170 K). Using a pulsed Laval nozzle apparatus coupled with pulsed laser photolysis laser-induced fluorescence, the low temperature reaction kinetics for the removal of 1CH2 with nitrogen, hydrogen, methane, ethane, ethene, acetylene, and oxygen, have been studied. The results revealed an increase in the removal rate of 1CH2 at temperatures below 200 K, with a sharp increase of around a factor of 5 observed at 45±5 K. In addition to measuring total removal rates of 1CH2, the fraction of 1CH2 removed via electronic relaxation verses chemical reaction to products has also been investigated. Results for the reactive species ethane, ethene, and acetylene at 45±5 K, and for hydrogen and methane at 73±9 K indicate that following reactions with 1CH2, removal of 1CH2 is predominantly due to electronic relaxation (> 95 %) and not chemical reaction to products. This is in agreement with previous studies that show that with decreasing temperature, the fraction of reactive removal of 1CH2 to chemical products decreases while the fraction of removal by electronic relaxation increases[4][5]. These results indicate that 1CH2 formed in Titan's atmosphere will be rapidly relaxed to it's ground state via collisions with both reactive and non-reactive species, and thus will play a less significant role in the formation of larger hydrocarbons than previously thought. However for a full understanding of the implications of these results, the new measurements are to be included in a 1D model of Titan's atmosphere to determine the impact of the laboratory measurements on observation/model agreement. [1] K. Gannon et. al., J. Phys. Chem. A, (2010), 114, 9413 [2] E.H. Wilson, S.K. Atreya, J. Geophys. Res., (2004), 109, 6002 [3] M. Fulchignoni, Nature, (2005), 438, 785 [4] K. Gannon, Faraday Discuss., (2010), 147, 173 [5] K. Gannon, J. Phys. Chem. A, (2008), 112, 9575

Magnetic phase diagram, static properties and relaxation of the insulating spin glass Co 1- xMn x(SCN) 2(CH 3OH) 2

NASA Astrophysics Data System (ADS)

DeFotis, G. C.; Just, E. M.; Pugh, V. J.; Coffey, G. A.; Hogg, B. D.; Fitzhenry, S. L.; Marmorino, J. L.; Krovich, D. J.; Chamberlain, R. V.

1999-07-01

The magnetic behavior of Co 1- xMn x(SCN) 2(CH 3OH) 2 has been studied by DC magnetization and susceptibility measurements on mixtures spanning the complete composition range. The pure components are a quasi-two-dimensional Heisenberg antiferromagnet (Mn system) and a three-dimensional Ising antiferromagnet (Co system). The crystal structure of the cobalt constituent is determined, and is closely related to that of the manganese constituent. Competing orthogonal spin anisotropies should occur in mixtures, and frustration effects arising from competing ferromagnetic and antiferromagnetic interactions may also arise. The Curie and Weiss constants, in χM= C/( T- θ), vary regularly with composition. C versus x is essentially linear while θ versus x shows a definite curvature, analysis of which reveals that the unlike-ion exchange interaction is antiferromagnetic and stronger than the like-ion interactions. The magnetic susceptibility is field dependent, more markedly so with increasing x. Plots of M/ H versus T exhibit maxima at low temperatures only for mixtures substantially richer in cobalt than manganese. Magnetic transition temperatures are estimated from these data. Magnetization versus field isotherms evolve with composition and with temperature; those for x=0.24 5 and 0.16 9 exhibit S-shapes for temperatures at or below the identified transitions. The nonlinear susceptibility versus temperature for x=0.24 5 displays structure but does not diverge. The temperature dependence of the thermoremanent magnetization (TRM) for x=0.24 5 shows characteristic features but does not follow any simple form. The time-dependence of the TRM is fitted at a series of temperatures employing a stretched exponential decay form. The thermal variation of the fit parameters is systematic and suggests that temperatures just below 3 K and slightly above 6 K have special significance. Over a limited temperature range the TRM is found to scale approximately as T log10(t/τ 0) , with τ0≈10 -12 s. Strong and weak irreversibility lines are determined for x=0.24 5; both vary as τg∝ h0.56, with zero-field temperatures of Ts(0)=5.5 5 K and Tw(0)=9.8 5 K, respectively. The exponent is closer to that recently predicted (0.53) for a short-range three-dimensional Ising spin glass than to the value 2/3 of the DeAlmeida-Thouless line in the infinite range mean-field Ising model. The existence of strong random anisotropy may account for the presence of a weak irreversibility line with the observed exponent. The T- x magnetic phase diagram exhibits a crossing of paramagnetic-ordered state phase boundaries and an associated tetracritical point at x≈0.20 5 and T≈2.6 0 K. Spin glass properties are apparent for compositions close to the tetracritical point.

Soil Methanotrophy Model (MeMo v1.0): a process-based model to quantify global uptake of atmospheric methane by soil

NASA Astrophysics Data System (ADS)

Murguia-Flores, Fabiola; Arndt, Sandra; Ganesan, Anita L.; Murray-Tortarolo, Guillermo; Hornibrook, Edward R. C.

2018-06-01

Soil bacteria known as methanotrophs are the sole biological sink for atmospheric methane (CH4), a potent greenhouse gas that is responsible for ˜ 20 % of the human-driven increase in radiative forcing since pre-industrial times. Soil methanotrophy is controlled by a plethora of factors, including temperature, soil texture, moisture and nitrogen content, resulting in spatially and temporally heterogeneous rates of soil methanotrophy. As a consequence, the exact magnitude of the global soil sink, as well as its temporal and spatial variability, remains poorly constrained. We developed a process-based model (Methanotrophy Model; MeMo v1.0) to simulate and quantify the uptake of atmospheric CH4 by soils at the global scale. MeMo builds on previous models by Ridgwell et al. (1999) and Curry (2007) by introducing several advances, including (1) a general analytical solution of the one-dimensional diffusion-reaction equation in porous media, (2) a refined representation of nitrogen inhibition on soil methanotrophy, (3) updated factors governing the influence of soil moisture and temperature on CH4 oxidation rates and (4) the ability to evaluate the impact of autochthonous soil CH4 sources on uptake of atmospheric CH4. We show that the improved structural and parametric representation of key drivers of soil methanotrophy in MeMo results in a better fit to observational data. A global simulation of soil methanotrophy for the period 1990-2009 using MeMo yielded an average annual sink of 33.5 ± 0.6 Tg CH4 yr-1. Warm and semi-arid regions (tropical deciduous forest and open shrubland) had the highest CH4 uptake rates of 602 and 518 mg CH4 m-2 yr-1, respectively. In these regions, favourable annual soil moisture content ( ˜ 20 % saturation) and low seasonal temperature variations (variations < ˜ 6 °C) provided optimal conditions for soil methanotrophy and soil-atmosphere gas exchange. In contrast to previous model analyses, but in agreement with recent observational data, MeMo predicted low fluxes in wet tropical regions because of refinements in formulation of the influence of excess soil moisture on methanotrophy. Tundra and mixed forest had the lowest simulated CH4 uptake rates of 176 and 182 mg CH4 m-2 yr-1, respectively, due to their marked seasonality driven by temperature. Global soil uptake of atmospheric CH4 was decreased by 4 % by the effect of nitrogen inputs to the system; however, the direct addition of fertilizers attenuated the flux by 72 % in regions with high agricultural intensity (i.e. China, India and Europe) and by 4-10 % in agriculture areas receiving low rates of N input (e.g. South America). Globally, nitrogen inputs reduced soil uptake of atmospheric CH4 by 1.38 Tg yr-1, which is 2-5 times smaller than reported previously. In addition to improved characterization of the contemporary soil sink for atmospheric CH4, MeMo provides an opportunity to quantify more accurately the relative importance of soil methanotrophy in the global CH4 cycle in the past and its capacity to contribute to reduction of atmospheric CH4 levels under future global change scenarios.

Perovskite-based solar cells with inorganic inverted hybrid planar heterojunction structure

NASA Astrophysics Data System (ADS)

Lai, Wei-Chih; Lin, Kun-Wei; Guo, Tzung-Fang; Chen, Peter; Liao, Yuan-Yu

2018-01-01

We demonstrated the good performance of inorganic inverted CH3NH3PbI3 perovskite-based solar cells (SCs) with glass/ITO/NiOx/CH3NH3PbI3 perovskite/C60/ room temperature (RT)-sputtered ZnO/Al structure. We adopted spin coating and RT sputtering for the deposition of NiOx and ZnO, respectively. The inorganic hole and electron transport layer of NiOx and RT-sputtered ZnO, respectively, could improve the open-circuit voltage (VOC), short-circuit current density (JSC), and power conversion efficiency (η%) of the SCs. We obtained inorganic inverted CH3NH3PbI3 perovskite-based SCs with a JSC of 21.96 A/cm2, a VOC of 1.02 V, a fill factor (FF%) of 68.2%, and an η% of 15.3% despite the sputtering damage of the RT-sputtered ZnO deposition. Moreover, the RT-sputtered ZnO could function as a diffusion barrier for Al, moisture, and O2. The inorganic inverted CH3NH3PbI3 perovskite-based SCs demonstrated improved storage reliability.

Effects of experimental warming and mowing on greenhouse gas fluxes in an alpine meadow on the Tibetan Plateau

NASA Astrophysics Data System (ADS)

Wang, Jinsong; Quan, Quan; Sun, Jian; Niu, Shuli

2017-04-01

Rapid climate change and intensified human activities on the Tibetan Plateau may alter the magnitude and direction of greenhouse gas (GHG) emissions, affecting the climate change impact on these fragile ecosystems. We conducted a controlled experiment to investigate the effects of warming and mowing (simulation of grazing) on soil CO2, CH4 and N2O fluxes in an alpine meadow in eastern Tibetan Plateau between August 2015 and July 2016. Three levels of temperature (C, ambient temperature; W1, < 2 °C warming at 5 cm soil depth by infrared heaters; and W2, > 2 °C warming) were combined with two levels of mowing treatment (UM, un-mowing; and M, mowing). GHG fluxes were measured once an hour using static chamber. Both CO2 emission and CH4 uptake rates showed a seasonal fluctuation, with the maximum value occurred in late summer and the minimum in winter. However, N2O flux did not show a strong seasonal pattern. High level of warming (W2) regardless of mowing significantly increased CO2 emission and CH4 uptake by 15.4 % and 38.2 % averaged over the year, compared with no-warming (C). Moderate warming (W1) did not have significant effects on either CO2 or CH4 fluxes. N2O flux was reduced by 54.1% by W2 and 15.7% by W1 warming. Mowing alone increased CH4 uptake and N2O emission by 18.0 % and 12.7%, respectively, but had no significant effect on CO2 flux. The interactions between warming and mowing were detected in CO2 and CH4 fluxes. Among all treatments, W2UM in general had the highest rates of CO2 emission and CH4 uptake but the lowest rate of N2O flux, while CUM and CM showed the opposite. In addition, warming induced increase in CH4 uptake and decline in N2O release had very limited ability to offset the enhanced CO2 emission, resulting in a net positive feedback of the three GHGs to climate warming. Furthermore, daily CO2 flux increased exponentially with soil temperature at 5 cm. CH4 flux correlated negatively with soil temperature but positively with soil moisture.

High-temperature charge density wave correlations in La1.875Ba0.125CuO4 without spin–charge locking

PubMed Central

Lorenzana, J.; Seibold, G.; Peng, Y. Y.; Amorese, A.; Yakhou-Harris, F.; Kummer, K.; Brookes, N. B.; Konik, R. M.; Thampy, V.; Gu, G. D.; Ghiringhelli, G.; Braicovich, L.

2017-01-01

Although all superconducting cuprates display charge-ordering tendencies, their low-temperature properties are distinct, impeding efforts to understand the phenomena within a single conceptual framework. While some systems exhibit stripes of charge and spin, with a locked periodicity, others host charge density waves (CDWs) without any obviously related spin order. Here we use resonant inelastic X-ray scattering to follow the evolution of charge correlations in the canonical stripe-ordered cuprate La1.875Ba0.125CuO4 across its ordering transition. We find that high-temperature charge correlations are unlocked from the wavevector of the spin correlations, signaling analogies to CDW phases in various other cuprates. This indicates that stripe order at low temperatures is stabilized by the coupling of otherwise independent charge and spin density waves, with important implications for the relation between charge and spin correlations in the cuprates. PMID:29114049

Reactions of VX, HD, and their simulants with NaY and AgY zeolites. Desulfurization of VX on AgY

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

Wagner, G.W.; Bartram, P.W.

1999-11-09

The room-temperature reactions of the chemical warfare agents VX (O-ethyl S-2-(diisopropylamino)-ethyl methylphosphonothioate), HD (2,2{prime}-dichloroethyl sulfide, or mustard), and their common simulants, O,S-diethyl phenylphosphonothioate (DEPPT) and 2-chloroethyl phenyl sulfide (CEPS), with NaY and silver-exchanged (AgY) zeolites have been studied using solid-state magic angle spinning NMR. VX hydrolyzes via exclusive cleavage of the P{single{underscore}bond}S bond on both NaY and AgY to yield ethyl methylphosphonate (EMPA). The reaction is significantly faster on AgY than on NaY, suggesting catalysis by silver. On AgY, an intermediate silver salt of EMPA is apparently formed which is slowly converted to ethyl 2-(diisopropylamino)ethyl methylphosphonate (QB, the desulfurized analoguemore » of VX) in about a 78% yield. DEPPT similarly hydrolyzes via P{single{underscore}bond}S cleavage on AgY to yield an apparent silver salt of ethyl phenylphosphonate, which does not undergo further reaction to the desulfurized analogue. No reaction is observed for DEPPT on NaY. HD on AgY forms both vinyl sulfide and the cyclic ether 1,4-thioxane. HD reacts faster on NaY to exclusively form the CH-TG sulfonium ion (HOCH{sub 2}CH{sub 2}SCH{sub 2}CH{sub 2}S{sup +}[CH{sub 2}CH{sub 2}OH]{sub 2}). CEPS also reacts faster on NaY, forming 2-hydroxyethyl phenyl sulfide. On AgY, CEPS does not give the vinyl product, but does yield the ether product PhSCH{sub 2}CH{sub 2}OCH{sub 2}CH{sub 2}SPh. A mechanism is proposed for the silver-catalyzed hydrolysis of VX, the desulfurization of the cleaved thiol, and the formation of QB.« less

Permafrost Thaw Induces Methane Oxidation in Transitional Thaw Stages in a Subarctic Peatland

NASA Astrophysics Data System (ADS)

Perryman, C. R.; Kashi, N. N.; Malhotra, A.; McCalley, C. K.; Varner, R. K.

2015-12-01

Rising temperatures in the subarctic are accelerating permafrost thaw and increasing methane (CH4) emissions from subarctic peatlands. Methanotrophs in these peatlands can consume/oxidize CH4, potentially mitigating CH4 emissions in these peatlands. Oxidation rates can exceed 90% of CH4 production in some settings, depending on O2 and CH4 availability and environmental conditions. Malhotra and Roulet identified 10 thaw stages in Stordalen Mire near Abisko, Sweden (68°21'N,18°49'E ) with variable vegetation, environmental conditions, and associated CH4 emissions. We investigated potential methane oxidation rates across these thaw stages. Peat cores were extracted from two depths at each stage and incubated in 350ml glass jars at in situ temperatures and CH4 concentrations. Headspace samples were collected from each incubation jar over a 48-hour period and analyzed for CH4 concentration using flame ionization detection gas chromatography (GC-FID). Oxidation rates ranged from <0.1 to 17 μg of CH4 per gram of dry biomass per day. Water table depth and pore water pH were the strongest environmental correlates of oxidation (sample size = 56, p < 0.001). The highest potential oxidation rates were observed in collapsing palsa sites and recently collapsed sedge-dominated open water sites near palsa mounds. Our results suggest that permafrost thaw induces high CH4 oxidation rates by creating conditions ideal for both methanogenic and methanotrophic microbial communities. Our results also reinforce the importance of incorporating transitional thaw stages in landscape level carbon budgets of thawing peatlands emphasized by Malhotra and Roulet. Forthcoming microbial analysis and stable isotope analysis will further elucidate the factors controlling methane oxidation rates at Stordalen Mire.

Environmental factors controlling methane emissions from peatlands in northern Minnesota

NASA Technical Reports Server (NTRS)

Dise, Nancy B.; Gorham, Eville; Verry, Elon S.

1993-01-01

The environmental factors affecting the emission of methane from peatlands were investigated by correlating CH4 emission data for two years, obtained from five different peatland ecosystems in northern Minnesota, with peat temperature, water table position, and degree of peat humification. The relationship obtained between the CH4 flux and these factors was compared to results from a field manipulation experiment in which the water table was artificially raised in three experimental plots within the driest peatland. It was found that peat temperature, water table position, and degree of peat humification explained 91 percent of the variance in log CH4 flux, successfully predicted annual CH4 emission from individual wetlands, and predicted the change in flux due to the water table manipulation. Raising the water table in the bog corrals by an average of 6 cm in autumn 1989 and 10 cm in summer 1990 increased CH4 emission by 2.5 and 2.2 times, respectively.

Metabolic and trophic interactions modulate methane production by Arctic peat microbiota in response to warming

PubMed Central

Tveit, Alexander Tøsdal; Urich, Tim; Frenzel, Peter; Svenning, Mette Marianne

2015-01-01

Arctic permafrost soils store large amounts of soil organic carbon (SOC) that could be released into the atmosphere as methane (CH4) in a future warmer climate. How warming affects the complex microbial network decomposing SOC is not understood. We studied CH4 production of Arctic peat soil microbiota in anoxic microcosms over a temperature gradient from 1 to 30 °C, combining metatranscriptomic, metagenomic, and targeted metabolic profiling. The CH4 production rate at 4 °C was 25% of that at 25 °C and increased rapidly with temperature, driven by fast adaptations of microbial community structure, metabolic network of SOC decomposition, and trophic interactions. Below 7 °C, syntrophic propionate oxidation was the rate-limiting step for CH4 production; above this threshold temperature, polysaccharide hydrolysis became rate limiting. This change was associated with a shift within the functional guild for syntrophic propionate oxidation, with Firmicutes being replaced by Bacteroidetes. Correspondingly, there was a shift from the formate- and H2-using Methanobacteriales to Methanomicrobiales and from the acetotrophic Methanosarcinaceae to Methanosaetaceae. Methanogenesis from methylamines, probably stemming from degradation of bacterial cells, became more important with increasing temperature and corresponded with an increased relative abundance of predatory protists of the phylum Cercozoa. We concluded that Arctic peat microbiota responds rapidly to increased temperatures by modulating metabolic and trophic interactions so that CH4 is always highly produced: The microbial community adapts through taxonomic shifts, and cascade effects of substrate availability cause replacement of functional guilds and functional changes within taxa. PMID:25918393

Temperature dependence of magneto-transport properties in Co{sub 2}Fe(Ga{sub 0.5}Ge{sub 0.5})/Cu lateral spin valves

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

Ikhtiar,; Mitani, S.; Hono, K.

2016-02-08

The non-local spin signals of Co{sub 2}Fe(Ga{sub 0.5}Ge{sub 0.5})/Cu lateral spin valves with sub-micron size dimensions were measured with varying temperatures. The non-local spin signal reaches 54 mΩ at 4 K, while it degrades down to 13 mΩ at room temperature. Analysis based on the one-dimensional spin diffusion model clarifies the dominant source for degrading of the spin signal is suppression of the spin diffusion length in Cu, not the spin polarization, indicating Co{sub 2}Fe(Ga{sub 0.5}Ge{sub 0.5}) keeps half-metallic nature even at room temperature. The temperature dependence of non-local spin signal was found to exhibit a downturn at 36 K. The presence of magneticmore » impurities, detrimental effect of which becomes more pronounced for diffusive transport in long Cu wires, is suggested to cause the observed downturn in non-local spin signals.« less

Electrical spin injection from CoFe2O4 into p-Si semiconductor across MgO tunnel barrier for spin electronics

NASA Astrophysics Data System (ADS)

Panda, J.; Maji, Nilay; Nath, T. K.

2017-05-01

The room temperature spin injection and detection in non magnetic p-Si semiconductor have been studied in details in our CoFe2O4 (CFO)/MgO/p-Si heterojunction. The 3-terminal tunnel contacts have been made on the device for transport measurements. The electrical transport properties have been investigated at different isothermal conditions in the temperature range of 10-300 K. The spin accumulation in non magnetic p-Si semiconductor has been observed at different bias current under the applied magnetic field parallel to the film plane in the temperature range of 40-300 K. We have observed a giant spin accumulation in p-Si semiconductor using MgO/CFO tunnel contact. The Hanley effect is used to control the reduction of spin accumulation by applying magnetic field perpendicular to the carrier spin in the p-Si. The accumulated spin signal decays as a function of applied magnetic field for fixed bias current. These results will enable utilization of the spin degree of freedom in complementary Si devices and its further development.

Room temperature electrical spin injection into GaAs by an oxide spin injector

PubMed Central

Bhat, Shwetha G.; Kumar, P. S. Anil

2014-01-01

Spin injection, manipulation and detection are the integral parts of spintronics devices and have attracted tremendous attention in the last decade. It is necessary to judiciously choose the right combination of materials to have compatibility with the existing semiconductor technology. Conventional metallic magnets were the first choice for injecting spins into semiconductors in the past. So far there is no success in using a magnetic oxide material for spin injection, which is very important for the development of oxide based spintronics devices. Here we demonstrate the electrical spin injection from an oxide magnetic material Fe3O4, into GaAs with the help of tunnel barrier MgO at room temperature using 3-terminal Hanle measurement technique. A spin relaxation time τ ~ 0.9 ns for n-GaAs at 300 K is observed along with expected temperature dependence of τ. Spin injection using Fe3O4/MgO system is further established by injecting spins into p-GaAs and a τ of ~0.32 ns is obtained at 300 K. Enhancement of spin injection efficiency is seen with barrier thickness. In the field of spin injection and detection, our work using an oxide magnetic material establishes a good platform for the development of room temperature oxide based spintronics devices. PMID:24998440

Cold season emissions dominate the Arctic tundra methane budget

NASA Astrophysics Data System (ADS)

Zona, Donatella; Gioli, Beniamino; Commane, Róisín; Lindaas, Jakob; Wofsy, Steven C.; Miller, Charles E.; Dinardo, Steven J.; Dengel, Sigrid; Sweeney, Colm; Karion, Anna; Chang, Rachel Y.-W.; Henderson, John M.; Murphy, Patrick C.; Goodrich, Jordan P.; Moreaux, Virginie; Liljedahl, Anna; Watts, Jennifer D.; Kimball, John S.; Lipson, David A.; Oechel, Walter C.

2016-01-01

Arctic terrestrial ecosystems are major global sources of methane (CH4); hence, it is important to understand the seasonal and climatic controls on CH4 emissions from these systems. Here, we report year-round CH4 emissions from Alaskan Arctic tundra eddy flux sites and regional fluxes derived from aircraft data. We find that emissions during the cold season (September to May) account for ≥50% of the annual CH4 flux, with the highest emissions from noninundated upland tundra. A major fraction of cold season emissions occur during the "zero curtain" period, when subsurface soil temperatures are poised near 0 °C. The zero curtain may persist longer than the growing season, and CH4 emissions are enhanced when the duration is extended by a deep thawed layer as can occur with thick snow cover. Regional scale fluxes of CH4 derived from aircraft data demonstrate the large spatial extent of late season CH4 emissions. Scaled to the circumpolar Arctic, cold season fluxes from tundra total 12 ± 5 (95% confidence interval) Tg CH4 y-1, ∼25% of global emissions from extratropical wetlands, or ∼6% of total global wetland methane emissions. The dominance of late-season emissions, sensitivity to soil environmental conditions, and importance of dry tundra are not currently simulated in most global climate models. Because Arctic warming disproportionally impacts the cold season, our results suggest that higher cold-season CH4 emissions will result from observed and predicted increases in snow thickness, active layer depth, and soil temperature, representing important positive feedbacks on climate warming.

Cold season emissions dominate the Arctic tundra methane budget.

PubMed

Zona, Donatella; Gioli, Beniamino; Commane, Róisín; Lindaas, Jakob; Wofsy, Steven C; Miller, Charles E; Dinardo, Steven J; Dengel, Sigrid; Sweeney, Colm; Karion, Anna; Chang, Rachel Y-W; Henderson, John M; Murphy, Patrick C; Goodrich, Jordan P; Moreaux, Virginie; Liljedahl, Anna; Watts, Jennifer D; Kimball, John S; Lipson, David A; Oechel, Walter C

2016-01-05

Arctic terrestrial ecosystems are major global sources of methane (CH4); hence, it is important to understand the seasonal and climatic controls on CH4 emissions from these systems. Here, we report year-round CH4 emissions from Alaskan Arctic tundra eddy flux sites and regional fluxes derived from aircraft data. We find that emissions during the cold season (September to May) account for ≥ 50% of the annual CH4 flux, with the highest emissions from noninundated upland tundra. A major fraction of cold season emissions occur during the "zero curtain" period, when subsurface soil temperatures are poised near 0 °C. The zero curtain may persist longer than the growing season, and CH4 emissions are enhanced when the duration is extended by a deep thawed layer as can occur with thick snow cover. Regional scale fluxes of CH4 derived from aircraft data demonstrate the large spatial extent of late season CH4 emissions. Scaled to the circumpolar Arctic, cold season fluxes from tundra total 12 ± 5 (95% confidence interval) Tg CH4 y(-1), ∼ 25% of global emissions from extratropical wetlands, or ∼ 6% of total global wetland methane emissions. The dominance of late-season emissions, sensitivity to soil environmental conditions, and importance of dry tundra are not currently simulated in most global climate models. Because Arctic warming disproportionally impacts the cold season, our results suggest that higher cold-season CH4 emissions will result from observed and predicted increases in snow thickness, active layer depth, and soil temperature, representing important positive feedbacks on climate warming.

Cold season emissions dominate the Arctic tundra methane budget

PubMed Central

Zona, Donatella; Gioli, Beniamino; Lindaas, Jakob; Wofsy, Steven C.; Miller, Charles E.; Dinardo, Steven J.; Dengel, Sigrid; Sweeney, Colm; Karion, Anna; Chang, Rachel Y.-W.; Henderson, John M.; Murphy, Patrick C.; Goodrich, Jordan P.; Moreaux, Virginie; Liljedahl, Anna; Watts, Jennifer D.; Kimball, John S.; Lipson, David A.; Oechel, Walter C.

2016-01-01

Arctic terrestrial ecosystems are major global sources of methane (CH4); hence, it is important to understand the seasonal and climatic controls on CH4 emissions from these systems. Here, we report year-round CH4 emissions from Alaskan Arctic tundra eddy flux sites and regional fluxes derived from aircraft data. We find that emissions during the cold season (September to May) account for ≥50% of the annual CH4 flux, with the highest emissions from noninundated upland tundra. A major fraction of cold season emissions occur during the “zero curtain” period, when subsurface soil temperatures are poised near 0 °C. The zero curtain may persist longer than the growing season, and CH4 emissions are enhanced when the duration is extended by a deep thawed layer as can occur with thick snow cover. Regional scale fluxes of CH4 derived from aircraft data demonstrate the large spatial extent of late season CH4 emissions. Scaled to the circumpolar Arctic, cold season fluxes from tundra total 12 ± 5 (95% confidence interval) Tg CH4 y−1, ∼25% of global emissions from extratropical wetlands, or ∼6% of total global wetland methane emissions. The dominance of late-season emissions, sensitivity to soil environmental conditions, and importance of dry tundra are not currently simulated in most global climate models. Because Arctic warming disproportionally impacts the cold season, our results suggest that higher cold-season CH4 emissions will result from observed and predicted increases in snow thickness, active layer depth, and soil temperature, representing important positive feedbacks on climate warming. PMID:26699476

Centennial to millennial variations of atmospheric methane during the early Holocene

NASA Astrophysics Data System (ADS)

Yang, Ji-Woong; Ahn, Jinho; Brook, Edward

2015-04-01

Atmospheric CH4 is one of the most important greenhouse gases. Ice core studies revealed strong correlations between millennial CH4 variations and Greenland climate during the last glacial period. However, millennial to sub-millennial CH4 variations during interglacial periods are not well studied. Recently, several high-resolution data sets have been produced for the late Holocene, but it is difficult to distinguish natural- from anthropogenic changes. In contrast, the methane budget of the early Holocene is not affected by anthropogenic disturbances, thus may help us better understand natural CH4 control mechanisms under interglacial climate boundary conditions. Here we present our new high-precision and high-resolution atmospheric CH4 record from Siple Dome ice core, Antarctica that covers the early Holocene. We used our new wet extraction system at Seoul National University that shows a good precision of ~1 ppb. Our data show several tens of ppb of centennial- to millennial CH4 variations and an anti-correlative evolution with Greenland climate on the millennial time scale. The CH4 record could have been affected by many different types of forcing, including temperature, precipitation (monsoon intensity), biomass burning, sea surface temperature, and solar activity. According to our data, early Holocene CH4 is well correlated with records of hematite stained grains (HSG) in North Atlantic sediment records, within age uncertainties. A red-noise spectral analysis yields peaks at frequencies of ~1270 and ~80 years, which are similar to solar frequencies, but further investigations are needed to determine major controlling factor of atmospheric CH4during the early Holocene.

Cold season emissions dominate the Arctic tundra methane budget

DOE PAGES

Zona, Donatella; Gioli, Beniamino; Commane, Róisín; ...

2015-12-22

Arctic terrestrial ecosystems are major global sources of methane (CH 4); hence, it is important to understand the seasonal and climatic controls on CH 4 emissions from these systems. Here, we report year-round CH 4 emissions from Alaskan Arctic tundra eddy flux sites and regional fluxes derived from aircraft data. We find that emissions during the cold season (September to May) account for ≥ 50% of the annual CH 4 flux, with the highest emissions from noninundated upland tundra. A major fraction of cold season emissions occur during the “zero curtain” period, when subsurface soil temperatures are poised near 0more » °C. The zero curtain may persist longer than the growing season, and CH 4 emissions are enhanced when the duration is extended by a deep thawed layer as can occur with thick snow cover. Regional scale fluxes of CH 4 derived from aircraft data demonstrate the large spatial extent of late season CH 4 emissions. Scaled to the circumpolar Arctic, cold season fluxes from tundra total 12 ± 5 (95% confidence interval) Tg CH 4 y –1, ~25% of global emissions from extratropical wetlands, or ~6% of total global wetland methane emissions. Here, the dominance of late-season emissions, sensitivity to soil environmental conditions, and importance of dry tundra are not currently simulated in most global climate models. Because Arctic warming disproportionally impacts the cold season, our results suggest that higher cold-season CH 4 emissions will result from observed and predicted increases in snow thickness, active layer depth, and soil temperature, representing important positive feedbacks on climate warming.« less

Temperature Dependence of the Energy Levels of Methylammonium Lead Iodide Perovskite from First-Principles.

PubMed

Saidi, Wissam A; Poncé, Samuel; Monserrat, Bartomeu

2016-12-15

Environmental effects and intrinsic energy-loss processes lead to fluctuations in the operational temperature of solar cells, which can profoundly influence their power conversion efficiency. Here we determine from first-principles the effects of temperature on the band gap and band edges of the hybrid pervoskite CH 3 NH 3 PbI 3 by accounting for electron-phonon coupling and thermal expansion. From 290 to 380 K, the computed band gap change of 40 meV coincides with the experimental change of 30-40 meV. The calculation of electron-phonon coupling in CH 3 NH 3 PbI 3 is particularly intricate as the commonly used Allen-Heine-Cardona theory overestimates the band gap change with temperature, and excellent agreement with experiment is only obtained when including high-order terms in the electron-phonon interaction. We also find that spin-orbit coupling enhances the electron-phonon coupling strength but that the inclusion of nonlocal correlations using hybrid functionals has little effect. We reach similar conclusions in the metal-halide perovskite CsPbI 3 . Our results unambiguously confirm for the first time the importance of high-order terms in the electron-phonon coupling by direct comparison with experiment.

On the methane paradox: Transport from shallow water zones rather than in situ methanogenesis is the major source of CH4 in the open surface water of lakes

NASA Astrophysics Data System (ADS)

Encinas Fernández, Jorge; Peeters, Frank; Hofmann, Hilmar

2016-10-01

Estimates of global methane (CH4) emissions from lakes and the contributions of different pathways are currently under debate. In situ methanogenesis linked to algae growth was recently suggested to be the major source of CH4 fluxes from aquatic systems. However, based on our very large data set on CH4 distributions within lakes, we demonstrate here that methane-enriched water from shallow water zones is the most likely source of the basin-wide mean CH4 concentrations in the surface water of lakes. Consistently, the mean surface CH4 concentrations are significantly correlated with the ratio between the surface area of the shallow water zone and the entire lake, fA,s/t, but not with the total surface area. The categorization of CH4 fluxes according to fA,s/t may therefore improve global estimates of CH4 emissions from lakes. Furthermore, CH4 concentrations increase substantially with water temperature, indicating that seasonally resolved data are required to accurately estimate annual CH4 emissions.

Controls on northern wetland methane emissions: insights from regional synthesis studies and the Alaska Peatland Experiment (APEX)

NASA Astrophysics Data System (ADS)

Turetsky, M. R.; Euskirchen, E. S.; Czimczik, C. I.; Waldrop, M. P.; Olefeldt, D.; Fan, Z.; Kane, E. S.; McGuire, A. D.; Harden, J. W.

2014-12-01

Wetlands are the largest natural source of atmospheric methane. Static chambers have been used to quantify variation in wetland CH4 flux for many decades. Regional to global scale synthesis studies of static chamber measurements show that relationships between temperature, water availability and CH4 emissions depend on wetland type (bog, fen, swamp), region (tropical, temperate, arctic) and disturbance. For example, while water table position and temperature serve as the dominant controls on bog and swamp CH4 flux, vegetation is an important control on emissions from fens. These studies highlight the fact that wetland types have distinct controls on CH4 emissions; however, it is unlikely that modeling of wetland CH4 flux will improve without a better mechanistic understanding of the processes underlying CH4 production, transport, and oxidation. At the Alaska Peatland Experiment, we are quantifying CH4 emission using static chambers, automated chambers, and towers. Our sites vary in permafrost regime, including groundwater fens without permafrost, forested peat plateaus with intact permafrost, and collapse scar bogs formed through permafrost thaw. Experimental studies that examine plant and microbial responses to altered water table position and soil temperature are complemented by a gradient approach, where we use a space-for-time substitutions to examine the consequences of thaw on time-scales of decades to centuries. Our results thus far have documented the importance of soil rewetting in governing large CH4 fluxes from northern wetland soils. Accounting for CH4, our collapse scar bog significantly contributed to the global warming potential of the landscape. A major objective of our work is to explore the role of permafrost C release in greenhouse gas fluxes from wetland soils, which we are assessing using radiocarbon as a natural tracer. We have shown, for example, that ebullition of CH4 is dominated by recently fixed C, but a significant fraction of CH4 in bubbles is derived from old C released during thaw. The APEX time series datasets are being used in a variety of modeling studies, from small-scale soil pore and microbial controls on gas production and transport to regional scale assessments of how carbon cycle feedbacks to climate vary with wetland type and abundance.

Regimes of an atmospheric pressure nanosecond repetitively pulsed discharge for methane partial oxidation

NASA Astrophysics Data System (ADS)

Maqueo, P. D. G.; Maier, M.; Evans, M. D. G.; Coulombe, S.; Bergthorson, J. M.

2018-04-01

The operation of a nanosecond repetitively pulsed discharge for partial oxidation of CH4 is characterized at atmospheric pressure and room temperature. Two regimes are observed: diffuse and filamentary. The first is a low power regime, characterized by low rotational temperatures around 400 K. The second is much more energetic with rotational temperatures close to 600 K. Both have vibrational temperatures of at least 10 times their rotational temperatures. The average electron number density was determined to be 8.9×1015 and 4.0×1017 cm-3, respectively, showing an increase in the ionization fraction in the more powerful filamentary regime. Results of CH4 conversion to H2, CO, CO2 and C2H6 are presented for the filamentary regime, while the diffuse regime shows no measurable conversion ability. As expected, oxidative mixtures show higher conversion ability than pure CH4. A maximum conversion efficiency of 26.3% and a maximum energy efficiency of 19.7% were reached for the oxidative mixtures.

Thermomagnetic, dielectric and EPR studies on four new multiferroics

NASA Astrophysics Data System (ADS)

Ramachandran, Vasanth

Multiferroics are materials which exhibit at least two or all three of the ferroic (ferroelectric, ferromagnetic and ferroelastic) orders co-existing in them, and are of high current interest in both the fundamental research and in the discovery of new multifunctional materials. This dissertation presents thermomagnetic, dielectric and electron paramagnetic resonance (EPR) studies on some new multiferroics. The primary focus of this work is on these four compounds: [(CH3)2NH2]Mn(HCOO)3, K3Fe5F15, Pb(Fe1/2Nb1/2)O 3, and MnV2O4. Chapter 3 discusses our discovery of multiferroic behavior of the metal-organic framework (MOF) compound dimethylammonium manganese formate, [(CH3)2NH2]Mn(HCOO) 3, with the aid of single crystal heat capacity and EPR measurements on the compound. Simultaneous occurrence of ferroelectric and antiferromagnetic long-range orders in this compound established its multiferroic nature. Chapter 4 describes the multiferroic nature of the 'tetragonal tungsten bronze'-type ferroelectric potassium iron fluoride, K3Fe5 F15, studied by magnetic susceptibility, magnetization, dielectric and EPR characterization of single crystal and polycrystalline samples. A weak ferromagnetic (FM) ordering due to spin canting caused by the antisymmetric exchange interaction between the Fe ions, and its influence on the dielectric constant evident by the observation of an anomaly around the FM ordering temperature, together indicate an intrinsic magnetoelectric coupling present in this compound. Chapter 5 describes multiferroic behavior of the complex oxide perovskite lead iron niobate, Pb(Fe1/2Nb1/2)O3 abbreviated as PFN. Systematic (9.4, 34, 381, 683 GHz) EPR and magnetic susceptibility measurements on polycrystalline PFN samples show an antiferromagnetic (AFM) ordering, the presence of a small finite internal field well above the AFM ordering temperature, and the first observation of an anomaly in the susceptibility near the ferroelectric Curie point, together implying the presence of magnetoelectric effect. Chapter 6 presents ac and dc magnetic susceptibility experiments on the magnetoelastic spinel compound manganese vanadate, MnV2O4. The compound is shown to exhibit a re-entrant spin glass behavior. The results and perspectives presented here should contribute to the advancement and fundamental understanding of multiferroic materials.

Physical properties of i-R-Cd quasicrystals(R = Y, Gd-Tm)

NASA Astrophysics Data System (ADS)

Kong, Tai; Bud'Ko, Sergey L.; Jesche, Anton; Goldman, Alan I.; Kreyssig, Andreas; Dennis, Kevin W.; Ramazanoglu, Mehmet; Canfield, Paul C.; McArthur, John

2014-03-01

Detailed characterization of recently discovered i-R-Cd (R = Y, Gd-Tm) binary quasicrystals by means of room-temperature powder x-ray diffraction, dc and ac magnetization, resistivity and specific heat measurements will be presented. i-Y-Cd is weakly diamagnetic. The dc magnetization of i-R-Cd (R = Gd, Ho-Tm) shows typical spin-glass type splitting between field-cooled (FC) and zero-field-cooled (ZFC) data. i-Tb-Cd and i-Dy-Cd do not show a clear cusp in their ZFC dc magnetization. ac magnetization measured on i-Gd-Cd indicates a clear frequency-dependence and the third-order non-linear magnetization, χ3, is consistent with a spin-glass transition. The resistivity for i-R-Cd is of order 100 μΩ cm and weakly temperature-dependent. No feature that can be associated with long-range magnetic order was observed in any of the measurements. Characteristic freezing temperatures for i-R-Cd (R = Gd-Tm) deviate from ideal de Gennes scaling. This work is supported by the US DOE, Basic Energy Sciences under Contract No. DE-AC02-07CH11358.

Synergistic effects of plasma-catalyst interactions for CH4 activation.

PubMed

Kim, Jongsik; Go, David B; Hicks, Jason C

2017-05-24

The elucidation of catalyst surface-plasma interactions is a challenging endeavor and therefore requires thorough and rigorous assessment of the reaction dynamics on the catalyst in the plasma environment. The first step in quantifying and defining catalyst-plasma interactions is a detailed kinetic study that can be used to verify appropriate reaction conditions for comparison and to discover any unexpected behavior of plasma-assisted reactions that might prevent direct comparison. In this paper, we provide a kinetic evaluation of CH 4 activation in a dielectric barrier discharge plasma in order to quantify plasma-catalyst interactions via kinetic parameters. The dry reforming of CH 4 with CO 2 was studied as a model reaction using Ni supported on γ-Al 2 O 3 at temperatures of 790-890 K under atmospheric pressure, where the partial pressures of CH 4 (or CO 2 ) were varied over a range of ≤25.3 kPa. Reaction performance was monitored by varying gas hourly space velocity, plasma power, bulk gas temperature, and reactant concentration. After correcting for gas-phase plasma reactions, a linear relationship was observed in the log of the measured rate constant with respect to reciprocal power (1/power). Although thermal catalysis displays typical Arrhenius behavior for this reaction, plasma-assisted catalysis occurs from a complex mixture of sources and shows non-Arrhenius behavior. However, an energy barrier was obtained from the relationship between the reaction rate constant and input power to exhibit ≤∼20 kJ mol -1 (compared to ∼70 kJ mol -1 for thermal catalysis). Of additional importance, the energy barriers measured during plasma-assisted catalysis were relatively consistent with respect to variations in total flow rates, types of diluent, or bulk reaction temperature. These experimental results suggest that plasma-generated vibrationally-excited CH 4 favorably interacts with Ni sites at elevated temperatures, which helps reduce the energy barrier required to activate CH 4 and enhance CH 4 reforming rates.

Studies of Energy-Relevant Materials by Nuclear Magnetic Resonance

NASA Astrophysics Data System (ADS)

Cui, Jinfang

In this thesis, we have used nuclear magnetic resonance (NMR) as a local probe to microscopically study three different families of energy-relevant complex materials, namely the 122 Fe-based superconductors Ca(Fe1-xCox)2As2, GeTe-based thermoelectric tellurides GeTe and detonation nanodiamond. In Chapter 3 and Chapter 4, we investigated the Co substitution effects on static and dynamic magnetic properties of the single-crystalline Ca(Fe 1-xCox)2As2 (x = 0, 0.023, 0.028, 0.033, 0.059) via 75As NMR and resistivity measurements. Robustness of the Fe magnetic moments was evidenced by only slight decreases of Hint, although T N is strongly suppressed with Co substitution in antiferromagnetic (AFM) state. In the paramagnetic (PM) state, the temperature dependence of Knight shift K for all crystals shows similar T-dependence of magnetic susceptibility chi. The spin fluctuations with the q = 0 components are suppressed with Delta/k B. On the other hand, the growth of the stripe-type AFM fluctuations with q = (pi, 0) or (0, pi) upon cooling in the PM state for all samples is evidenced by the T-dependence of (1/ T1Tchi). A pseudogap-like phenomenon, i.e., suppression of the AFM spin fluctuations, was discovered with decreasing temperature below a x-independent characteristic temperature T* ( 100 K) in samples with x ≥ 0.028. In addition, clear evidence for the coexistence and competition of the stripe-type antiferromagnetic and ferromagnetic (FM) spin correlations was given by modified Korringa ratio analysis in Chapter 4. In Chapter 5, we have carried out 125Te NMR measurements to study the electronic properties of Ge50Te50, Ag 2Ge48Te50 and Sb2Ge48Te 50. NMR shift K and 1/T1T of Ge50Te50 are nearly temperature independent at T < 50 K and both increase slightly with increasing temperature at high temperatures. A two-band model, where one band overlaps the Fermi level and the other band is separated from the Fermi level by an energy gap, has been used to explain these behaviors. The first-principle calculation revealed that the metallic band originates from the Ge vacancy while the semiconductor-like band may be related to the fine structure of the density of states near the Fermi level. At low temperature, we found conduction carriers are free carriers with no significant electron correlations, while Korringa ratio increases slightly at high temperature, suggesting the slight enhancement of the electron correlation. In Chapter 6 and Chapter 7, we have used 13C NMR spectral editing technique to accurately analyze the surface composition of pristine purified, heat-treated (at 800 °C), and air-oxidized detonation nanodiamond. We have resolved ten peaks of C=O, COO, C=C, O-C-O, C-OH, C-N, CH, subsurface C, core C, and C-C-N. The aromatic fraction is only 1.1%, which corresponds to less than 1/20 of an aromatic surface layer. We have also shown that other surface functional groups (CH, COH, etc.) accounts for most of the surface sites, making up 11.5% of all C in pristine nanodiamond. The signal of carbon bonded to nitroge was observed selectively based on increased chemical-shift anisotropy due to breaking of the local symmetry. Furthermore, we used modified 13C{1H} REDOR experiments to observe the signals from carbons at different depths from the surface and estimate their quantities.

Tests of stratospheric models - The reactions of atomic chlorine with O3 and CH4 at low temperature

NASA Technical Reports Server (NTRS)

Demore, W. B.

1991-01-01

The rate-constant ratio of the photochemical reactions of atomic chlorine with O3 and CH4 was determined using data from laboratory experiments on competitive chlorination of O3/CH4 mixtures at stratospheric temperatures (197-217 K). Two experimental approaches were used: (1) measuring the k1/k2 ratio for the reactions of atomic chlorine with ozone and methane and (2) testing for some of the ClO/CH3O2 chemistry. The chlorine and ozone concentrations were monitored by UV-Vis spectroscopy, and the CH3Cl concentration was measured by FTIR. The results on the k1/k2 ratio are in excellent agreement with the current NASA recommendation (DeMore et al., 1990), being only 12 percent higher. On the other hand, results on the ClO + CH3O2 reaction do not support the rate constant suggested by Simon et al. (1989).

Nutrient Controls on Methane Emissions in a Permafrost Thaw Subarctic Peatland

NASA Astrophysics Data System (ADS)

Kashi, N. N.; Perryman, C. R.; Malhotra, A.; Marek, E. A.; Giesler, R.; Varner, R. K.

2015-12-01

Permafrost peatlands in northern latitudes are large reservoirs of sequestered carbon that are vulnerable to climate change. While peatlands account for a small fraction of total global land surfaces, their potential to release sequestered carbon in response to higher temperatures is of concern. Of particular relevance is the conversion of these carbon stores into methane (CH4), a strong greenhouse gas with a global warming potential 20 times greater than that of CO2 over a 100-year time frame. Here, we explore how key nutrients impact the consumption of CH4 at the Stordalen Mire in Abisko, Sweden, a discontinuous permafrost peatland with expanding thaw over the last century. Peatland CH4 emissions are highly spatially variable due to multiple emission pathways and strong dependence on several environmental factors. Among controls on CH4 emissions, such as temperature and water table depth, primary production of wetland vegetation is also a strong factor in the variability of CH4 emissions. Plant community shifts among permafrost thaw stages subsequently change nutrient cycling and availability, which in turn impacts primary production. Early stages of permafrost thaw are mosaicked with a variety of vascular plants and mosses. We analyzed potential enzymatic activities of chitinase, glucosidase, and phosphatase as proxies for organic nitrogen, carbon, and phosphorus cycling, respectively, in tandem with potential CH4 oxidation rates. In addition, stoichiometric ratios of carbon, nitrogen, and phosphorus concentrations are used to illustrate nutrient limitation controls on CH4 oxidation rates. While CH4 emissions are low throughout initial thaw stages, < 7 CH4 mg m-2 day-1, we found they had the highest rates of potential CH4 oxidation. These permafrost thaw-induced CH4 oxidation rates are 5 and 11 times higher, in the surface and depth of the peat profile respectively, than subsequent aerobic permafrost thaw stages. As CH4 emissions are low in intact permafrost peatlands, these high rates of potential CH4 oxidation indicate the importance of plant communities and the methanotrophic microbes they harbor.

Trajectory dynamics study of the Ar + CH4 dissociation reaction at high temperatures: the importance of zero-point-energy effects.

PubMed

Marques, J M C; Martínez-Núñez, E; Fernandez-Ramos, A; Vazquez, S A

2005-06-23

Large-scale classical trajectory calculations have been performed to study the reaction Ar + CH4--> CH3 +H + Ar in the temperature range 2500 < or = T/K < or = 4500. The potential energy surface used for ArCH4 is the sum of the nonbonding pairwise potentials of Hase and collaborators (J. Chem. Phys. 2001, 114, 535) that models the intermolecular interaction and the CH4 intramolecular potential of Duchovic et al. (J. Phys. Chem. 1984, 88, 1339), which has been modified to account for the H-H repulsion at small bending angles. The thermal rate coefficient has been calculated, and the zero-point energy (ZPE) of the CH3 product molecule has been taken into account in the analysis of the results; also, two approaches have been applied for discarding predissociative trajectories. In both cases, good agreement is observed between the experimental and trajectory results after imposing the ZPE of CH3. The energy-transfer parameters have also been obtained from trajectory calculations and compared with available values estimated from experiment using the master equation formalism; in general, the agreement is good.

Phase structure of higher spin black hole

NASA Astrophysics Data System (ADS)

Chen, Bin; Long, Jiang; Wang, Yi-Nan

2013-03-01

In this paper, we investigate the phase structure of the black holes with one single higher spin hair, focusing specifically on the spin 3 and spin widetilde{4} black holes. Based on dimensional analysis and the requirement of thermodynamic consistency, we derive a universal formula relating the entropy with the conserved charges for arbitrary AdS 3 higher spin black holes. Then we use it to study the phase structure of the higher spin black holes. We find that there are six branches of solutions in the spin 3 gravity, eight branches of solutions in the spin widetilde{4} gravity and twelve branches of solutions in the G 2 gravity. In each case, all the branches are related by a simple angle shift in the entropy functions. In the spin 3 case, we reproduce all the results found before. In the spin widetilde{4} case, we find that at low temperature it lies in the BTZ branch while at high temperature it undergoes a phase transition to one of the two other branches, depending on the signature of the chemical potential, a reflection of charge conjugate asymmetry found before.

Measurements of an Anomalous Global Methane Increase During 1998

NASA Technical Reports Server (NTRS)

Dlugokencky, E. J.; Walter, B. P.; Masarie, K. A.; Lang, P. M.; Kasischke, E. S.; Hansen, James E. (Technical Monitor)

2001-01-01

Measurements of atmospheric methane from a globally distributed network of air sampling sites indicate that the globally averaged CH4 growth rate increased from an average of 3.9 ppb/yr during 1995-1997 to 12.7 +/- 0.6 ppb in 1998. The global growth rate then decreased to 2.6 +/- 0.6 ppb during 1999, indicating that the large increase in 1998 was an anomaly and not a return to the larger growth rates observed during the late 1970s and early 1980s. The increased growth rate represents an anomalous increase in the imbalance between CH4 sources and sinks equal to approximately 24 Tg CH4 during 1998. Wetlands and boreal biomass burning are sources that may have contributed to the anomaly. During 1998, the globally averaged temperature anomaly was +0.67 C, the largest temperature anomaly in the modern record. A regression model based on temperature and precipitation anomalies was used to calculate emission anomalies of 11.6 Tg CH4 from wetlands north of 30 N and 13 Tg CH4 for tropical wetlands during 1998 compared to average emissions calculated for 1982-1993. In 1999, calculated wetland emission anomalies were negative for high northern latitudes and the tropics, contributing to the low growth rate observed in 1999. Also 1998 was a severe fire year in boreal regions where approximately 1.3x10(exp 5) sq km of forest and peat land burned releasing an estimated 5.7 Tg CH4

Application of stable isotope measurements and microbiological analysis for detecting methanogenic activity in a temperate forest wetland

NASA Astrophysics Data System (ADS)

Itoh, M.; Katsuyama, C.; Kondo, N.; Ohte, N.; Kato, K.

2009-12-01

Generally, forest soils act as a sink for methane (CH4). However, wetlands in riparian zones are recently reported to be “hot spots” of CH4 emissions, especially in forests under a humid climate. To understand how environmental conditions (i.e. hydrological and/or geomorphic condition) control on CH4 production, we investigated both methanogenic pathways (CO2/H2 reduction and acetate fermentation) and metahanogenic microbial communities in a wetland in a temperate forest catchment, central Japan. We used stable carbon isotopic analysis for detecting change in methanogenic pathways, and applied microbiological analysis for understanding the structure of methanogenic community. CH4 emission rates in wetland were strongly dependent on soil temperatures, and were highest in summer and lowest in winter. δ13CO2 increased with CH4 production in every summer, suggesting preferential use of 12CO2 as substrate for CO2/H2 reduction methanogenesis during high CH4 production period. δ13CH4 also increased in summer with δ13CO2. δ13CH4 changed more wildly than δ13CO2 did in summer with normal precipitation when CH4 production was strongly activated under high temperature and high groundwater table condition. This indicates increase in acetoclastic methanogenesis under hot and wet condition, considering that acetclastic methnogens produce heavier CH4 than that from CO2/H2 reducing pathway. Methanogen community composition estimated by cloning and sequence analyses implied that both acetoclastic and CO2/H2 reducing methanogens prevailed in wetland soil sampled in summer. This was consistent with the results of isotope measuremaents. Our results contribute to understand fully how the CH4 production changes with environmental conditions, with considering the activities of both main methanogenic pathway (from CO2 and acetate).

Enhanced winter soil frost reduces methane emission during the subsequent growing season in a boreal peatland.

PubMed

Zhao, Junbin; Peichl, Matthias; Nilsson, Mats B

2016-02-01

Winter climate change may result in reduced snow cover and could, consequently, alter the soil frost regime and biogeochemical processes underlying the exchange of methane (CH4 ) in boreal peatlands. In this study, we investigated the short-term (1-3 years) vs. long-term (11 years) effects of intensified winter soil frost (induced by experimental snow exclusion) on CH4 exchange during the following growing season in a boreal peatland. In the first 3 years (2004-2006), lower CH4 emissions in the treatment plots relative to the control coincided with delayed soil temperature increase in the treatment plots at the beginning of the growing season (May). After 11 treatment years (in 2014), CH4 emissions were lower in the treatment plots relative to the control over the entire growing season, resulting in a reduction in total growing season CH4 emission by 27%. From May to July 2014, reduced sedge leaf area coincided with lower CH4 emissions in the treatment plots compared to the control. From July to August, lower dissolved organic carbon concentrations in the pore water of the treatment plots explained 72% of the differences in CH4 emission between control and treatment. In addition, greater Sphagnum moss growth in the treatment plots resulted in a larger distance between the moss surface and the water table (i.e., increasing the oxic layer) which may have enhanced the CH4 oxidation potential in the treatment plots relative to the control in 2014. The differences in vegetation might also explain the lower temperature sensitivity of CH4 emission observed in the treatment plots relative to the control. Overall, this study suggests that greater soil frost, associated with future winter climate change, might substantially reduce the growing season CH4 emission in boreal peatlands through altering vegetation dynamics and subsequently causing vegetation-mediated effects on CH4 exchange. © 2015 John Wiley & Sons Ltd.

Methanogen community composition and rates of methane consumption in Canadian High Arctic permafrost soils.

PubMed

Allan, J; Ronholm, J; Mykytczuk, N C S; Greer, C W; Onstott, T C; Whyte, L G

2014-04-01

Increasing permafrost thaw, driven by climate change, has the potential to result in organic carbon stores being mineralized into carbon dioxide (CO2) and methane (CH4) through microbial activity. This study examines the effect of increasing temperature on community structure and metabolic activity of methanogens from the Canadian High Arctic, in an attempt to predict how warming will affect microbially controlled CH4 soil flux. In situ CO2 and CH4 flux, measured in 2010 and 2011 from ice-wedge polygons, indicate that these soil formations are a net source of CO2 emissions, but a CH4 sink. Permafrost and active layer soil samples were collected at the same sites and incubated under anaerobic conditions at warmer temperatures, with and without substrate amendment. Gas flux was measured regularly and indicated an increase in CH4 flux after extended incubation. Pyrosequencing was used to examine the effects of an extended thaw cycle on methanogen diversity and the results indicate that in situ methanogen diversity, based on the relative abundance of the 16S ribosomal ribonucleic acid (rRNA) gene associated with known methanogens, is higher in the permafrost than in the active layer. Methanogen diversity was also shown to increase in both the active layer and permafrost soil after an extended thaw. This study provides evidence that although High Arctic ice-wedge polygons are currently a sink for CH4, higher arctic temperatures and anaerobic conditions, a possible result of climate change, could result in this soil becoming a source for CH4 gas flux. © 2013 Society for Applied Microbiology and John Wiley & Sons Ltd.

Compact CH 4 sensor system based on a continuous-wave, low power consumption, room temperature interband cascade laser

DOE PAGES

Dong, Lei; Li, Chunguang; Sanchez, Nancy P.; ...

2016-01-05

A tunable diode laser absorption spectroscopy-based methane sensor, employing a dense-pattern multi-pass gas cell and a 3.3 µm, CW, DFB, room temperature interband cascade laser (ICL), is reported. The optical integration based on an advanced folded optical path design and an efficient ICL control system with appropriate electrical power management resulted in a CH 4 sensor with a small footprint (32 x 20 x 17 cm 3) and low-power consumption (6 W). Polynomial and least-squares fit algorithms are employed to remove the baseline of the spectral scan and retrieve CH 4 concentrations, respectively. An Allan-Werle deviation analysis shows that themore » measurement precision can reach 1.4 ppb for a 60 s averaging time. Continuous measurements covering a seven-day period were performed to demonstrate the stability and robustness of the reported CH 4 sensor system.« less

Compact CH 4 sensor system based on a continuous-wave, low power consumption, room temperature interband cascade laser

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

Dong, Lei; Li, Chunguang; Sanchez, Nancy P.

A tunable diode laser absorption spectroscopy-based methane sensor, employing a dense-pattern multi-pass gas cell and a 3.3 µm, CW, DFB, room temperature interband cascade laser (ICL), is reported. The optical integration based on an advanced folded optical path design and an efficient ICL control system with appropriate electrical power management resulted in a CH 4 sensor with a small footprint (32 x 20 x 17 cm 3) and low-power consumption (6 W). Polynomial and least-squares fit algorithms are employed to remove the baseline of the spectral scan and retrieve CH 4 concentrations, respectively. An Allan-Werle deviation analysis shows that themore » measurement precision can reach 1.4 ppb for a 60 s averaging time. Continuous measurements covering a seven-day period were performed to demonstrate the stability and robustness of the reported CH 4 sensor system.« less

Spectral fingerprints of Earth-like planets around FGK stars.

PubMed

Rugheimer, Sarah; Kaltenegger, Lisa; Zsom, Andras; Segura, Antígona; Sasselov, Dimitar

2013-03-01

We present model atmospheres for an Earth-like planet orbiting the entire grid of main sequence FGK stars with effective temperatures ranging from Teff=4250 K to Teff=7000 K in 250 K intervals. We have modeled the remotely detectable spectra of Earth-like planets for clear and cloudy atmospheres at the 1 AU equivalent distance from the VIS to IR (0.4 to 20 μm) to compare detectability of features in different wavelength ranges in accordance with the James Webb Space Telescope and future design concepts to characterize exo-Earths. We have also explored the effect of the stellar UV levels as well as spectral energy distribution on a terrestrial atmosphere, concentrating on detectable atmospheric features that indicate habitability on Earth, namely, H2O, O3, CH4, N2O, and CH3Cl. The increase in UV dominates changes of O3, OH, CH4, N2O, and CH3Cl, whereas the increase in stellar temperature dominates changes in H2O. The overall effect as stellar effective temperatures and corresponding UV increase is a lower surface temperature of the planet due to a bigger part of the stellar flux being reflected at short wavelengths, as well as increased photolysis. Earth-like atmosphere models show more O3 and OH but less stratospheric CH4, N2O, CH3Cl, and tropospheric H2O (but more stratospheric H2O) with increasing effective temperature of main sequence stars. The corresponding detectable spectral features, on the other hand, show different detectability depending on the wavelength observed. We concentrate on directly imaged planets here as a framework to interpret future light curves, direct imaging, and secondary eclipse measurements of atmospheres of terrestrial planets in the habitable zone at varying orbital positions.

Seasonal dynamics of methane emissions from a subarctic fen in the Hudson Bay Lowlands

NASA Astrophysics Data System (ADS)

Hanis, K. L.; Tenuta, M.; Amiro, B. D.; Papakyriakou, T. N.

2013-07-01

Ecosystem-scale methane (CH4) flux (FCH4) over a subarctic fen at Churchill, Manitoba, Canada was measured to understand the magnitude of emissions during spring and fall shoulder seasons, and the growing season in relation to physical and biological conditions. FCH4 was measured using eddy covariance with a closed-path analyser in four years (2008-2011). Cumulative measured annual FCH4 (shoulder plus growing seasons) ranged from 3.0 to 9.6 g CH4 m-2 yr-1 among the four study years, with a mean of 6.5 to 7.1 g CH4 m-2 yr-1 depending upon gap-filling method. Soil temperatures to depths of 50 cm and air temperature were highly correlated with FCH4, with near-surface soil temperature at 5 cm most correlated across spring, fall, and the shoulder and growing seasons. The response of FCH4 to soil temperature at the 5 cm depth and air temperature was more than double in spring to that of fall. Emission episodes were generally not observed during spring thaw. Growing season emissions also depended upon soil and air temperatures but the water table also exerted influence, with FCH4 highest when water was 2-13 cm below and lowest when it was at or above the mean peat surface.

Seasonal dynamics of methane emissions from a subarctic fen in the Hudson Bay Lowlands

NASA Astrophysics Data System (ADS)

Hanis, K. L.; Tenuta, M.; Amiro, B. D.; Papakyriakou, T. N.

2013-03-01

Ecosystem-scale methane (CH4) flux (FCH4) over a subarctic fen at Churchill, Manitoba, Canada was measured to understand the magnitude of emissions during spring and fall shoulder seasons, and the growing season in relation to physical and biological conditions. FCH4 was measured using eddy covariance with a closed-path analyzer in four years (2008-2011). Cumulative measured annual FCH4 (shoulder plus growing seasons) ranged from 3.0 to 9.6 g CH4 m-2 yr-1 among the four study years, with a mean of 6.5 to 7.1 g CH4 m-2 yr-1 depending upon gap-filling method. Soil temperatures to depths of 50 cm and air temperature were highly correlated with FCH4, with near surface soil temperature at 5 cm most correlated across spring, fall, and the whole season. The response of FCH4 to soil temperature at the 5 cm depth and air temperature was more than double in spring to that of fall. Emission episodes were generally not observed during spring thaw. Growing season emissions also depended upon soil and air temperatures but water table also exerted influence with FCH4 highest when water was 2-13 cm below and least when it was at or above the mean peat surface.

Methanogenesis, Mesospheric Clouds, and Global Habitability

NASA Technical Reports Server (NTRS)

Pueschel, Rudolf F.; Condon, Estelle P. (Technical Monitor)

2000-01-01

Hyperthermophilic methanogens can exist in a deep hot biosphere up to 110 C, or 10 km deep. Methane (CH4) itself is thermodynamically stable to depths of 300 km. Geologic (microbial plus abiogenic thermal) methane is transported upward, attested to by its association with helium, to form petroleum pools. Near or at the surface, geologic CH4 mixes with other natural and with anthropogenic CH4 yielding annual emissions into the atmosphere of 500 Tg, of which 200 Tg are natural and 300 Tg are man-made. The atmospheric lifetime of CH4, a greenhouse gas 20 times more effective than CO2 in raising global temperatures, is approximately 10 years. It is removed from the atmosphere mainly by reactions with hydroxyl radical (OH) to form CO2, but also by dry soil and by conversion to H2O in the stratosphere and middle atmosphere. A sudden rise in atmospheric temperatures by 9-12 C some 55 million years ago has been explained by the release in a few thousand years of three trillion tons of CH4 out of 15 trillion tons that had formed beneath the sea floor. What prevented this CH4-induced greenhouse effect from running away? An analog to the CH4-burp of 55 million years ago is the CH4-doubling over the past century which resulted in a increase in upper level H2O from 4.3 ppmv to 6 ppmv. This 30% increase in H2O vapor yielded a tenfold increase in brightness of polar mesospheric clouds because of a strong dependence of the ice particle nucleation rate on the water saturation ratios. Models show that at a given temperature the optical depth of mesospheric clouds scales as [H2O]beta with beta varying between 4 and 8. Radiative transfer tools applied to mesospheric particles suggest that an optical depth of approximately one, or 1000 times the current mesospheric cloud optical depth, would result in tropospheric cooling of about 10 K. Assuming beta=6, a thousandfold increase in optical thickness would require a three-fold increase of H2O, or a 20-fold increase of CH4. At the current rate of anthropogenic emissions this is expected to occur within the next 1000 years. This timescale is also commensurate with what has been assumed for the CH4- burp 55 million years ago.

Assessing the High Temperature, High Pressure Subsurface for Anaerobic Methane Oxidation

NASA Astrophysics Data System (ADS)

Harris, R. L.; Bartlett, D.; Byrnes, A. W.; Walsh, K. M.; Lau, C. Y. M.; Onstott, T. C.

2017-12-01

The anaerobic oxidation of methane (AOM) is an important sink in the global methane (CH4) budget. ANMEs are known to oxidize CH4 either independently or in consortia with bacteria, coupling the reduction of electron acceptors such as, SO42-, NO2-, NO3-, Mn4+, or Fe3+. To further constrain the contribution of AOM to the global CH4 budget, it is important to assess unexplored environments where AOM is thermodynamically possible such as the high pressure, high temperature deep biosphere. Provided plausible electron acceptor availability, increased temperature and pCH4 yield favorable Gibbs free energies for AOM reactions and the production of ATP (Fig. 1). To date, only sulfate-dependent AOM metabolism has been documented under high temperature conditions (50-72˚C), and AOM has not been assessed above 10.1 MPa. Given that ANMEs share close phylogenetic and metabolic heritage with methanogens and that the most heat-tolerant microorganism known is a barophilic methanogen, there possibly exist thermophilic ANMEs. Here we describe preliminary results from high pressure, high temperature stable isotope tracer incubation experiments on deep biosphere samples. Deep sub-seafloor sediments collected by IODP 370 from the Nankai Trough (257 - 865 m below seafloor) and deep fracture fluid from South Africa (1339 m below land surface) were incubated anaerobically in hydrostatic pressure vessels at 40 MPa in simulated in situ temperatures (40˚ - 80˚C). Sediments and fracture fluid were incubated in sulfate-free artificial seawater, a 2:98 13CH4:N2 headspace, and treated with one of the potential electron acceptors listed above in addition to kill and endogenous activity (i.e. no added electron acceptor) controls. Stable isotope analysis of dissolved inorganic carbon (DIC) suggests that AOM occurred within 60 days of incubation for all investigated electron acceptors and temperatures except 50˚C. Sulfate-dependent AOM rates are consistent with those previously reported in the literature, while the highest rate of AOM was measured in Nankai Trough sediments from 616 m incubated at 70˚C with 10 mM NO2- (0.44 ± .01 µmol 13CO2 day-1 g-1 dry weight sediment). Further analysis is required to investigate the identities and functional adaptations of CH4-cycling organisms active under high pressure and high temperature.

Assessment of a landfill methane emission screening method using an unmanned aerial vehicle mounted thermal infrared camera - A field study.

PubMed

Fjelsted, L; Christensen, A G; Larsen, J E; Kjeldsen, P; Scheutz, C

2018-05-28

An unmanned aerial vehicle (UAV)-mounted thermal infrared (TIR) camera's ability to delineate landfill gas (LFG) emission hotspots was evaluated in a field test at two Danish landfills (Hedeland landfill and Audebo landfill). At both sites, a test area of 100 m 2 was established and divided into about 100 measuring points. The relationship between LFG emissions and soil surface temperatures were investigated through four to five measuring campaigns, in order to cover different atmospheric conditions along with increasing, decreasing and stable barometric pressure. For each measuring campaign, a TIR image of the test area was obtained followed by the measurement of methane (CH 4 ) and carbon dioxide (CO 2 ) emissions at each measuring point, using a static flux chamber. At the same time, soil temperatures measured on the surface, at 5 cm and 10 cm depths, were registered. At the Hedeland landfill, no relationship was found between LFG emissions and surface temperatures. In addition, CH 4 emissions were very limited, on average 0.92-4.52 g CH 4  m -2  d -1 , and only measureable on the two days with decreasing barometric pressure. TIR images from Hedeland did not show any significant temperature differences in the test area. At the Audebo landfill, an area with slightly higher surface temperatures was found in the TIR images, and the same pattern with slightly higher temperatures was found at a depth of 10 cm. The main LFG emissions were found in the area with the higher surface temperatures. LFG emissions at Audebo were influenced significantly by changes in barometric pressure, and the average CH 4 emissions varied between 111 g m -2  d -1 and 314 g m -2  d -1 , depending on whether the barometric pressure gradient had increased or decreased, respectively. The temperature differences observed in the TIR images from both landfills were limited to between 0.7 °C and 1.2 °C. The minimum observable CH 4 emission for the TIR camera to identify an emission hotspot was 150 g CH 4  m -2  d -1 from an area of more than 1 m 2 . Copyright © 2018 Elsevier Ltd. All rights reserved.

Impact of elevated CO2, water table, and temperature changes on CO2 and CH4 fluxes from arctic tundra soils

NASA Astrophysics Data System (ADS)

Zona, Donatella; Haynes, Katherine; Deutschman, Douglas; Bryant, Emma; McEwing, Katherine; Davidson, Scott; Oechel, Walter

2015-04-01

Large uncertainties still exist on the response of tundra C emissions to future climate due, in part, to the lack of understanding of the interactive effects of potentially controlling variables on C emissions from Arctic ecosystems. In this study we subjected 48 soil cores (without active vegetation) from dominant arctic wetland vegetation types, to a laboratory manipulation of elevated atmospheric CO2, elevated temperature, and altered water table, representing current and future conditions in the Arctic for two growing seasons. To our knowledge this experiment comprised the most extensively replicated manipulation of intact soil cores in the Arctic. The hydrological status of the soil was the most dominant control on both soil CO2 and CH4 emissions. Despite higher soil CO2 emission occurring in the drier plots, substantial CO2 respiration occurred under flooded conditions, suggesting significant anaerobic respirations in these arctic tundra ecosystems. Importantly, a critical control on soil CO2 and CH4 fluxes was the original vascular plant cover. The dissolved organic carbon (DOC) concentration was correlated with cumulative CH4 emissions but not with cumulative CO2 suggesting C quality influenced CH4 production but not soil CO2 emissions. An interactive effect between increased temperature and elevated CO2 on soil CO2 emissions suggested a potential shift of the soils microbial community towards more efficient soil organic matter degraders with warming and elevated CO2. Methane emissions did not decrease over the course of the experiment, even with no input from vegetation. This result indicated that CH4 emissions are not carbon limited in these C rich soils. Overall CH4 emissions represented about 49% of the sum of total C (C-CO2 + C-CH4) emission in the wet treatments, and 15% in the dry treatments, representing a dominant component of the overall C balance from arctic soils.

Influence of disturbance on carbon exchange in a permafrost collapse and adjacent burned forest

USGS Publications Warehouse

Myers-Smith, I. H.; McGuire, A.D.; Harden, J.W.; Chapin, F. S.

2007-01-01

We measured CO2 and CH4 exchange from the center of a Sphagnum-dominated permafrost collapse, through an aquatic most, and into a recently burned black spruce forest on the Tanana River floodplain in interior Alaska. In the anomalously dry growing season of 2004, both the collapse and the surrounding burned area were net sink, s for CO2, with a mean daytime net ecosystem exchange of -1.4 ??mol CO2 m-2 s-1, while the moat was a CH4 source with a mean flux of 0.013 ??mol CH4 m-2 s-1. Regression analyses identified temperature as the dominant factor affecting intragrowing season variation in CO2 exchange and soil moisture as the primary control influencing CH4 emissions. CH4 emissions during the wettest portion of the growing season were four times higher than during the driest periods. If temperatures continue to warm, peatlahd vegetation will likely expand with permafrost degradation, resulting in greater carbon accumulation and methane emissions for the landscape as a whole. Copyright 2007 by the American Geophysical Union.

Choice of precipitant and calcination temperature of precursor for synthesis of NiCo2O4 for control of CO-CH4 emissions from CNG vehicles.

PubMed

Trivedi, Suverna; Prasad, Ram

2018-03-01

Compressed natural gas (CNG) is most appropriate an alternative of conventional fuel for automobiles. However, emissions of carbon-monoxide and methane from such vehicles adversely affect human health and environment. Consequently, to abate emissions from CNG vehicles, development of highly efficient and inexpensive catalysts is necessary. Thus, the present work attempts to scan the effects of precipitants (Na 2 CO 3 , KOH and urea) for nickel cobaltite (NiCo 2 O 4 ) catalysts prepared by co-precipitation from nitrate solutions and calcined in a lean CO-air mixture at 400°C. The catalysts were used for oxidation of a mixture of CO and CH 4 (1:1). The catalysts were characterized by X-ray diffractometer, Brunauer-Emmett-Teller surface-area, X-ray photoelectron spectroscopy; temperature programmed reduction and Scanning electron microscopy coupled with Energy-Dispersive X-Ray Spectroscopy. The Na 2 CO 3 was adjudged as the best precipitant for production of catalyst, which completely oxidized CO-CH 4 mixture at the lowest temperature (T 100 =350°C). Whereas, for catalyst prepared using urea, T 100 =362°C. On the other hand the conversion of CO-CH 4 mixture over the catalyst synthesized by KOH limited to 97% even beyond 400°C. Further, the effect of higher calcination temperatures of 500 and 600°C was examined for the best catalyst. The total oxidation of the mixture was attained at higher temperatures of 375 and 410°C over catalysts calcined at 500 and 600°C respectively. Thus, the best precipitant established was Na 2 CO 3 and the optimum calcination temperature of 400°C was found to synthesize the NiCo 2 O 4 catalyst for the best performance in CO-CH 4 oxidation. Copyright © 2017. Published by Elsevier B.V.

Statistical assessment of dumpsite soil suitability to enhance methane bio-oxidation under interactive influence of substrates and temperature.

PubMed

Bajar, Somvir; Singh, Anita; Kaushik, C P; Kaushik, Anubha

2017-05-01

Biocovers are considered as the most effective and efficient way to treat methane (CH 4 ) emission from dumpsites and landfills. Active methanotrophs in the biocovers play a crucial role in reduction of emissions through microbiological methane oxidation. Several factors affecting methane bio-oxidation (MOX) have been well documented, however, their interactive effect on the oxidation process needs to be explored. Therefore, the present study was undertaken to investigate the suitability of a dumpsite soil to be employed as biocover, under the influence of substrate concentrations (CH 4 and O 2 ) and temperature at variable incubation periods. Statistical design matrix of Response Surface Methodology (RSM) revealed that MOX rate up to 69.58μgCH 4 g -1 dw h -1 could be achieved under optimum conditions. MOX was found to be more dependent on CH 4 concentration at higher level (30-40%, v/v), in comparison to O 2 concentration. However, unlike other studies MOX was found in direct proportionality relationship with temperature within a range of 25-35°C. The results obtained with the dumpsite soil biocover open up a new possibility to provide improved, sustained and environmental friendly systems to control even high CH 4 emissions from the waste sector. Copyright © 2017 Elsevier Ltd. All rights reserved.

Eddy Covariance Measurements of Methane Emissions from a Dairy Farm Waste Lagoon

NASA Astrophysics Data System (ADS)

Sokol, A. B.; Lauvaux, T.; Richardson, S.; Hlywiak, J.; Davis, K. J.; Hristov, A. N.

2016-12-01

Livestock manure management in dairy operations is a known source of methane (CH4), a potent greenhouse gas. Anaerobic waste lagoons are a common manure management technique; thus, their associated CH4 emissions are relevant to national greenhouse gas inventories and local air quality. Our objective was to characterize the variability of summertime CH4 emissions from a lagoon at a dairy facility in central Pennsylvania. Continuous flux measurements were taken over two weeks in July using the eddy covariance method, which uses high-frequency gas concentration and three-dimensional wind speed measurements to calculate turbulent fluxes from a source area. After data filtration based on turbulence characteristics and source area, the average CH4 flux density from the lagoon was estimated to be 99 μmol m-2 s-1. This implies daily lagoon emissions of 881 kg CH4, corresponding to an average emission rate of 340 g CH4 per cow per day. We observed no apparent relationship between emissions and air temperature or relative humidity, though an extended measurement period is needed to better quantify the relationship that is expected to exist between air and/or slurry temperature and CH4 flux. Our measured per-area emission rate is toward the high end of the range of estimates found in the literature. These results contribute to greenhouse gas inventory development and could have important implications for emission mitigation strategies.

Generation of Hydrogen and Methane during Experimental Low-Temperature Reaction of Ultramafic Rocks with Water

NASA Astrophysics Data System (ADS)

McCollom, Thomas M.; Donaldson, Christopher

2016-06-01

Serpentinization of ultramafic rocks is widely recognized as a source of molecular hydrogen (H2) and methane (CH4) to support microbial activity, but the extent and rates of formation of these compounds in low-temperature, near-surface environments are poorly understood. Laboratory experiments were conducted to examine the production of H2 and CH4 during low-temperature reaction of water with ultramafic rocks and minerals. Experiments were performed by heating olivine or harzburgite with aqueous solutions at 90°C for up to 213 days in glass bottles sealed with butyl rubber stoppers. Although H2 and CH4 increased steadily throughout the experiments, the levels were very similar to those found in mineral-free controls, indicating that the rubber stoppers were the predominant source of these compounds. Levels of H2 above background were observed only during the first few days of reaction of harzburgite when CO2 was added to the headspace, with no detectable production of H2 or CH4 above background during further heating of the harzburgite or in experiments with other mineral reactants. Consequently, our results indicate that production of H2 and CH4 during low-temperature alteration of ultramafic rocks may be much more limited than some recent experimental studies have suggested. We also found no evidence to support a recent report suggesting that spinels in ultramafic rocks may stimulate H2 production. While secondary silicates were observed to precipitate during the experiments, formation of these deposits was dominated by Si released by dissolution of the glass bottles, and reaction of the primary silicate minerals appeared to be very limited. While use of glass bottles and rubber stoppers has become commonplace in experiments intended to study processes that occur during serpentinization of ultramafic rocks at low temperatures, the high levels of H2, CH4, and SiO2 released during heating indicate that these reactor materials are unsuitable for this purpose.

High-excitation lines of deuterated formaldehyde (HDCO) in the Orion Molecular Cloud

NASA Astrophysics Data System (ADS)

Loren, R. B.; Wootten, A.

1985-12-01

Five HDCO lines (up to 35 cm-1) have been detected in the narrow OMC-1 kinematic component. The best estimate of the [HDCO]/[H2CO] abundance ratio in OMC-1 is 0.01-0.03, at least an order of magnitude greater than the observed [DCO+]/[HCO+] abundance ratio. The [DCO+]/[HCO+] ratio greatly exceeds the [HDCO]/[H2CO] ratio in cold clouds where the enhancement of both HDCO and DCO+ abundances originates from H2D+. H2D+ is abundant only at temperatures lower than found in OMC- 1. The combination of a low [DCO+]/[HCO+] and high [HDCO]/[H2CO] abundance ratio in OMC-1 requires a different HDCO formation route at high temperature. This alternate HDCO formation path can occur because the exothermicity of the ion exchange reaction of HD and CH3+ is greater than for the HD + H3+ reaction. The CH2D+ thus formed survives to higher temperatures than H2D+. Subsequent reactions with H2 lead to CH4D+ which by electronic recombination forms CH2D. The HDCO (H2CO) forms in the neutral-neutral reaction of CH2D (CH3) and O. These reactions are not competitive in forming a variety of deuterated molecules at low temperatures since electronic recombination rapidly removes CH2D+ and CH4D+ ions while the abundant H2D+ ion is slow to recombine, as reported by Smith and Adam in 1984.

Dehydrogenation of ammonia-borane by cationic Pd(II) and Ni(II) complexes in a nitromethane medium: hydrogen release and spent fuel characterization.

PubMed

Kim, Sung-Kwan; Hong, Sung-Ahn; Son, Ho-Jin; Han, Won-Sik; Michalak, Artur; Hwang, Son-Jong; Kang, Sang Ook

2015-04-28

A highly electrophilic cationic Pd(II) complex, [Pd(MeCN)4][BF4]2 (1), brings about the preferential activation of the B-H bond in ammonia-borane (NH3·BH3, AB). At room temperature, the reaction between 1 in CH3NO2 and AB in tetraglyme leads to Pd nanoparticles and formation of spent fuels of the general formula MeNHxBOy as reaction byproducts, while 2 equiv. of H2 is efficiently released per AB equiv. at room temperature within 60 seconds. For a mechanistic understanding of dehydrogenation by 1, the chemical structures of spent fuels were intensely characterized by a series of analyses such as elemental analysis (EA), X-ray photoelectron spectroscopy (XPS), solid state magic-angle-spinning (MAS) NMR spectra ((2)H, (13)C, (15)N, and (11)B), and cross polarization (CP) MAS methods. During AB dehydrogenation, the involvement of MeNO2 in the spent fuels showed that the mechanism of dehydrogenation catalyzed by 1 is different from that found in the previously reported results. This AB dehydrogenation derived from MeNO2 is supported by a subsequent digestion experiment of the AB spent fuel: B(OMe)3 and N-methylhydroxylamine ([Me(OH)N]2CH2), which are formed by the methanolysis of the AB spent fuel (MeNHxBOy), were identified by means of (11)B NMR and single crystal structural analysis, respectively. A similar catalytic behavior was also observed in the AB dehydrogenation catalyzed by a nickel catalyst, [Ni(MeCN)6][BF4]2 (2).

Understanding the Temporal Variation of CO2 and CH4 Fluxes in a Subtropical Seasonal Wetland

NASA Astrophysics Data System (ADS)

Gomez-Casanovas, N.; DeLucia, N.; DeLucia, E. H.; Boughton, E.; Bernacchi, C.

2017-12-01

The magnitude of the net greenhouse gas (GHG) sink strength of wetlands and mechanisms driving C fluxes remain uncertain, particularly for subtropical and tropical wetlands that are responsible for the majority of wetland CH4 emissions globally. We determined the exchange of CO2 and CH4 fluxes between a subtropical wetland and the atmosphere, and investigated how changes in water table (WT), soil temperature (ST), and Gross Primary Productivity (GPP) alter CH4 fluxes. Measurements were made using the eddy covariance technique from June, 2013 to December, 2015. As GPP was greater than ecosystem respiration, wetland was consistently a net sink of CO2 from the atmosphere (-480 gC m-2 in 2013, -275 gC m-2 in 2014 and -258 gC m-2 in 2015). Though variable among years, wetland was a net source of CH4 to the atmosphere (24.5 gC m-2 in 2013, 26.1 gC m-2 in 2014, 32.7 gC m-2 in 2015). WT and ST were strong drivers of net CH4 fluxes. Fluxes of CH4 exponentially increased with WT near the soil surface, and they were maximal and sustained after 3 days or more of preceding flooding suggesting that flooding duration and intensity drives CH4 emissions in this system. GPP also exerted a strong control on these fluxes, particularly when water was near the soil surface. The system emitted an average of 2 g more C-CH4 m-2 during the wet seasons of 2013 and 2015 than the wet season of 2014 due to higher WT, and increases in flooding days and cumulative GPP for days with water at near-surface (GPPWT). Although WT was higher during the dry season of 2015 than the wet season of 2014, CH4 fluxes were similar likely because of increased ST and GPPWT in the wet season of 2014. The contribution of CH4 fluxes during the dry season to annual fluxes was 41% in 2014 and 48% in 2015. Wetland was a strong sink of C, and it was a net sink of GHGs in 2014 and a net source in 2015 mainly attributable to increases in net CH4 emissions. Climate models predict that subtropical and tropical regions will experience more frequent floods and droughts as well as higher temperatures, conditions that will likely alter ecosystem attributes such as GPP. Our results indicate that CH4 emissions from subtropical wetlands will likely respond to projected changes in precipitation, temperature and productivity, substantially affecting the net GHG sink strength of these systems in future climate scenarios.

Deriving Temperatures from the Homopause of Jupiter

NASA Astrophysics Data System (ADS)

Kim, Sang J.

2015-11-01

Recently, Kim et al. (Icarus, 2015) derived homopause temperatures from several places on the north and south polar regions of Jupiter by analyzing the 3-μm spectro-images of CH4, which were obtained using the Gemini Near-Infrared Spectrograph (GNIRS). The spectral resolution of the data was R~18,000, which is enough to resolve the sharp 3-μm emission lines of the P and Q branches of CH4. From the next year’s JUNO encounter with Jupiter, we are expecting low resolution spectra from JUNO’s IR 2-5 μm spectrograph, whose resolution is only R~300 at 3 μm. We will present a method to derive homopause temperatures from low-resolution spectra utilizing the gross envelopes of the P, Q, R branch lines of CH4. We will discuss possible sciences extracted from the constructed maps of homopause temperatures over the auroral or non-auroral regions of Jupiter.

Phase behaviour and conductivity of supporting electrolytes in supercritical difluoromethane and 1,1-difluoroethane.

PubMed

Han, Xue; Ke, Jie; Suleiman, Norhidayah; Levason, William; Pugh, David; Zhang, Wenjian; Reid, Gillian; Licence, Peter; George, Michael W

2016-06-07

We present investigations into a variety of supporting electrolytes and supercritical fluids probing the phase and conductivity behaviour of these systems and show that they not only provide sufficient electrical conductivity for an electrodeposition bath, but match the requirements imposed by the different precursors and process parameters, e.g. increased temperature, for potential deposition experiments. The two supercritical fluids that have been explored in this study are difluoromethane (CH2F2) and 1,1-difluoroethane (CHF2CH3). For CH2F2, the phase behaviour and electrical conductivity of eight ionic compounds have been studied. Each compound consists of a cation and an anion from the selected candidates i.e. tetramethylammonium ([N(CH3)4](+)), tetrabutylammonium ([N((n)C4H9)4](+)), 1-ethyl-3-methylimidazolium ([EMIM](+)) and 1-butyl-3-methylimidazolium ([BMIM](+)) for cations, and tetrakis(perfluoro-tert-butoxy)aluminate ([Al(OC(CF3)3)4](-)), chloride (Cl(-)), trifluoromethyl sulfonimide ([NTf2](-)) and tris(pentafluoroethyl)trifluorophosphate ([FAP](-)) for anions. For CHF2CH3, [N((n)C4H9)4][BF4] and [N((n)C4H9)4][B{3,5-C6H3(CF3)2}4] have been investigated for comparison with the previously measured solubility and conductivity in CH2F2. We have found that [N((n)C4H9)4][Al(OC(CF3)3)4], [N((n)C4H9)4][FAP] and [N(CH3)4][FAP] have much higher molar conductivity in scCH2F2 at similar conditions than [N((n)C4H9)4][BF4], a widely used commercial electrolyte. Additionally, scCHF2CH3 shows potential for use as the solvent for supercritical fluid electrodeposition, especially at high temperatures since high density of this fluid can be achieved at lower operating pressures than similar fluids that can be used to produce electrochemical baths with comparable conductivity.

An Emergent Spin-Filter at the interface between Ferromagnetic and Insulating Layered Oxides

NASA Astrophysics Data System (ADS)

Liu, Yaohua

2014-03-01

Complex oxide heterostructures are of keen interest because modified bonding at the interfaces can give rise to fundamentally new phenomena and valuable functionalities. Particularly, an induced magnetization is widely observed at epitaxial interfaces between layered transition-metal oxides; however, much less effort has been spent on investigating how it affects the charge transport properties. To this end, we have studied magnetic tunneling junctions consisting of ferromagnetic manganite La0.7Ca0.3MnO3 (LCMO) and insulating cuprate PrBa2Cu3O7 (PBCO). Contrary to the typically observed steady increase of the tunnel magnetoresistance with decreasing temperature, this system exhibits an anomalous decrease at low temperatures. Polarized neutron reflectometry (PNR) and x-ray magnetic circular dichroism (XMCD) studies on LCMO/PBCO/LCMO trilayers show that the saturation magnetization of the LCMO contacts increase as the temperature decreases. In other words, degradation of the ferromagnetic contacts is ruled out as a cause. Interestingly, there exists induced net Cu moments, which indicates that the spin degeneracy of the conduction band of the PBCO barrier is lifted and thus the barrier becomes spin selective. Our calculations, within the Wentzel-Kramers-Brillouin approximation, show that the complex temperature dependence can arise from a competition between the high positive spin polarization of the manganite electrodes and a negative spin-filter effect from the interfacial Cu magnetization. This work illustrates that the interface-induced magnetization in layered oxide heterostructures can have non-trivial effects on the macroscopic transport properties. Work performed in collaboration with FA Cuellar, Z Sefrioui, C Leon, J Santamaria (Universidad Complutense de Madrid), JW Freeland, SGE te Velthuis (ANL) and MR Fitzsimmons (LANL). Work at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Basic Energy Sciences under contract no. DE-AC02-06CH11357.

Effect of substitution group on dielectric properties of 4H-pyrano [3, 2-c] quinoline derivatives thin films

NASA Astrophysics Data System (ADS)

H, M. Zeyada; F, M. El-Taweel; M, M. El-Nahass; M, M. El-Shabaan

2016-07-01

The AC electrical conductivity and dielectrical properties of 2-amino-6-ethyl-5-oxo-4-(3-phenoxyphenyl)-5,6-dihydro-4H-pyrano[3, 2-c]quinoline-3-carbonitrile (Ph-HPQ) and 2-amino-4-(2-chlorophenyl)-6-ethyl-5-oxo-5,6-dihydro-4H-pyrano [3, 2-c] quinoline-3-carbonitrile (Ch-HPQ) thin films were determined in the frequency range of 0.5 kHz-5 MHz and the temperature range of 290-443 K. The AC electrical conduction of both compounds in thin film form is governed by the correlated barrier hopping (CBH) mechanism. Some parameters such as the barrier height, the maximum barrier height, the density of charges, and the hopping distance were determined as functions of temperature and frequency. The phenoxyphenyl group has a greater influence on those parameters than the chlorophenyl group. The AC activation energies were determined at different frequencies and temperatures. The dielectric behaviors of Ph-HPQ and Ch-HPQ were investigated using the impedance spectroscopy technique. The impedance data are presented in Nyquist diagrams for different temperatures. The Ch-HPQ films have higher impedance than the Ph-HPQ films. The real dielectric constant and dielectric loss show a remarkable dependence on the frequency and temperature. The Ph-HPQ has higher dielectric constants than the Ch-HPQ.

Quantifying landscape-level methane fluxes in subarctic Finland using a multiscale approach.

PubMed

Hartley, Iain P; Hill, Timothy C; Wade, Thomas J; Clement, Robert J; Moncrieff, John B; Prieto-Blanco, Ana; Disney, Mathias I; Huntley, Brian; Williams, Mathew; Howden, Nicholas J K; Wookey, Philip A; Baxter, Robert

2015-10-01

Quantifying landscape-scale methane (CH4 ) fluxes from boreal and arctic regions, and determining how they are controlled, is critical for predicting the magnitude of any CH4 emission feedback to climate change. Furthermore, there remains uncertainty regarding the relative importance of small areas of strong methanogenic activity, vs. larger areas with net CH4 uptake, in controlling landscape-level fluxes. We measured CH4 fluxes from multiple microtopographical subunits (sedge-dominated lawns, interhummocks and hummocks) within an aapa mire in subarctic Finland, as well as in drier ecosystems present in the wider landscape, lichen heath and mountain birch forest. An intercomparison was carried out between fluxes measured using static chambers, up-scaled using a high-resolution landcover map derived from aerial photography and eddy covariance. Strong agreement was observed between the two methodologies, with emission rates greatest in lawns. CH4 fluxes from lawns were strongly related to seasonal fluctuations in temperature, but their floating nature meant that water-table depth was not a key factor in controlling CH4 release. In contrast, chamber measurements identified net CH4 uptake in birch forest soils. An intercomparison between the aerial photography and satellite remote sensing demonstrated that quantifying the distribution of the key CH4 emitting and consuming plant communities was possible from satellite, allowing fluxes to be scaled up to a 100 km(2) area. For the full growing season (May to October), ~ 1.1-1.4 g CH4  m(-2) was released across the 100 km(2) area. This was based on up-scaled lawn emissions of 1.2-1.5 g CH4  m(-2) , vs. an up-scaled uptake of 0.07-0.15 g CH4  m(-2) by the wider landscape. Given the strong temperature sensitivity of the dominant lawn fluxes, and the fact that lawns are unlikely to dry out, climate warming may substantially increase CH4 emissions in northern Finland, and in aapa mire regions in general. © 2015 The Authors. Global Change Biology Published by John Wiley & Sons Ltd.

Carbon gas exchange at a southern Rocky Mountain wetland, 1996-1998

USGS Publications Warehouse

Wickland, K.P.; Striegl, Robert G.; Mast, M.A.; Clow, D.W.

2001-01-01

Carbon dioxide (CO2) and methane (CH4) exchange between the atmosphere and a subalpine wetland located in Rocky Mountain National Park, Colorado, at 3200 m elevation were measured during 1996-1998. Respiration, net CO2 flux, and CH4 flux were measured using the closed chamber method during snow-free periods and using gas diffusion calculations during snow-covered periods. The ranges of measured flux were 1.2-526 mmol CO2 m-2 d-1 (respiration), -1056-100 mmol CO2 m-2 d-1 (net CO2 exchange), and 0.1-36.8 mmol CH4 m-2 d-1 (a positive value represents efflux to the atmosphere). Respiration and CH4 emission were significantly correlated with 5 cm soil temperature. Annual respiration and CH4 emission were modeled by applying the flux-temperature relationships to a continuous soil temperature record during 1996-1998. Gross photosynthesis was modeled using a hyperbolic equation relating gross photosynthesis, photon flux density, and soil temperature. Modeled annual flux estimates indicate that the wetland was a net source of carbon gas to the atmosphere each of the three years: 8.9 mol C m-2 yr-1 in 1996, 9.5 mol C m-2 yr-1 in 1997, and 9.6 mol C m-2 yr-1 in 1998. This contrasts with the long-term carbon accumulation of ???0.7 mol m-2 yr-1 determined from 14C analyses of a peat core collected from the wetland.

An unusual stable mononuclear Mn(III) bis-terpyridine complex exhibiting Jahn-Teller compression: electrochemical synthesis, physical characterisation and theoretical study.

PubMed

Romain, Sophie; Duboc, Carole; Neese, Frank; Rivière, Eric; Hanton, Lyall R; Blackman, Allan G; Philouze, Christian; Leprêtre, Jean-Claude; Deronzier, Alain; Collomb, Marie-Noëlle

2009-01-01

The mononuclear manganese bis-terpyridine complex [Mn(tolyl-terpy)(2)](X)(3) (1(X)(3); X=BF(4), ClO(4), PF(6); tolyl-terpy=4'-(4-methylphenyl)-2,2':6',2"-terpyridine), containing Mn in the unusual +III oxidation state, has been isolated and characterised. The 1(3+) ion is a rare example of a mononuclear Mn(III) complex stabilised solely by neutral N ligands. Complex 1(3+) is obtained by electrochemical oxidation of the corresponding Mn(II) compound 1(2+) in anhydrous acetonitrile. Under these conditions the cyclic voltammogram of 1(2+) exhibits not only the well-known Mn(II)/Mn(III) oxidation at E(1/2)=+0.91 V versus Ag/Ag(+) (+1.21 V vs. SCE) but also a second metal-based oxidation process corresponding to Mn(III)/Mn(IV) at E(1/2)=+1.63 V (+1.93 V vs. SCE). Single crystals of 1(PF(6))(3)2 CH(3)CN were obtained by an electrocrystallisation procedure. X-ray analysis unambiguously revealed its tetragonally compressed octahedral geometry and high-spin character. The electronic properties of 1(3+) were investigated in detail by magnetic measurements and theoretical calculations, from which a D value of +4.82 cm(-1) was precisely determined. Density functional and complete active space self consistent field ab initio calculations both correctly predict a positive sign of D, in agreement with the compressed tetragonal distortion observed in the X-ray structure of 1(PF(6))(3)2 CH(3)CN. The different contributions to D were calculated, and the results show that 1) the spin-orbit coupling part (+2.593 cm(-1)) is predominant compared to the spin-spin interaction (+1.075 cm(-1)) and 2) the excited triplet states make the dominant contribution to the total D value.

Tropospheric photooxidation of CF3CH2CHO and CF3(CH2)2CHO initiated by Cl atoms and OH radicals

NASA Astrophysics Data System (ADS)

Antiñolo, M.; Jiménez, E.; Notario, A.; Martínez, E.; Albaladejo, J.

2009-11-01

The absolute rate coefficients for the tropospheric reactions of chlorine (Cl) atoms and hydroxyl (OH) radicals with CF3CH2CHO and CF3(CH2)2CHO were measured as a function of temperature (263-371 K) and pressure (50-215 Torr of He) by pulsed UV laser photolysis techniques. Vacuum UV resonance fluorescence was employed to detect and monitor the time evolution of Cl atoms. Laser induced fluorescence was used in this work as a detection of OH radicals as a function of reaction time. No pressure dependence of the bimolecular rate coefficients, kCl and kOH, was found at all temperatures. At room temperature kCl and kOH were (in 10-11 cm3 molecule-1 s-1): kCl(CF3CH2CHO) = (1.55±0.53); kCl(CF3(CH2)2CHO) = (3.39±1.38); kOH(CF3CH2CHO) = (0.259±0.050); kOH(CF3(CH2)2CHO) = (1.28±0.24). A slightly negative temperature dependence of kCl was observed for CF3CH2CHO and CF3(CH2)2CHO, and kOH(CF3CH2CHO). In contrast, kOH(CF3(CH2)2CHO) did not exhibit a temperature dependence in the studied ranged. Arrhenius expressions for these reactions were: kCl(CF3CH2CHO) =(4.4±1.0) × 10-11 exp{-(316±68)/T} cm3 molecule-1 s-1, kCl(CF3(CH2)2CHO) = (2.9±0.7) × 10-10 exp{-625±80)/T} cm3 molecule-1 s-1, kOH(CF3CH2CHO) = (7.8±2.2) × 10-12 exp{-(314±90)/T} cm3 molecule-1 s-1. The atmospheric impact of the homogeneous removal by OH radicals and Cl atoms of these fluorinated aldehydes is discussed in terms of the global atmospheric lifetimes, taking into account different degradation pathways. The calculated lifetimes show that atmospheric oxidation of CF3(CH2)xCHO are globally dominated by OH radicals, however reactions initiated by Cl atoms can act as a source of free radicals at dawn in the troposphere.

Tropospheric photooxidation of CF3CH2CHO and CF3(CH2)2CHO initiated by Cl atoms and OH radicals

NASA Astrophysics Data System (ADS)

Antiñolo, M.; Jiménez, E.; Notario, A.; Martínez, E.; Albaladejo, J.

2010-02-01

The absolute rate coefficients for the tropospheric reactions of chlorine (Cl) atoms and hydroxyl (OH) radicals with CF3CH2CHO and CF3(CH2)2CHO were measured as a function of temperature (263-371 K) and pressure (50-215 Torr of He) by pulsed UV laser photolysis techniques. Vacuum UV resonance fluorescence was employed to detect and monitor the time evolution of Cl atoms. Laser induced fluorescence was used in this work for the detection of OH radicals as a function of reaction time. No pressure dependence of the bimolecular rate coefficients, kCl and kOH, was found at all temperatures. At room temperature kCl and kOH were (in 10-11 cm3 molecule-1 s-1): kCl(CF3CH2CHO) = (1.55±0.53); kCl(CF3(CH2)2CHO) = (3.39±1.38); kCl(CF3CH2CHO) = (0.259±0.050); kCl(CF3(CH2)2CHO) = (1.28±0.24). A slightly positive temperature dependence of kCl was observed for CF3CH2CHO and CF3(CH2)2CHO, and kOH(CF3CH2CHO). In contrast, kOH(CF3(CH2)2CHO) did not exhibit a temperature dependence over the range investigated. Arrhenius expressions for these reactions were: kCl(CF3CH2CHO) = (4.4±1.0)×10-11 exp{-(316±68)/T} cm3 molecule-1 s-1 kCl(CF3(CH2)2CHO) = (2.9±0.7)×10-10 exp{-(625±80)/T} cm3 molecule-1 s-1 kOH(CF3CH2CHO) = (7.8±2.2)×10-12 exp{-(314±90)/T} cm3 molecule-1 s-1 The atmospheric impact of the homogeneous removal by OH radicals and Cl atoms of these fluorinated aldehydes is discussed in terms of the global atmospheric lifetimes, taking into account different degradation pathways. The calculated lifetimes show that atmospheric oxidation of CF3(CH2)x CHO are globally dominated by OH radicals, however reactions initiated by Cl atoms can act as a source of free radicals at dawn in the troposphere.

Mott-metal transition in layered perovskite iridate thin films via field-effect doping

NASA Astrophysics Data System (ADS)

Cheema, Suraj; Turcaud, Jeremy; Nelson, Chris; Salahuddin, Sayeef; Ramesh, Ramamoorthy

We report on electrostatic gating of spin-orbit coupled Mott insulator Sr2IrO4 (Sr214) via ferroelectric field effect doping. Field effect doping has been used to modulate electronic phenomena in emerging 2D systems and strongly correlated oxides, but 5 d systems with large spin-orbit coupling have yet to be explored. Upon switching the polarization field of ferroelectric Pb(Zr20Ti80)O3 (PZT) to the down-poled (electron-accumulation) state, temperature-dependent resistivity measurements indicate extremely metallic behavior in the ultrathin Sr214 channel. This work successfully closes the Mott gap in Sr214 in a ''clean'' doping environment free of chemical disorder, thereby strengthening the link to the isostrucutral high-Tc cuprates, as Sr214 has been predicted to host d-wave superconductivity upon electron doping the parent antiferromagnetic insulating phase. Furthermore, the metallic behavior in Sr214 persists for thickness beyond the expected screening length, suggestive of a collective carrier delocalization mechanism. Electrostatically doped carriers prove to be a useful method for tuning the competition between spin-orbit and Coulomb interactions in order to trigger novel phase transitions, such as the Mott-metal crossover. This work was supported by the Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy, under Contract No. DE-AC02-05CH11231.

Structure, phase transitions, and isotope effects in [(CH3)4N]2PuCl6

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

Wilson, Richard E.

2015-11-02

The single crystal X-ray diffraction structure of [(CH3)4N]2PuCl6 is presented for the first time, resolving long standing confusion and speculation regarding the structure of this compound in the literature. A temperature dependent study of this compound shows that the structure of [(CH3)4N]2PuCl6 undergoes no fewer than two phase transitions between 100 and 360 K. The phase of [(CH3)4N]2PuCl6 at room temperature is Fd-3c a = 26.012(3) Å. At 360 K, the structure is in space group Fm-3m with a = 13.088(1) Å. The plutonium octahedra and tetramethylammonium cations undergo a rotative displacement and the degree of rotation varies with temperature,more » giving rise to the phase transition from Fm-3m to Fd-3c as the crystal is cooled. Synthesis and structural studies of the deuterated salt [(CD3)4N]2PuCl6 suggest that there is an isotopic effect associated with this phase transition as revealed by a changing transition temperature in the deuterated versus protonated compound indicating that the donor-acceptor interactions between the tetramethylammonium cations and the hexachloroplutonate anions are driving the phase transformation.« less

A pan-Arctic synthesis of CH4 and CO2 production from anoxic soil incubations

USGS Publications Warehouse

Treat, C.C.; Natali, Susan M.; Ernakovich, Jessica; Iverson, Colleen M.; Lupasco, Massimo; McGuire, A. David; Norby, Richard J.; Roy Chowdhury, Taniya; Richter, Andreas; Šantrůčková, Hana; Schädel, C.; Schuur, Edward A.G.; Sloan, Victoria L.; Turetsky, Merritt R.; Waldrop, Mark P.

2015-01-01

Permafrost thaw can alter the soil environment through changes in soil moisture, frequently resulting in soil saturation, a shift to anaerobic decomposition, and changes in the plant community. These changes, along with thawing of previously frozen organic material, can alter the form and magnitude of greenhouse gas production from permafrost ecosystems. We synthesized existing methane (CH4) and carbon dioxide (CO2) production measurements from anaerobic incubations of boreal and tundra soils from the geographic permafrost region to evaluate large-scale controls of anaerobic CO2 and CH4 production and compare the relative importance of landscape-level factors (e.g., vegetation type and landscape position), soil properties (e.g., pH, depth, and soil type), and soil environmental conditions (e.g., temperature and relative water table position). We found fivefold higher maximum CH4 production per gram soil carbon from organic soils than mineral soils. Maximum CH4 production from soils in the active layer (ground that thaws and refreezes annually) was nearly four times that of permafrost per gram soil carbon, and CH4 production per gram soil carbon was two times greater from sites without permafrost than sites with permafrost. Maximum CH4 and median anaerobic CO2 production decreased with depth, while CO2:CH4 production increased with depth. Maximum CH4 production was highest in soils with herbaceous vegetation and soils that were either consistently or periodically inundated. This synthesis identifies the need to consider biome, landscape position, and vascular/moss vegetation types when modeling CH4 production in permafrost ecosystems and suggests the need for longer-term anaerobic incubations to fully capture CH4 dynamics. Our results demonstrate that as climate warms in arctic and boreal regions, rates of anaerobic CO2 and CH4 production will increase, not only as a result of increased temperature, but also from shifts in vegetation and increased ground saturation that will accompany permafrost thaw.

High-temperature charge density wave correlations in La 1.875Ba 0.125CuO 4 without spin–charge locking

DOE PAGES

Miao, H.; Lorenzana, J.; Seibold, G.; ...

2017-11-07

Although all superconducting cuprates display charge-ordering tendencies, their low-temperature properties are distinct, impeding efforts to understand the phenomena within a single conceptual framework. While some systems exhibit stripes of charge and spin, with a locked periodicity, others host charge density waves (CDWs) without any obviously related spin order. Here we use resonant inelastic X-ray scattering to follow the evolution of charge correlations in the canonical stripe-ordered cuprate La 1.875Ba 0.125CuO 4 across its ordering transition. We find that high-temperature charge correlations are unlocked from the wavevector of the spin correlations, signaling analogies to CDW phases in various other cuprates. Thismore » indicates that stripe order at low temperatures is stabilized by the coupling of otherwise independent charge and spin density waves, with important implications for the relation between charge and spin correlations in the cuprates.« less

High-temperature charge density wave correlations in La 1.875Ba 0.125CuO 4 without spin–charge locking

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

Miao, H.; Lorenzana, J.; Seibold, G.

Although all superconducting cuprates display charge-ordering tendencies, their low-temperature properties are distinct, impeding efforts to understand the phenomena within a single conceptual framework. While some systems exhibit stripes of charge and spin, with a locked periodicity, others host charge density waves (CDWs) without any obviously related spin order. Here we use resonant inelastic X-ray scattering to follow the evolution of charge correlations in the canonical stripe-ordered cuprate La 1.875Ba 0.125CuO 4 across its ordering transition. We find that high-temperature charge correlations are unlocked from the wavevector of the spin correlations, signaling analogies to CDW phases in various other cuprates. Thismore » indicates that stripe order at low temperatures is stabilized by the coupling of otherwise independent charge and spin density waves, with important implications for the relation between charge and spin correlations in the cuprates.« less

MIL-53 frameworks in mixed-matrix membranes and cross-linked ZIF-8/matrimidRTM mixed-matrix membranes for gas separation

NASA Astrophysics Data System (ADS)

Hsieh, Josephine Ordonez

Mixed matrix membranes (MMMs) are hybrid materials consisting of two phases: an inorganic nanoscale particle as the discrete phase, and a polymeric material as the continuous phase. The incorporation of inorganic particles into a polymer can improve a membrane's overall separation performance. MMMs incorporating metal-organic frameworks (MOFs) have exhibited promising gas separation performance. MOFs are inorganic-organic crystals constructed from metal ions that are linked by polydentate ligands. Zeolitic imidazolate frameworks (ZIFs) are a sub-class of MOFs that uses imidazole analogues as ligands. In these studies, the MOF MIL-53 and ZIF-8 were successfully synthesized and characterized by a battery of analytical techniques including XRD, FTIR, TGA, N2 adsorption, and SEM, and were incorporated into MMMs with Matrimid® polymer. In chapter 1, MIL-53/Matrimid® MMMs containing MIL-53-ht (open-pore form) were fabricated, characterized and obtained permeability values higher than Matrimid®. Selectivities decreased for the gas pairs of O2/N2, H2/O2, H2/CO2, and H2/N2. However, slight enhancement of the CO2/CH4 selectivity was observed for the MIL-53-ht/Matrimid® compared to that of Matrimid ®. The MIL-53-as/Matrimid® MMM also showed an increase in permeability as well as an increase in selectivity for the gas pairs H2/O2, CO2/CH4, H 2/CH4, and H2/N2. The MIL-53-lt/Matrimid ® MMM showed that it does not retain its closed-pore form in the MMM due to chloroform solvent opening the pores and eventually polymer confinement of the MIL 53 framework in the MMM. In chapter 2, easy synthesis and fabrication of the MIL-53 MOF membrane was realized using a seeded growth method with a commercially available alumina TLC plate. The MOF membrane had a well-intergrown and dense layer of MIL-53 crystals on the surface of the alumina substrate. The MIL-53 crystals were also converted to the MIL-53-lt (closed-pore form) after heating at 330 °C and cooling to room temperature, which confirms the breathing ability of the MOF. In chapter 3, a comprehensive approach for membrane materials in order to achieve high productivity and separation efficiency was applied by incorporating additives into polymers and cross-linking the resulting MMM that could lead to increase and simultaneous selectivity enhancement. ZIF-8 was used as an additive in these MMMs. ZIF-8 can readily absorb small gases such, as H 2 and CO2 due to its 3.4 Å pore aperture. ZIF-8/Matrimid ® MMMs were fabricated with a spin-coated Matrimid® layer on one surface and cross-linked with EDA vapor. This membrane morphology could lead to enhanced selectivities due to the cross-linked layer, at the same time maintain the high permeability of the bulk MMM. The permeabilities decreased for the cross-linked, spin-coated Matrimid® ZIF-8/Matrimid ® MMMs. However, there was enhancement in selectivities for H 2/CO2, H2/N2, H2/O 2 and H2/CH4 gas pairs, which can be due to reduction of diffusive pathways for larger gas molecules. Compared to uncross-linked ZIF-8/Matrimid® MMMs, the cross-linked, spin-coated Matrimid ® ZIF-8/Matrimid® MMMs lie close to the Robeson's upper bound for H2/CO2 suggesting its potential for this gas pair separation.

Environmental and vegetation controls on the spatial variability of CH4 emission from wet-sedge and tussock tundra ecosystems in the Arctic.

PubMed

McEwing, Katherine Rose; Fisher, James Paul; Zona, Donatella

Despite multiple studies investigating the environmental controls on CH 4 fluxes from arctic tundra ecosystems, the high spatial variability of CH 4 emissions is not fully understood. This makes the upscaling of CH 4 fluxes from plot to regional scale, particularly challenging. The goal of this study is to refine our knowledge of the spatial variability and controls on CH 4 emission from tundra ecosystems. CH 4 fluxes were measured in four sites across a variety of wet-sedge and tussock tundra ecosystems in Alaska using chambers and a Los Gatos CO 2 and CH 4 gas analyser. All sites were found to be sources of CH 4 , with northern sites (in Barrow) showing similar CH 4 emission rates to the southernmost site (ca. 300 km south, Ivotuk). Gross primary productivity (GPP), water level and soil temperature were the most important environmental controls on CH 4 emission. Greater vascular plant cover was linked with higher CH 4 emission, but this increased emission with increased vascular plant cover was much higher (86 %) in the drier sites, than the wettest sites (30 %), suggesting that transport and/or substrate availability were crucial limiting factors for CH 4 emission in these tundra ecosystems. Overall, this study provides an increased understanding of the fine scale spatial controls on CH 4 flux, in particular the key role that plant cover and GPP play in enhancing CH 4 emissions from tundra soils.

Heterospin systems constructed from [Cu2Ln]3+ and [Ni(mnt)2]1-,2- Tectons: First 3p-3d-4f complexes (mnt = maleonitriledithiolato).

PubMed

Madalan, Augustin M; Avarvari, Narcis; Fourmigué, Marc; Clérac, Rodolphe; Chibotaru, Liviu F; Clima, Sergiu; Andruh, Marius

2008-02-04

New heterospin complexes have been obtained by combining the binuclear complexes [{Cu(H(2)O)L(1)}Ln(O(2)NO)(3)] or [{CuL(2)}Ln(O(2)NO)(3)] (L(1) = N,N'-propylene-di(3-methoxysalicylideneiminato); L(2) = N,N'-ethylene-di(3-methoxysalicylideneiminato); Ln = Gd(3+), Sm(3+), Tb(3+)), with the mononuclear [CuL(1)(2)] and the nickel dithiolene complexes [Ni(mnt)(2)](q)- (q = 1, 2; mnt = maleonitriledithiolate), as follows: (1)infinity[{CuL(1)}(2)Ln(O(2)NO){Ni(mnt)(2)}].Solv.CH(3)CN (Ln = Gd(3+), Solv = CH(3)OH (1), Ln = Sm(3+), Solv = CH(3)CN (2)) and [{(CH(3)OH)CuL(2)}(2)Sm(O(2)NO)][Ni(mnt)(2)] (3) with [Ni(mnt)2]2-, [{(CH(3)CN)CuL(1)}(2)Ln(H(2)O)][Ni(mnt)(2)]3.2CH(3)CN (Ln = Gd(3+) (4), Sm(3+) (5), Tb(3+) (6)), and [{(CH(3)OH)CuL(2)}{CuL(2)}Gd(O(2)NO){Ni(mnt)(2)}][Ni(mnt)(2)].CH(2)Cl(2) (7) with [Ni(mnt))(2]*-. Trinuclear, almost linear, [CuLnCu] motifs are found in all the compounds. In the isostructural 1 and 2, two trans cyano groups from a [Ni(mnt)2]2- unit bridge two trimetallic nodes through axial coordination to the Cu centers, thus leading to the establishment of infinite chains. 3 is an ionic compound, containing discrete [{(CH(3)OH)CuL(2)}(2)Sm(O(2)NO)](2+) cations and [Ni(mnt)(2)](2-) anions. Within the series 4-6, layers of discrete [CuLnCu](3+) motifs alternate with stacks of interacting [Ni(mnt)(2)](*-) radical anions, for which two overlap modes, providing two different types of stacks, can be disclosed. The strength of the intermolecular interactions between the open-shell species is estimated through extended Hückel calculations. In compound 7, [Ni(mnt)(2)](*-) radical anions coordinate group one of the Cu centers of a trinuclear [Cu(2)Gd] motif through a CN, while discrete [Ni(mnt)(2)](*-) units are also present, overlapping in between, but also with the coordinated ones. Furthermore, the [Cu(2)Gd] moieties dimerize each other upon linkage by two nitrato groups, both acting as chelate toward the gadolinium ion from one unit and monodentate toward a Cu ion from the other unit. The magnetic properties of the gadolinium-containing complexes have been determined. Ferromagnetic exchange interactions within the trinuclear [Cu(2)Gd] motifs occur. In the compounds 4 and 7, the [Ni(mnt)(2)](*-) radical anions contribution to the magnetization is clearly observed in the high-temperature regime, and most of it vanishes upon temperature decrease, very likely because of the rather strong antiferromagnetic exchange interactions between the open-shell species. The extent of the exchange interaction in the compound 7, which was found to be antiferromagnetic, between the coordinated Cu center and the corresponding [Ni(mnt)(2)](*-) radical anion, bearing mostly a 3p spin type, was estimated through CASSCF/CASPT2 calculations. Compound 6 exhibits a slow relaxation of the magnetization.

Quasi-two-dimensional spin correlations in the triangular lattice bilayer spin glass LuCoGaO 4

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

Fritsch, Katharina; Ross, Kathyrn A.; Granroth, Garrett E.

Here we present a single-crystal time-of-flight neutron scattering study of the static and dynamic spin correlations in LuCoGaO 4, a quasi-two-dimensional dilute triangular lattice antiferromagnetic spin-glass material. This system is based on Co 2+ ions that are randomly distributed on triangular bilayers within the YbFe 2O 4 type, hexagonal crystal structure. Antiferromagnetic short-range two-dimensional correlations at wave vectors Q = (1/3,1/3, L) develop within the bilayers at temperatures as high as |Θ CW| ~100 K and extend over roughly five unit cells at temperatures below T g = 19 K. These two-dimensional static correlations are observed as diffuse rods ofmore » neutron scattering intensity along c * and display a continuous spin freezing process in their energy dependence. Aside from exhibiting these typical spin-glass characteristics, this insulating material reveals a novel gapped magnetic resonant spin excitation at ΔE ~12 meV localized around Q = (1 / 3, 1 / 3,L) . The temperature dependence of the spin gap associated with this two-dimensional excitation correlates with the evolution of the static correlations into the spin-glass state ground state. Lastly, we associate it with the effect of the staggered exchange field acting on the S eff = 1/2 Ising-like doublet of the Co 2+ moments.« less

Quasi-two-dimensional spin correlations in the triangular lattice bilayer spin glass LuCoGaO 4

DOE PAGES

Fritsch, Katharina; Ross, Kathyrn A.; Granroth, Garrett E.; ...

2017-09-13

Here we present a single-crystal time-of-flight neutron scattering study of the static and dynamic spin correlations in LuCoGaO 4, a quasi-two-dimensional dilute triangular lattice antiferromagnetic spin-glass material. This system is based on Co 2+ ions that are randomly distributed on triangular bilayers within the YbFe 2O 4 type, hexagonal crystal structure. Antiferromagnetic short-range two-dimensional correlations at wave vectors Q = (1/3,1/3, L) develop within the bilayers at temperatures as high as |Θ CW| ~100 K and extend over roughly five unit cells at temperatures below T g = 19 K. These two-dimensional static correlations are observed as diffuse rods ofmore » neutron scattering intensity along c * and display a continuous spin freezing process in their energy dependence. Aside from exhibiting these typical spin-glass characteristics, this insulating material reveals a novel gapped magnetic resonant spin excitation at ΔE ~12 meV localized around Q = (1 / 3, 1 / 3,L) . The temperature dependence of the spin gap associated with this two-dimensional excitation correlates with the evolution of the static correlations into the spin-glass state ground state. Lastly, we associate it with the effect of the staggered exchange field acting on the S eff = 1/2 Ising-like doublet of the Co 2+ moments.« less

Low-temperature conversion of methane to methanol on CeO x/Cu 2O catalysts: Water controlled activation of the C–H Bond

DOE PAGES

Zuo, Zhijun; Ramírez, Pedro J.; Senanayake, Sanjaya D.; ...

2016-10-10

Here, an inverse CeO 2/Cu 2O/Cu(111) catalyst is able to activate methane at room temperature producing C, CH x fragments and CO x species on the oxide surface. The addition of water to the system leads to a drastic change in the selectivity of methane activation yielding only adsorbed CH x fragments. At a temperature of 450 K, in the presence of water, a CH 4 → CH 3OH catalytic transformation occurs with a high selectivity. OH groups formed by the dissociation of water saturate the catalyst surface, removing sites that could decompose CH x fragments, and generating centers onmore » which methane can directly interact to yield methanol.« less

Effect of temperature on continuous dry fermentation of swine manure.

PubMed

Deng, Liangwei; Chen, Chuang; Zheng, Dan; Yang, Hongnan; Liu, Yi; Chen, Ziai

2016-07-15

Laboratory-scale experiments were performed on the dry digestion of solid swine manure in a semi-continuous mode using 4.5 L down plug-flow anaerobic reactors with an organic loading rate of 3.46 kg volatile solids (VS) m(-3) d(-1) to evaluate the effects of temperature (15, 25 and 35 °C). At 15 °C, biogas production was the poorest due to organic overload and acidification, with a methane yield of 0.036 L CH4 g(-1) VS added and a volumetric methane production rate of 0.125 L CH4 L(-1) d(-1). The methane yield and volumetric methane production rate at 25 °C (0.226 L CH4 g(-1) VS added and 0.783 L CH4 L(-1) d(-1), respectively) were 6.24 times higher than those at 15 °C. However, the methane yield (0.237 L CH4 g(-1) VS added) and the volumetric methane production rate (0.821 L CH4 L(-1) d(-1)) at 35 °C were only 4.86% higher than those at 25 °C, which indicated similar results were obtained at 25 °C and 35 °C. The lower biogas production at 35 °C in dry digestion compared with that in wet digestion could be attributed to ammonia inhibition. For a single pig farm, digestion of solid manure is accomplished in small-scale domestic or small-farm bioreactors, for which operating temperatures of 35 °C are sometimes difficult to achieve. Considering biogas production, ammonia inhibition and net energy recovery, an optimum temperature for dry digestion of solid swine manure is 25 °C. Copyright © 2016 Elsevier Ltd. All rights reserved.

Climate-driven increase of natural wetland methane emissions offset by human-induced wetland reduction in China over the past three decades

USGS Publications Warehouse

Zhu, Qiuan; Peng, Changhui; Liu, Jinxun; Jiang, Hong; Fang, Xiuqin; Chen, Huai; Niu, Zhichun; Gong, Peng; Lin, Guanghui; Wang, Meng; Yang, Yanzheng; Chang, Jie; Ge, Ying; Xiang, Wenhua; Deng, Xiangwen; He, Jin-Sheng

2016-01-01

Both anthropogenic activities and climate change can affect the biogeochemical processes of natural wetland methanogenesis. Quantifying possible impacts of changing climate and wetland area on wetland methane (CH4) emissions in China is important for improving our knowledge on CH4 budgets locally and globally. However, their respective and combined effects are uncertain. We incorporated changes in wetland area derived from remote sensing into a dynamic CH4 model to quantify the human and climate change induced contributions to natural wetland CH4 emissions in China over the past three decades. Here we found that human-induced wetland loss contributed 34.3% to the CH4 emissions reduction (0.92 TgCH4), and climate change contributed 20.4% to the CH4 emissions increase (0.31 TgCH4), suggesting that decreasing CH4 emissions due to human-induced wetland reductions has offset the increasing climate-driven CH4 emissions. With climate change only, temperature was a dominant controlling factor for wetland CH4 emissions in the northeast (high latitude) and Qinghai-Tibet Plateau (high altitude) regions, whereas precipitation had a considerable influence in relative arid north China. The inevitable uncertainties caused by the asynchronous for different regions or periods due to inter-annual or seasonal variations among remote sensing images should be considered in the wetland CH4 emissions estimation.

Climate-driven increase of natural wetland methane emissions offset by human-induced wetland reduction in China over the past three decades

PubMed Central

Zhu, Qiuan; Peng, Changhui; Liu, Jinxun; Jiang, Hong; Fang, Xiuqin; Chen, Huai; Niu, Zhenguo; Gong, Peng; Lin, Guanghui; Wang, Meng; Wang, Han; Yang, Yanzheng; Chang, Jie; Ge, Ying; Xiang, Wenhua; Deng, Xiangwen; He, Jin-Sheng

2016-01-01

Both anthropogenic activities and climate change can affect the biogeochemical processes of natural wetland methanogenesis. Quantifying possible impacts of changing climate and wetland area on wetland methane (CH4) emissions in China is important for improving our knowledge on CH4 budgets locally and globally. However, their respective and combined effects are uncertain. We incorporated changes in wetland area derived from remote sensing into a dynamic CH4 model to quantify the human and climate change induced contributions to natural wetland CH4 emissions in China over the past three decades. Here we found that human-induced wetland loss contributed 34.3% to the CH4 emissions reduction (0.92 TgCH4), and climate change contributed 20.4% to the CH4 emissions increase (0.31 TgCH4), suggesting that decreasing CH4 emissions due to human-induced wetland reductions has offset the increasing climate-driven CH4 emissions. With climate change only, temperature was a dominant controlling factor for wetland CH4 emissions in the northeast (high latitude) and Qinghai-Tibet Plateau (high altitude) regions, whereas precipitation had a considerable influence in relative arid north China. The inevitable uncertainties caused by the asynchronous for different regions or periods due to inter-annual or seasonal variations among remote sensing images should be considered in the wetland CH4 emissions estimation. PMID:27892535

Recovery of Methane Consumption by Secondary Forests in the Amazon River Basin

NASA Astrophysics Data System (ADS)

Webster, K. D.; Meredith, L. K.; Piccini, W.; Pedrinho, A.; Nüsslein, K.; Van Haren, J. L. M.; Camargo, P. B. D.; Mui, T. S.; Saleska, S. R.

2017-12-01

Methane (CH4) is a major greenhouse gas in Earth's atmosphere and its atmospheric global mole fraction has roughly doubled since the start of the industrial revolution. The tropics are thought to be a major CH4 emitter, with the Amazon River Basin estimated to contribute 7 % of the annual flux to the atmosphere. The Amazon has experienced extensive land use change during the past 30 years, but we lack an understanding of the qualitative and quantitative effects of land use change on CH4 flux from the Amazon and the associated reasons. To illuminate the factors controlling CH4 flux across land use gradients in the Amazon we measured the CH4 fluxes and will measure the associated stable isotopic composition from pastures, primary forests, and secondary forests, at Ariquemes (Western Amazon, more deforested), and Santarem (Eastern Amazon, less deforested), Brazil. The sites near Santarem were sampled in June of 2016 and the sites near Ariquemes were sampled in March and April of 2017, both at the end of the wet season. Little difference was observed between land use types in Santarem with each land use type slightly consuming atmospheric CH4. However, pasture fluxes at Ariquemes were higher (+520 μg-C m-2 hr-1) than in primary (0 μg-C m-2 hr-1) and secondary forests (-20 μg-C m-2 hr-1; p = 6*10-4). CH4 flux from individual Santarem sites was not correlated with environmental variables. CH4 flux from Airquemes was correlated with several parameters across all samples including soil temperature (p = 7*10-4), and soil humidity (p = 0.02). Despite the fact that pastures experienced higher soil temperatures than forest soils this appears to be a low predictor of CH4 flux from these environments as it was seen at both Santarem and Ariquemes. The analysis of the stable isotopic composition of CH4 from these chambers will aid in understanding the competing processes of microbial CH4 consumption and production in these soils and why pastures may become CH4 sources and secondary forests are able to regain the function as a CH4 sink in some instances. Support: NSF, FAPESP-Biota, CNPq, CAPES.

Room temperature spin valve effect in NiFe/WS2/Co junctions

PubMed Central

Iqbal, Muhammad Zahir; Iqbal, Muhammad Waqas; Siddique, Salma; Khan, Muhammad Farooq; Ramay, Shahid Mahmood

2016-01-01

The two-dimensional (2D) layered electronic materials of transition metal dichalcogenides (TMDCs) have been recently proposed as an emerging canddiate for spintronic applications. Here, we report the exfoliated single layer WS2-intelayer based spin valve effect in NiFe/WS2/Co junction from room temperature to 4.2 K. The ratio of relative magnetoresistance in spin valve effect increases from 0.18% at room temperature to 0.47% at 4.2 K. We observed that the junction resistance decreases monotonically as temperature is lowered. These results revealed that semiconducting WS2 thin film works as a metallic conducting interlayer between NiFe and Co electrodes. PMID:26868638

Room temperature spin valve effect in NiFe/WS₂/Co junctions.

PubMed

Iqbal, Muhammad Zahir; Iqbal, Muhammad Waqas; Siddique, Salma; Khan, Muhammad Farooq; Ramay, Shahid Mahmood

2016-02-12

The two-dimensional (2D) layered electronic materials of transition metal dichalcogenides (TMDCs) have been recently proposed as an emerging canddiate for spintronic applications. Here, we report the exfoliated single layer WS2-intelayer based spin valve effect in NiFe/WS2/Co junction from room temperature to 4.2 K. The ratio of relative magnetoresistance in spin valve effect increases from 0.18% at room temperature to 0.47% at 4.2 K. We observed that the junction resistance decreases monotonically as temperature is lowered. These results revealed that semiconducting WS2 thin film works as a metallic conducting interlayer between NiFe and Co electrodes.

[Methane fluxes and controlling factors in the intertidal zone of the Yellow River estuary in autumn].

PubMed

Jiang, Huan-Huan; Sun, Zhi-Gao; Wang, Ling-Ling; Mou, Xiao-Jie; Sun, Wan-Long; Song, Hong-Li; Sun, Wen-Guang

2012-02-01

The characteristics of methane (CH4) fluxes from tidal wetlands of the Yellow River estuary were observed in situ with static-chamber and GC methods in September and October 2009, and the key factors affecting CH4 fluxes were discussed. From the aspect of space, the CH4 flux ranges in high tidal wetland, middle tidal wetland, low tidal wetland, bare flat are - 0.206-1.264, -0.197-0.431, -0.125-0.659 and -0.742-1.767 mg x (m2 x h)(-1), the day average fluxes are 0.089, 0.038, 0.197 and 0.169 mg x (m2 x h)(-1), respectively, indicating that the tidal wetlands are the sources of CH4 and the source function of CH4 differed among the four study sites, in the order of low tidal wetland > bare flat > high tidal wetland > middle tidal wetland. From the aspect of time, the ranges of CH4 fluxes from the tidal wetland ecosystems are -0.444-1.767 and - 0.742- 1.264 mg x (m2 x h)(-1), and the day average fluxes are 0.218 and 0.028 mg x (m2 x h)(-1) in September and October, respectively. The CH4 fluxes in each tidal wetland in September are higher than those in October except that the high tidal wetland acts as weak sink in September. Further studies indicate that the changes of environmental factors in the Yellow River estuary are complicated, and the CH4 fluxes are affected by multiple factors. The differences of CH4 fluxes characteristics among different tidal wetlands in autumn are probably related to temperature (especially atmospheric temperature) and vegetation growth status, while the effects of water or salinity condition and tide status on the CH4 flux characteristics might not be ignored.

Determining the spin dependent mean free path in Co90Fe10 using giant magnetoresistance

NASA Astrophysics Data System (ADS)

Shakespear, K. F.; Perdue, K. L.; Moyerman, S. M.; Checkelsky, J. G.; Harberger, S. S.; Tamboli, A. C.; Carey, M. J.; Sparks, P. D.; Eckert, J. C.

2005-05-01

The spin dependent mean free path in Co90Fe10 is determined as a function of temperature down to 5K using two different spin valve structures. At 5K the spin dependent mean free path for one structure was measured to be 9.4±1.4nm, decreasing by a factor of 3 by 350K. For the other structure, it is 7.5±0.5nm at 5K and decreased by a factor of 1.5 by 350K. In both cases, the spin dependent mean free path approaches the typical thickness of ferromagnetic layers in spin valves at room temperature and, thus, has an impact on the choice of design parameters for the development of new spintronic devices.

Electron spin resonance in the superconducting state of Ba0.6K0.4Fe2As2

NASA Astrophysics Data System (ADS)

Dlamini, Zolile Wiseman; Srinivasan, A.; Ma, Yanwei; Srinivasu, V. V.

2018-05-01

We report the observation of electron spin resonance (ESR) signals in a single crystal of Ba0.6K0.4Fe2As2 grown by self-flux method. We observed two narrow resonant absorption signals at g-values of 4.3 and 1.99. Significantly, these signals are stronger in intensity at 5 K. They become weaker as the temperature is increased and finally vanish at Tc. The resonance at g = 4.3 (signal I) shows different temperature dependence of intensity for parallel and perpendicular orientations of the magnetic field to the iron arsenide plane. However, the resonance at g = 1.99 (signal 2) does not show much difference in temperature dependence of intensity for the two orientations. Further, temperature dependence of the linewidth of the two signals are also different. We propose that these two signals have their origin in fluctuations in the spin system as magnetic fluctuations are believed to be the origin of superconductivity in iron pnictides. Temperature dependence of intensity of signal I is indicative of Fe cluster formation in the scenario of coexistence of spin density wave and superconducting phase for this composition of the crystal.

An Effective-Hamiltonian Approach to CH5+, Using Ideas from Atomic Spectroscopy

NASA Astrophysics Data System (ADS)

Hougen, Jon T.

2016-06-01

In this talk we present the first steps in the design of an effective Hamiltonian for the vibration-rotation energy levels of CH5+. Such a Hamiltonian would allow calculation of energy level patterns anywhere along the path travelled by a hypothetical CH5+ (or CD5+) molecule as it passes through various coupling cases, and might thus provide some hints for assigning the observed high-resolution spectra. The steps discussed here, which have not yet addressed computational problems, focus on mapping the vibration-rotation problem in CH5+ onto the five-electron problem in the boron atom, using ideas and mathematical machinery from Condon and Shortley's book on atomic spectroscopy. The mapping ideas are divided into: (i) a mapping of particles, (ii) a mapping of coordinates (i.e., mathematical degrees of freedom), and (iii) a mapping of quantum mechanical interaction terms. The various coupling cases along the path correspond conceptually to: (i) the analog of a free-rotor limit, where the H atoms see the central C atom but do not see each other, (ii) the low-barrier and high-barrier tunneling regimes, and (iii) the rigid-molecule limit, where the H atoms remain locked in some fixed molecular geometry. Since the mappings considered here often involve significant changes in mathematics, a number of interesting qualitative changes occur in the basic ideas when passing from B to CH5+, particularly in discussions of: (i) antisymmetrization and symmetrization ideas, (ii) n,l,ml,ms or n,l,j,mj quantum numbers, and (iii) Russell-Saunders computations and energy level patterns. Some of the mappings from B to CH5+ to be discussed are as follows. Particles: the atomic nucleus is replaced by the C atom, the electrons are replaced by protons, and the empty space between particles is replaced by an "electron soup." Coordinates: the radial coordinates of the electrons map onto the five local C-H stretching modes, the angular coordinates of the electrons map onto three rotational degrees of freedom and seven bending vibrational degrees of freedom. The half-integral electron spins map onto half-integral proton spins or onto integral deuterium spins (for CD5+). Interactions: the Coulomb attraction between nucleus and electrons maps onto a Morse-oscillator C-H stretching potential, spin-orbit interaction maps onto proton-spin-overall-rotation interaction, and Coulomb repulsion between electrons maps onto some kind of proton repulsion that leads to the equilibrium geometry.

Experimental characterization of enhanced SNCR process with carbonaceous gas additives.

PubMed

Yao, Ting; Duan, Yufeng; Yang, Zhizhong; Li, Yuan; Wang, Linwei; Zhu, Chun; Zhou, Qiang; Zhang, Jun; She, Min; Liu, Meng

2017-06-01

Carbonaceous gases such as CO and alkanes are commonly used as additives to enhance the selective non-catalytic reduction (SNCR) performance due to their high reducibility. This study compared the effect of CO and CH 4 on NO reduction in a tubular reactor with simulated flue gas. The enhancement of C 3 H 8 on SNCR process was tested at extremely low temperature, i.e. 650 °C. Experimental results suggested that reactions between NH 3 and SO 2 were favored at low temperatures and the competition for NH 3 between SO 2 and NO was influenced by gas additives. A maximum downward shift of 25 °C and 100 °C in temperature window for 50% NO reduction efficiency was obtained with the addition of CO and CH 4 , respectively. Considerable CO emission was observed with addition of CH 4 . The addition of CH 4 contributed to the formation of a self-accelerating reaction route within NO/O 2 /NH 3 SNCR reaction system. NO 2 produced from NO accelerates the oxidation of CH 4 to CO, while the oxidation of CH 4 returns to enhance the NO reduction globally. Optimal NO reduction of 44% was achieved with addition of C 3 H 8 at 650 °C. Substantial portion of C 3 H 8 was partially oxidized to CO and the remaining was converted into C 2 H 4 and C 3 H 6 during the SNCR process. Oxidative dehydrogenation of C 3 H 8 was involved. High reactivity of C 3 H 6 and C 2 H 4 favored the further oxidation and cracking to produce CO. These differences in oxidation behavior significantly influence the promotion capacities of CO, CH 4 and C 3 H 8 for NO reduction. Copyright © 2017 Elsevier Ltd. All rights reserved.

Characteristics of the spin-trapping reaction of a free radical derived from AAPH: further development of the ORAC-ESR assay.

PubMed

Nakajima, A; Matsuda, E; Masuda, Y; Sameshima, H; Ikenoue, T

2012-06-01

The characteristics of the spin-trapping reaction in the oxygen radical absorbance capacity (ORAC)-electron spin resonance (ESR) assay were examined, focusing on the kind of spin traps. 2,2-Azobis(2-amidinopropane) dihydrochloride (AAPH) was used as a free radical initiator. The spin adducts of the AAPH-derived free radical were assigned as those of the alkoxyl radical, RO· (R=H(2)N(HN)C-C(CH(3))(2)). Among the spin traps tested, 5,5-dimethyl-1-pyrroline N-oxide (DMPO), 5,5-dimethyl-4-phenyl-1-pyrroline N-oxide (4PDMPO), 5-(2,2-dimethyl-1,3-propoxycyclophosphoryl)-5-methyl-1-pyrroline N-oxide (CYPMPO), and 5-diethoxyphosphoryl-5-methyl-1-pyrroline N-oxide (DEPMPO) were applicable to the ORAC-ESR assay. Optimal formation of spin-trapped radical adduct was observed with 1 mM AAPH, 10 mM spin trap, and 5 s UV irradiation. The calibration curve (the Stern-Volmer's plot) for each spin trap showed good linearity, and their slopes, k (SB)/k (ST), were estimated to be 87.7±2.3, 267±15, 228±9, and 213±16 for DMPO, 4PDMPO, CYPMPO, and DEPMPO, respectively. Though the k (SB)/k (ST) values for selected biosubstances varied with various spin traps, their ratios to Trolox (the relative ORAC values) were almost the same for all spin traps tested. The ORAC-ESR assay also had a very good reproducibility. The ORAC-ESR assay was conducted under stoichiometric experimental conditions. The present results demonstrate the superiority of the ORAC-ESR assay.

Explaining the Paleoproterozoic Rise of O2

NASA Astrophysics Data System (ADS)

Anbar, A. D.; Rye, R.; Kaufman, A. J.

2001-12-01

The Paleoproterozoic rise of atmospheric O2 is not understood. Geochemical evidence indicates pO2 \\leq 5 x 10-4 atm before ~ 2.2 Ga and >= 0.03 atm by 2.0 Ga [1]. Most models of this rapid oxygenation account for the timing in an ad hoc manner. In contrast, we suggest oxygenation was driven by rising solar luminosity, a hypothesis consistent with emerging geochemical evidence. Solar luminosity was { ~} 80 % of present value 2.75 Ga. Climate models indicate that pCO2 > 0.2 atm was required before 2.75 Ga if CO2 alone accounted for greenhouse enhancement that averted global glaciation [2]. Paleosols reveal pCO2 <= 10-1.4 atm between 2.75 and 2.2 Ga [3]. This constraint may extend earlier [4]. Given insufficient CO2, CH4 likely helped maintain surface temperature. pCH4 > 10-4 atm would have been adequate 2.75 Ga; Methanogens could sustain this level as long as pO2 was negligible [5]. Atmospheric CH4 and O2 are incompatible. If CH4 was a critical greenhouse gas, increases in pO2 caused global cooling. Temperature and photosynthetic O2 production are probably positively correlated between 273 and 300 K. Combined, these effects constituted a negative feedback on pO2: Excess O2 production cooled the surface, decreasing O2 production until pCH4 was restored. Methanogenesis was decoupled from this feedback as the bulk of Archean methanogens presumably lived in the deep ocean, insulated from surface temperature. Hence, the CH4 greenhouse acted as a cap on pO2 in the Archean. This cap would have eased as rising solar luminosity permitted "titration" of CH4 by increased O2 production; pO2 increased slowly as pCH4 decreased. This feedback suppressed pO2 until solar luminosity allowed the CO2-H2O greenhouse to maintain equable temperatures without appreciable CH4. This threshold was crossed { ~} 2.5 to 2.0 Ga [2], explaining Paleoproterozoic oxygenation. As Earth approached the threshold the CH4 buffer shrank and the likelihood of the feedback being temporarily overwhelmed by sudden O2 blooms increased. This hypothesis is consistent with observations of extreme climatic instability between 2.5 and 2.0 Ga, including evidence of at least two, possibly three, episodes of global glaciation 2.4 to 2.2 Ga [6]. We predict that Paleoproterozoic glacial episodes should be preceded by increased oxygen production- excess O2 production is predicted to cause pCH4 erosion and cooling. 13C-enriched carbonates underlying the glaciogenic Timeball Hill Fm, S. Africa [6] indicate enhanced carbon burial associated with such O2 production. Significantly, there is no evidence of glaciation following the largest Paleoproterozoic 13C excursion,{ ~} 2.2 Ga; solar luminosity at this time was sufficient to avoid glaciation despite pCH4 << 10-4 atm. Greenhouse considerations no longer limited the rise of pO2 after this time, consistent with paleosol and other evidence of oxygenation. Further study of 13C in Paleoproterozoic and late Archean carbonates are critical to test and extend this hypothesis. 1. Rye & Holland (1998), Am. J. Sci. 298, 621; 2. Kasting (1987), Precamb. Res. 34, 205; 3. Rye et al. (1995) Nature 378, 603; 4. Sleep & Zahnle (2001) JGR 106, 1373; 5. Pavlov et al. (2000) JGR 105, 11981; 6. Bekker et al. (2001), Am. J. Sci. 301, 601.

Spin-polarized exciton quantum beating in hybrid organic-inorganic perovskites

NASA Astrophysics Data System (ADS)

Odenthal, Patrick; Talmadge, William; Gundlach, Nathan; Wang, Ruizhi; Zhang, Chuang; Sun, Dali; Yu, Zhi-Gang; Valy Vardeny, Z.; Li, Yan S.

2017-09-01

Hybrid organic-inorganic perovskites have emerged as a new class of semiconductors that exhibit excellent performance as active layers in photovoltaic solar cells. These compounds are also highly promising materials for the field of spintronics due to their large and tunable spin-orbit coupling, spin-dependent optical selection rules, and their predicted electrically tunable Rashba spin splitting. Here we demonstrate the optical orientation of excitons and optical detection of spin-polarized exciton quantum beating in polycrystalline films of the hybrid perovskite CH3NH3PbClxI3-x. Time-resolved Faraday rotation measurement in zero magnetic field reveals unexpectedly long spin lifetimes exceeding 1 ns at 4 K, despite the large spin-orbit couplings of the heavy lead and iodine atoms. The quantum beating of exciton states in transverse magnetic fields shows two distinct frequencies, corresponding to two g-factors of 2.63 and -0.33, which we assign to electrons and holes, respectively. These results provide a basic picture of the exciton states in hybrid perovskites, and suggest they hold potential for spintronic applications.

Tracking the Fate of new C in Northern Peatlands by a Compound-Specific Stable Isotope-Labeling Approach coupled with multiple analytical techniques and gas fluxes analysis

NASA Astrophysics Data System (ADS)

Tfaily, M. M.; Hu, J.; Heyman, H. M.; Toyoda, J.; Jaegers, N. R.; Wilson, R.; Chanton, J.

2017-12-01

Predicted increases in temperatures in Northern peatlands are expected to drive substantial alterations to global carbon (C) cycling. In many peatlands, increased temperatures will drive the decomposition of old recalcitrant C pools, as well as a surge of new potentially labile C fluxes, as highly productive plant communities (e.g., sedges) take over these systems. The result will be a large increase in microbial decomposition of C and emissions of the greenhouse gases CO2 and CH4. Much attention and study has focused on the fate of old C, which may decompose as temperatures increase, but the fate of new C inputs resulting from increased plant production remains poorly understood. This "new C" cycle has potential to drive substantial climate forces. Particularly, if hydrologic changes increase anaerobic decomposition of new C (e.g., by priming effect), this then could drive larger contributions to gas emissions, and hence feedbacks related to climate change. In this study, we examined the priming effect, drivers, and dynamics of the "new C" that is stimulated by climate change in Northern peatlands soil using a stable isotope labeling approach in a long term incubation experiment using surface and deep soil samples. The aim was to understand: 1) how changes in labile carbon inputs drive microbial community composition in the surface and deeper in the peat column, 2) how microbial communities contribute to CH4 and CO2 fluxes, and 3) the impact of the labile new C on ecosystem C storage or release. We traced the fate of 13C-glucose added to decomposition incubations into (1) different organic matter (through high-resolution 21T FT-ICR-MS and GC-FTMS), then into (2) microbial community (16S rRNA), and finally into (3) greenhouse gases (CO2 and CH4 gas emissions). Furthermore, we employed in situ 13C magic angle spinning (MAS) NMR spectroscopy to study quantitatively and continuously the in situ migration or conversion of glucose into various metabolites by microbes in soil. This research represents a fully integrated study to achieve a mechanistic understanding of substrate transformation through the microbial loop and will help shed new light on the mechanistic basis of biological processes and how these processes change in response to community interactions and shifting environmental condition.

Role of regional wetland emissions in atmospheric methane variability

NASA Astrophysics Data System (ADS)

McNorton, J.; Gloor, E.; Wilson, C.; Hayman, G. D.; Gedney, N.; Comyn-Platt, E.; Marthews, T.; Parker, R. J.; Boesch, H.; Chipperfield, M. P.

2016-11-01

Atmospheric methane (CH4) accounts for 20% of the total direct anthropogenic radiative forcing by long-lived greenhouse gases. Surface observations show a pause (1999-2006) followed by a resumption in CH4 growth, which remain largely unexplained. Using a land surface model, we estimate wetland CH4 emissions from 1993 to 2014 and study the regional contributions to changes in atmospheric CH4. Atmospheric model simulations using these emissions, together with other sources, compare well with surface and satellite CH4 data. Modeled global wetland emissions vary by ±3%/yr (σ = 4.8 Tg), mainly due to precipitation-induced changes in wetland area, but the integrated effect makes only a small contribution to the pause in CH4 growth from 1999 to 2006. Increasing temperature, which increases wetland area, drives a long-term trend in wetland CH4 emissions of +0.2%/yr (1999 to 2014). The increased growth post-2006 was partly caused by increased wetland emissions (+3%), mainly from Tropical Asia, Southern Africa, and Australia.

Unimolecular Thermal Fragmentation of Ortho-Benzyne

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

Zhang, X.; Maccarone, A. T.; Nimlos, M. R.

2007-01-01

The ortho-benzyne diradical, o-C{sub 6}H{sub 4} has been produced with a supersonic nozzle and its subsequent thermal decomposition has been studied. As the temperature of the nozzle is increased, the benzyne molecule fragments: o-C{sub 6}H{sub 4} + {Delta} {yields} products. The thermal dissociation products were identified by three experimental methods: (i) time-of-flight photoionization mass spectrometry, (ii) matrix-isolation Fourier transform infrared absorption spectroscopy, and (iii) chemical ionization mass spectrometry. At the threshold dissociation temperature, o-benzyne cleanly decomposes into acetylene and diacetylene via an apparent retro-Diels-Alder process: o-C{sub 6}H{sub 4} + {Delta} {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH. The experimentalmore » {Delta}{sub rxn}H{sub 298}(o-C{sub 6}H{sub 4} {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH) is found to be 57 {+-} 3 kcal mol{sup -1}. Further experiments with the substituted benzyne, 3,6-(CH{sub 3}){sub 2}-o-C{sub 6}H{sub 2}, are consistent with a retro-Diels-Alder fragmentation. But at higher nozzle temperatures, the cracking pattern becomes more complicated. To interpret these experiments, the retro-Diels-Alder fragmentation of o-benzyne has been investigated by rigorous ab initio electronic structure computations. These calculations used basis sets as large as [C(7s6p5d4f3g2h1i)/H(6s5p4d3f2g1h)] (cc-pV6Z) and electron correlation treatments as extensive as full coupled cluster through triple excitations (CCSDT), in cases with a perturbative term for connected quadruples [CCSDT(Q)]. Focal point extrapolations of the computational data yield a 0 K barrier for the concerted, C{sub 2v}-symmetric decomposition of o-benzyne, E{sub b}(o-C{sub 6}H{sub 4} {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH) = 88.0 {+-} 0.5 kcal mol{sup -1}. A barrier of this magnitude is consistent with the experimental results. A careful assessment of the thermochemistry for the high temperature fragmentation of benzene is presented: C{sub 6}H{sub 6} {yields} H+[C{sub 6}H{sub 5}] {yields} H+[o-C{sub 6}H{sub 4}] {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH. Benzyne may be an important intermediate in the thermal decomposition of many alkylbenzenes (arenes). High engine temperatures above 1500 K may crack these alkylbenzenes to a mixture of alkyl radicals and phenyl radicals. The phenyl radicals will then dissociate first to benzyne and then to acetylene and diacetylene.« less

Unimolecular thermal fragmentation of ortho-benzene.

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

Zhang, X.; Maccarone, A. T.; Nimlos, M. R.

2007-01-01

The ortho-benzyne diradical, o-C{sub 6}H{sub 4} has been produced with a supersonic nozzle and its subsequent thermal decomposition has been studied. As the temperature of the nozzle is increased, the benzyne molecule fragments o-C{sub 6}H{sub 4}{sup +} {Delta} {yields} products. The thermal dissociation products were identified by three experimental methods: (i) time-of-flight photoionization mass spectrometry, (ii) matrix-isolation Fourier transform infrared absorption spectroscopy, and (iii) chemical ionization mass spectrometry. At the threshold dissociation temperature, o-benzyne cleanly decomposes into acetylene and diacetylene via an apparent retro-Diels-Alder process: o-C{sub 6}H{sub 4}{sup +}{Delta}{yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH. The experimental {Delta}{sub rxn}H{submore » 298}(o-C{sub 6}H{sub 4} {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH) is found to be 57 {+-} 3 kcal mol{sup -1}. Further experiments with the substituted benzyne, 3,6-(CH{sub 3}){sub 2}-o-C{sub 6}H{sub 2}, are consistent with a retro-Diels-Alder fragmentation. But at higher nozzle temperatures, the cracking pattern becomes more complicated. To interpret these experiments, the retro-Diels-Alder fragmentation of o-benzyne has been investigated by rigorous ab initio electronic structure computations. These calculations used basis sets as large as [C(7s6p5d4f3g2h1i)/H(6s5p4d3f2g1h)] (cc-pV6Z) and electron correlation treatments as extensive as full coupled cluster through triple excitations (CCSDT), in cases with a perturbative term for connected quadruples [CCSDT(Q)]. Focal point extrapolations of the computational data yield a 0 K barrier for the concerted, C{sub 2v}-symmetric decomposition of o-benzyne, E{sub b}(o-C{sub 6}H{sub 4} {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH) = 88.0 {+-} 0.5 kcal mol{sup -1}. A barrier of this magnitude is consistent with the experimental results. A careful assessment of the thermochemistry for the high temperature fragmentation of benzene is presented: C{sub 6}H{sub 6} {yields} H+[C{sub 6}H{sub 5}] {yields} H+[o-C{sub 6}H{sub 4}] {yields} HC {triple_bond} CH-HC {triple_bond} C-C {triple_bond} CH. Benzyne may be an important intermediate in the thermal decomposition of many alkylbenzenes (arenes). High engine temperatures above 1500 K may crack these alkylbenzenes to a mixture of alkyl radicals and phenyl radicals. The phenyl radicals will then dissociate first to benzyne and then to acetylene and diacetylene.« less

Investigating Titan's Atmospheric Chemistry at Low Temperature in Support of the NASA Cassini Mission

NASA Technical Reports Server (NTRS)

Sciamma-O'Brien, Ella; Salama, Farid

2013-01-01

Titan's atmosphere, composed mainly of N2 and CH4, is the siege of a complex chemistry induced by solar UV radiation and electron bombardment from Saturn's magnetosphere. This organic chemistry occurs at temperatures lower than 200 K and leads to the production of heavy molecules and subsequently solid aerosols that form the orange haze surrounding Titan. The Titan Haze Simulation (THS) experiment has been developed on the COSMIC simulation chamber at NASA Ames in order to study the different steps of Titan's atmospheric chemistry at low temperature and to provide laboratory data in support for Cassini data analysis. The chemistry is simulated by plasma in the stream of a supersonic expansion. With this unique design, the gas mixture is adiabatically cooled to Titan-like temperature (approx. 150 K) before inducing the chemistry by plasma discharge. Different gas mixtures containing N2, CH4, and the first products of the N2,-CH4 chemistry (C2H2, C2H4, C6H6...) but also heavier molecules such as PAHs or nitrogen containing PAHs can be injected. Both the gas phase and solid phase products resulting from the plasma-induced chemistry can be monitored and analyzed. Here we present the results of recent gas phase and solid phase studies that highlight the chemical growth evolution when injecting heavier hydrocarbon trace elements in the initial N2-CH4 mixture. Due to the short residence time of the gas in the plasma discharge, only the first steps of the chemistry have time to occur in a N2-CH4 discharge. However by adding acetylene and benzene to the initial N2-CH4 mixture, we can study the intermediate steps of Titan's atmospheric chemistry as well as specific chemical pathways. These results show the uniqueness of the THS experiment to help understand the first and intermediate steps of Titan fs atmospheric chemistry as well as specific chemical pathways leading to Titan fs haze formation.

Molecular simulation of CO2/CH4 adsorption in brown coal: Effect of oxygen-, nitrogen-, and sulfur-containing functional groups

NASA Astrophysics Data System (ADS)

Dang, Yong; Zhao, Lianming; Lu, Xiaoqing; Xu, Jing; Sang, Pengpeng; Guo, Sheng; Zhu, Houyu; Guo, Wenyue

2017-11-01

The CO2/CH4 adsorption behaviors in brown coal at the temperatures of 298, 313, and 373 K and in the pressure range of 0.005-10 MPa were investigated by molecular dynamics (MD), density functional theory (DFT), and grand canonical Monte Carlo (GCMC) simulations. The absolute adsorption isotherms of single-component CH4 and CO2 exhibit type-I Langmuir adsorption behavior showing a negative influence of temperature. For the binary CO2/CH4 mixture, brown coal shows super high selectivity of CO2 over CH4 at pressures below 0.2 MPa, which then decreases quickly and finally tends to be constant when the pressure increases. The high competitive adsorption of CO2 originates from the effects of (i) the large electrostatic contributions, (ii) the conducive micropore environment with pore sizes below 0.56 nm, and (iii) the stronger adsorption of CO2 with respect to CH4. These effects are strengthened by the high-density oxygen-containing, pyridine, and thiophene functional groups contained in brown coal, which provide abundant and strong adsorption sites for CO2, but show weaker affinity to CH4. Furthermore, the influence of various nitrogen- and sulfur-containing functional groups on the CO2 adsorption capacity was also investigated. The results indicate that the basicity of the oxygen- and nitrogen-containing groups has a large influence on the CO2 adsorption, while for the sulfur functional groups the determining factor is the polarity.

Magnetic field tunability of spin polarized excitations in a high temperature magnet

NASA Astrophysics Data System (ADS)

Holinsworth, Brian; Sims, Hunter; Cherian, Judy; Mazumdar, Dipanjan; Harms, Nathan; Chapman, Brandon; Gupta, Arun; McGill, Steve; Musfeldt, Janice

Magnetic semiconductors are at the heart of modern device physics because they naturally provide a non-zero magnetic moment below the ordering temperature, spin-dependent band gap, and spin polarization that originates from exchange-coupled magnetization or an applied field creating a spin-split band structure. Strongly correlated spinel ferrites are amongst the most noteworthy contenders for semiconductor spintronics. NiFe2O4, in particular, displays spin-filtering, linear magnetoresistance, and wide application in the microwave regime. To unravel the spin-charge interaction in NiFe2O4, we bring together magnetic circular dichroism, photoconductivity, and prior optical absorption with complementary first principles calculations. Analysis uncovers a metamagnetic transition modifying electronic structure in the minority channel below the majority channel gap, exchange splittings emerging from spin-split bands, anisotropy of excitons surrounding the indirect gap, and magnetic-field dependent photoconductivity. These findings open the door for the creation and control of spin-polarized excitations from minority channel charge charge transfer in NiFe2O4 and other members of the spinel ferrite family.

Low-temperature upgrading of low-calorific biogas for CO2 mitigation using DBD-catalyst hybrid reactor

NASA Astrophysics Data System (ADS)

Nozaki, Tomohiro; Tsukijihara, Hiroyuki; Fukui, Wataru; Okazaki, Ken

2006-10-01

Although huge amounts of biogas, which consists of 20-60% of CH4 in CO2/N2, can be obtained from landfills, coal mines, and agricultural residues, most of them are simply flared and wasted: because global warming potential of biogas is 5-15 times as potent as CO2. Poor combustibility of such biogas makes it difficult to utilize in conventional energy system. The purpose of this project is to promote the profitable recovery of methane from poor biogas via non-thermal plasma technology. We propose low-temperature steam reforming of biogas using DBD generated in catalyst beds. Methane is partially converted into hydrogen, and then fed into internal combustion engines for improved ignition stability as well as efficient operation. Low-temperature steam reforming is beneficial because exhaust gas from an engine can be used to activate catalyst beds. Space velocity (3600-15000 hr-1), reaction temperature (300-650^oC), and energy cost (30-150 kJ per mol CH4) have been investigated with simulated biogas (20-60% CH4 in mixtures of CO2/N2). The DBD enhances reaction rate of CH4 by a factor of ten at given catalyst temperatures, which is a rate-determining step of methane steam reforming, while species concentration of upgraded biogas was governed by thermodynamic equilibrium in the presence of catalyst.

High-sensitivity interference-free diagnostic for measurement of methane in shock tubes

NASA Astrophysics Data System (ADS)

Sur, Ritobrata; Wang, Shengkai; Sun, Kai; Davidson, David F.; Jeffries, Jay B.; Hanson, Ronald K.

2015-05-01

A sensitive CW laser absorption diagnostic for in-situ measurement of methane mole fraction at high temperatures is developed. The selected transitions for the diagnostic are a cluster of lines near 3148.8 cm-1 from the R-branch of the ν3 band of the CH4 absorption spectrum. The selected transitions have 2-3 times more sensitivity to CH4 concentration than the P-branch in the 3.3 μm region, lower interference from major interfering intermediate species in most hydrocarbon reactions, and applicability over a wide range of pressures and temperatures. Absorption cross-sections for a broad collection of hydrocarbons were simulated to evaluate interference absorption, and were generally found to be negligible near 3148.8 cm-1. However, minor interference from hot bands of C2H2 and C2H4 was observed and was characterized experimentally, revealing a weak dependence on wavelength. To eliminate such interferences, a two-color on-line and off-line measurement scheme is proposed to determine CH4 concentration. The colors selected, i.e., for on-line (3148.81 cm-1) and off-line (3148.66 cm-1), are characterized between 0.2-4 atm and 500 K-2100 K by absorption coefficient measurements in a shock tube. Minimum detectable levels of CH4 in shock tube experiments are reported for this range of temperatures and pressures. An example measurement is shown for sensitive detection of CH4 in a shock tube chemical kinetics experiment.

Atmospheric methane sources - Alaskan tundra bogs, an alpine fen, and a subarctic boreal marsh

NASA Technical Reports Server (NTRS)

Sebacher, D. I.; Harriss, R. C.; Grice, S. S.; Bartlett, K. B.; Sebacher, S. M.

1986-01-01

Methane (CH4) flux measurements from Alaska tundra bogs, an alpine fen, and a subarctic boreal marsh were obtained at field sites ranging from Prudhoe Bay on the coast of the Arctic Ocean to the Alaskan Range south of Fairbanks during August 1984. In the tundra, average CH4 emission rates varied from 4.9 mg CH4 per sq m per day (moist tundra) to 119 mg CH4 per sq m per day (waterlogged tundra). Fluxes averaged 40 mg CH4 per sq m per day from wet tussock meadows in the Brooks Range and 289 mg Ch4 per sq m per day from an alpine fen in the Alaskan Range. The boreal marsh had an average CH4 emission rate of 106 mg CH4 per sq m per day. Significant emissions were detected in tundra areas where peat temperatures were as low as 4 C, and permafrost was only 25 cm below the ground surface. Emission rates from the 17 sites sampled were found to be logarithmically related to water levels at the sites. Extrapolation of the data to an estimate of the total annual CH4 emission from all arctic and boreal wetlands suggests that these ecosystems are a major source of atmospheric CH4 and could account for up to 23 percent of global CH4 emissions from wetlands.

Eight- and six-coordinated Mn(II) complexes of heteroaromatic alcohol and aldehyde: Crystal structure, spectral, magnetic, thermal and antibacterial activity studies

NASA Astrophysics Data System (ADS)

Jabłońska-Wawrzycka, Agnieszka; Barszcz, Barbara; Zienkiewicz, Małgorzata; Hodorowicz, Maciej; Jezierska, Julia; Stadnicka, Katarzyna; Lechowicz, Łukasz; Kaca, Wiesław

2014-08-01

Crystal, molecular and electronic structure of new manganese(II) compounds: [Mn(2-CH2OHpy)2(NO3)2] (1), [Mn(4-CHO-5-MeIm)2(NO3)2] (2) and [Mn(4-CHO-5-MeIm)2Cl2] (3), where 2-hydroxymethylpyridine (2-CH2OHpy) and 5(4)-carbaldehyde-4(5)-methylimidazole (5(4)-CHO-4(5)-MeIm), have been characterised using X-ray, spectroscopic, magnetic and TG/DTG data. In compounds 1 and 2, the Mn(II) ion is eight-coordinated forming distorted pseudo-dodecahedron, that is rather unusual for the manganese(II) complexes, whereas in 3 the Mn(II) ion environment is a distorted octahedron. The high coordination number (CN = 8) of 1 and 2 results from bidentate character of the nitrate ligands. The X-band EPR spectra of compounds 2 and 3 exhibit fine structure signals resulting from zero-field splitting (ZFS) of the spin states for high spin d5 Mn(II), whereas for 1 the broad isotropic signals were observed. The estimation of ZFS for individual Mn(II) ions was carried out for all compounds using DFT calculations. The free ligands and their manganese(II) complexes have been tested in vitro against gram-positive and gram-negative bacteria in order to assess their antimicrobial properties.

Microscopic interpretation of magnetic ordering and critical slowing down in potassium ferrate

NASA Astrophysics Data System (ADS)

Corson, M. R.; Hoy, G. R.

1984-04-01

Experimental Mössbauer results are reported for the antiferromagnet K2FeO4 from 0.16 to 4.2 K which show significant spin-relaxation effects. The data are analyzed using the Clauser-Blume theory of stochastic spin relaxation, applied to the case spin S=1. This analysis yields the Néel temperature TN=3.60 K, and verifies the crystal-field parameters D=0.11 cm-1, and E=0.02 cm-1 in the presence of significant spin-fluctuation effects. The analysis also shows that, except in the critical region, the strength of the relaxation mechanism is temperature independent, indicating that the spin-spin interaction is the dominant relaxation mechanism in this temperature range. In the region of 3.60 K, the spin-relaxation rate is observed to decrease by a factor of 700, showing the critical slowing down of the iron ions' spin fluctuations in the critical region. Additionally, to fit the data between 3.50 and 3.70 K, it is necessary to include contributions from a range of values of reduced magnetization and relaxation rate. These results are discussed in terms of a proposed model including critical fluctuations.

Microbial Abundances Predict Methane and Nitrous Oxide Fluxes from a Windrow Composting System

PubMed Central

Li, Shuqing; Song, Lina; Gao, Xiang; Jin, Yaguo; Liu, Shuwei; Shen, Qirong; Zou, Jianwen

2017-01-01

Manure composting is a significant source of atmospheric methane (CH4) and nitrous oxide (N2O) that are two potent greenhouse gases. The CH4 and N2O fluxes are mediated by methanogens and methanotrophs, nitrifying and denitrifying bacteria in composting manure, respectively, while these specific bacterial functional groups may interplay in CH4 and N2O emissions during manure composting. To test the hypothesis that bacterial functional gene abundances regulate greenhouse gas fluxes in windrow composting systems, CH4 and N2O fluxes were simultaneously measured using the chamber method, and molecular techniques were used to quantify the abundances of CH4-related functional genes (mcrA and pmoA genes) and N2O-related functional genes (amoA, narG, nirK, nirS, norB, and nosZ genes). The results indicate that changes in interacting physicochemical parameters in the pile shaped the dynamics of bacterial functional gene abundances. The CH4 and N2O fluxes were correlated with abundances of specific compositional genes in bacterial community. The stepwise regression statistics selected pile temperature, mcrA and NH4+ together as the best predictors for CH4 fluxes, and the model integrating nirK, nosZ with pmoA gene abundances can almost fully explain the dynamics of N2O fluxes over windrow composting. The simulated models were tested against measurements in paddy rice cropping systems, indicating that the models can also be applicable to predicting the response of CH4 and N2O fluxes to elevated atmospheric CO2 concentration and rising temperature. Microbial abundances could be included as indicators in the current carbon and nitrogen biogeochemical models. PMID:28373862

Control of dissolved CH4 in a municipal UASB reactor effluent by means of a desorption - Biofiltration arrangement.

PubMed

Huete, A; de Los Cobos-Vasconcelos, D; Gómez-Borraz, T; Morgan-Sagastume, J M; Noyola, A

2018-06-15

The direct anaerobic treatment of municipal wastewater represents an adapted technology to the conditions of developing countries. In order to get an increased acceptance of this technology, a proper control of dissolved methane in the anaerobic effluents should be considered, as methane is a potent greenhouse gas. In this study, a pilot-scale system was operated for 168 days to recover dissolved methane from an effluent of an upflow anaerobic sludge blanket reactor and then oxidize it in a compost biofilter. The system operated at a constant air (0.9 m 3 /h ±0.09) and two air-to anaerobic effluent ratio (1:1 and 1:2). In both conditions (CH 4 concentration of 2.7 ± 0.87 and 4.3% ± 1.14, respectively) the desorption column recovered 99% of the dissolved CH 4 and approximately 30% ± 8.5 of H 2 S, whose desorption was limited due to the high pH (>8) of the effluent. The biofilter removed 70% ± 8 of the average CH 4 load (60 gCH 4 /m 3 h ± 13) and 100% of the H 2 S load at an empty bed retention time of 23 min. The average temperature inside the biofilter was 42 ± 9 °C due to the CH 4 oxidation reaction, indicating that temperature and moisture control is particularly important for CH 4 removal in compost biofilters. The system may achieve a 54% reduction of greenhouse gas emissions from dissolved CH 4 in this particular case. Copyright © 2017 Elsevier Ltd. All rights reserved.

Year-round simulated methane emissions from a permafrost ecosystem in Northeast Siberia

NASA Astrophysics Data System (ADS)

Castro-Morales, Karel; Kleinen, Thomas; Kaiser, Sonja; Zaehle, Sönke; Kittler, Fanny; Kwon, Min Jung; Beer, Christian; Göckede, Mathias

2018-05-01

Wetlands of northern high latitudes are ecosystems highly vulnerable to climate change. Some degradation effects include soil hydrologic changes due to permafrost thaw, formation of deeper active layers, and rising topsoil temperatures that accelerate the degradation of permafrost carbon and increase in CO2 and CH4 emissions. In this work we present 2 years of modeled year-round CH4 emissions into the atmosphere from a Northeast Siberian region in the Russian Far East. We use a revisited version of the process-based JSBACH-methane model that includes four CH4 transport pathways: plant-mediated transport, ebullition and molecular diffusion in the presence or absence of snow. The gas is emitted through wetlands represented by grid cell inundated areas simulated with a TOPMODEL approach. The magnitude of the summertime modeled CH4 emissions is comparable to ground-based CH4 fluxes measured with the eddy covariance technique and flux chambers in the same area of study, whereas wintertime modeled values are underestimated by 1 order of magnitude. In an annual balance, the most important mechanism for transport of methane into the atmosphere is through plants (61 %). This is followed by ebullition ( ˜ 35 %), while summertime molecular diffusion is negligible (0.02 %) compared to the diffusion through the snow during winter ( ˜ 4 %). We investigate the relationship between temporal changes in the CH4 fluxes, soil temperature, and soil moisture content. Our results highlight the heterogeneity in CH4 emissions at landscape scale and suggest that further improvements to the representation of large-scale hydrological conditions in the model will facilitate a more process-oriented land surface scheme and better simulate CH4 emissions under climate change. This is especially necessary at regional scales in Arctic ecosystems influenced by permafrost thaw.

Prediction on electronic structure of CH3NH3PbI3/Fe3O4 interfaces

NASA Astrophysics Data System (ADS)

Hou, Xueyao; Wang, Xiaocha; Mi, Wenbo; Du, Zunfeng

2018-01-01

The interfacial electronic structures of CH3NH3PbI3(MAPbI3)/Fe3O4 heterostructures are predicted by density functional theory. Four models (MAI/FeBO, PbI2/FeBO, MAI/FeA and PbI2/FeA) are included. Especially, a half-metal to semiconductor transition of Fe3O4 appears in PbI2/FeA model. A series of electric field is added to PbI2/FeA model, and a direct-indirect bandgap transition of Fe3O4 appears at a 500-kV/cm field. The electric field can control the bandgap of Fe3O4 in PbI2/FeA model by modulating the hybridization. The prediction of spin-related bandgap characteristic in MAPbI3/Fe3O4 is meaningful for further study.

In situ Low-temperature Pair Distribution Function (PDF) Analysis of CH4 and CO2 Hydrates

NASA Astrophysics Data System (ADS)

Cladek, B.; Everett, M.; McDonnell, M.; Tucker, M.; Keffer, D.; Rawn, C.

2017-12-01

Gas hydrates occur in ocean floor and sub-surface permafrost deposits and are stable at moderate to high pressures and low temperatures. They are a clathrate structure composed of hydrogen bonded water cages that accommodate a wide variety of guest molecules. CO2 and CH4 hydrates both crystallize as the cubic sI hydrate and can form a solid solution. Natural gas hydrates are interesting as a potential methane source and for CO2 sequestration. Long-range diffraction studies on gas hydrates give valuable structural information but do not provide a detailed understanding of the disordered gas molecule interactions with the host lattice. In-situ low temperature total scattering experiments combined with pair distribution function (PDF) analysis are used to investigate the gas molecule motions and guest-cage interactions. CO2 and methane hydrates exhibit different decomposition behavior, and CO2 hydrate has a smaller lattice parameter despite it being a relatively larger molecule. Total scattering studies characterizing both the short- and long-range order simultaneously help to elucidate the structural source of these phenomena. Low temperature neutron total scattering data were collected using the Nanoscale Ordered MAterials Diffractometer (NOMAD) beamline at the Spallation Neutron Source (SNS) on CO2 and CH4 hydrates synthesized with D2O. Guest molecule motion within cages and interactions between gases and cages are investigated through the hydrate stability and decomposition regions. Data were collected from 2-80 K at a pressure of 55 mbar on CO2 and CH4 hydrates, and from 80-270 K at 25 bar on CH4 hydrate. The hydrate systems were modeled with classical molecular dynamic (MD) simulations to provide an analysis of the total energy into guest-guest, guest-host and host-host contributions. Combined Reitveld and Reverse Monte Carlo (RMC) structure refinement were used to fit models of the data. This combined modeling and simulation characterizes the effects of CO2 and CH4 as guest molecules on the structure and decomposition of gas hydrates. Structure and thermodynamic studies will provide a more comprehensive understanding of CO2-CH4 solid solutions, exchange kinetics, and implications on hydrate structure.

CO2 and CH4 exchange by Phragmites australis under different climates

NASA Astrophysics Data System (ADS)

Serrano Ortiz, Penélope; Chojnickic, Bogdan H.; Sánchez-Cañete, Enrique P.; Kowalska, Natalia; López-Ballesteros, Ana; Fernández, Néstor; Urbaniak, Marek; Olejnik, Janusz; Kowalski, Andrew S.

2015-04-01

The key role of wetlands regarding global warming is the resulting balance between net CO2 assimilation, via photosynthesis, and CO2 and CH4 emissions, given the potential to release stored carbon, because of the high temperature sensitivity of heterotrophic soil respiration and anoxic conditions. However, it is still unknown whether wetlands will convert from long-term carbon sinks to sources as a result of climate change and other anthropogenic effects such as land use changes. Phragmites australis is one of the most common species found in wetlands and is considered the most globally widespread and productive plant species in this type of ecosystem. In this context, the main objective of this study is to analyse the GHG exchange (CO2 and CH4) of two wetlands with Phragmites australis as the dominant species under different climates using the eddy covariance (EC) technique. The first site, Padul, is located in southern Spain, with a sub-humid warm climate, characterised by a mean annual temperature of 16°C and annual precipitation of ca. 470 mm, with a very dry summer. The second site, Rzecin is located in Poland with a mean annual temperature of 8°C, and annual precipitation around 600mm with no dry season. The Padul EC station is equipped with two infrared gas analysers to measure CO2 and CH4 fluxes (LI-7200 and LI-7700 respectively) while the Rzecin EC station has the same CH4 sensor as Padul, but also a sensor measuring both GHG fluxes (DLT-100 Fast Methane Analyser, Los Gatos). In this study, we present: i) the results of a CH4 analyser inter-comparison campaign (LI-7700 vs. Los Gatos), ii) a comparative analysis of the functional behaviour of respiration and photosynthesis in both sites testing relationships between CO2 fluxes measured with the EC technique and meteorological variables such as temperature and direct or diffuse radiation and iii) the CH4 dynamicsat both sites by identifying, when possible, annual, seasonal and diurnal patterns.

Effect of annealing temperature on structural, morphological and electrical properties of nanoparticles TiO{sub 2} thin films by sol-gel method

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

Muaz, A. K. M.; Hashim, U., E-mail: uda@unimap.edu.my; Arshad, M. K. Md.

2016-07-06

In this paper, the sol-gel method is used to prepare nanoparticles titanium dioxide (TiO{sub 2}) thin films at different annealing temperature. The prepared sol was deposited on the p-SiO{sub 2} substrates by spin coating technique under room temperature. The nanoparticles TiO{sub 2} solution was synthesized using Ti{OCH(CH_3)_2}{sub 4} as a precursor with an methanol solution at a molar ratio 1:10. The prepared TiO{sub 2} sols will further validate through structural, morphological and electrical properties. From the X-ray diffraction (XRD) analysis, as-deposited films was found to be amorphous in nature and tend to transform into tetragonal anatase and rutile phase asmore » the films annealed at 573 and 773 K, respectively. The diversification of the surface roughness was characterized by atomic force microscopy (AFM) indicated the roughness and thickness very dependent on the annealing temperature. The two-point probe electrical resistance and conductance of nanoparticles TiO{sub 2} thin films were determined by the DC current-voltage (IV) analysis. From the I-V measurement, the electrical conductance increased as the films annealed at higher temperature.« less

Spin interactions in Graphene-Single Molecule Magnets Hybrids

NASA Astrophysics Data System (ADS)

Cervetti, Christian; Rettori, Angelo; Pini, Maria Gloria; Cornia, Andrea; Repollés, Aña; Luis, Fernando; Rauschenbach, Stephan; Dressel, Martin; Kern, Klaus; Burghard, Marko; Bogani, Lapo

2014-03-01

Graphene is a potential component of novel spintronics devices owing to its long spin diffusion length. Besides its use as spin-transport channel, graphene can be employed for the detection and manipulation of molecular spins. This requires an appropriate coupling between the sheets and the single molecular magnets (SMM). Here, we present a comprehensive characterization of graphene-Fe4 SMM hybrids. The Fe4 clusters are anchored non-covalently to the graphene following a diffusion-limited assembly and can reorganize into random networks when subjected to slightly elevated temperature. Molecules anchored on graphene sheets show unaltered static magnetic properties, whilst the quantum dynamics is profoundly modulated. Interaction with Dirac fermions becomes the dominant spin-relaxation channel, with observable effects produced by graphene phonons and reduced dipolar interactions. Coupling to graphene drives the spins over Villain's threshold, allowing the first observation of strongly-perturbative tunneling processes. Preliminary spin-transport experiments at low-temperature are further presented.

A Methane-Rich Early Mars: Implications for Habitability and the Emergence of Life

NASA Astrophysics Data System (ADS)

Wong, Michael L.; Friedson, Andrew James; Willacy, Karen; Shia, Run-Lie; Yung, Yuk; Russell, Michael J.

2017-10-01

We investigate the radiation and chemistry of a ~4.0 Ga, CH4-rich martian atmosphere in an effort to assess whether or not Mars was once habitable and suitable for the emergence of life. High atmospheric CH4 may be consistent with a mantle that does not reach the requisite pressure (24 GPa) and temperature (1900 K) for the silicate spinel-to-perovskite transition (Dale et al., 2012; McCammon, 1997; Wadhwa, 2001; Wood et al., 2006). Impact degassing from chondritic material can also contribute substantial amounts of CH4 to the atmosphere (Schaefer and Fegley, 2007). CH4 plays an important role in atmospheric radiation. Atmospheric models have demonstrated that a purely CO2 atmosphere, even one as massive as 7 bars, is incapable of heating Mars above an annual-mean surface temperature of 273 K (Forget et al., 2013), although recent studies show that recurring wet states could have been induced in an H2-rich atmosphere (Batalha et al., 2015, 2016). We show that CH4 alone is insufficient to warm early Mars above freezing—in fact it produces an anti-greenhouse effect—but it substantially raises middle atmospheric temperatures. We determine whether or not such high temperatures could prolong the photochemical lifetime of SO2, another potent greenhouse gas. We use RC1D, a non-gray 1-D radiative-convective equilibrium model, to calculate the atmospheric thermal structure consistent with the radiative heating and cooling associated with the composition computed at each chemical model time step. KINETICS, the Caltech/JPL chemistry transport model (e.g. Nair et al., 1994), determines the chemical makeup of the atmosphere, evaluating steady-state chemical profiles and the synthesis of astrobiologically relevant molecules. H2O is in vapor pressure equilibrium at the surface. We consider conditions forced by the faint-young Sun’s spectrum and luminosity. By coupling RC1D and KINETICS, we are able to paint a more realistic picture of Mars’s early climate, calculating the surface temperature under a CH4-rich atmosphere, and assessing the production of key electron acceptors, such as sulfate and nitrate.

CO2 and CH4 Production and CH4 Oxidation in Low Temperature Soil Incubations from Flat- and High-Centered Polygons, Barrow, Alaska, 2012

DOE Data Explorer

David E. Graham; Jianqiu Zheng; Taniya RoyChowdhury

2016-08-31

The dataset consists of respiration and methane production rates and methane oxidation potential obtained from soil microcosm studies carried out under controlled temperature and incubation conditions. Soils cores collected in 2012 represent the flat- and high-centered polygon active layers and permafrost (when present) from the NGEE Arctic Intensive Study Site 1, Barrow, Alaska.

Selective Adsorption and Selective Transport Diffusion of CO2-CH4 Binary Mixture in Coal Ultramicropores.

PubMed

Zhao, Yongliang; Feng, Yanhui; Zhang, Xinxin

2016-09-06

The adsorption and diffusion of the CO2-CH4 mixture in coal and the underlying mechanisms significantly affect the design and operation of any CO2-enhanced coal-bed methane recovery (CO2-ECBM) project. In this study, bituminous coal was fabricated based on the Wiser molecular model and its ultramicroporous parameters were evaluated; molecular simulations were established through Grand Canonical Monte Carlo (GCMC) and Molecular Dynamic (MD) methods to study the effects of temperature, pressure, and species bulk mole fraction on the adsorption isotherms, adsorption selectivity, three distinct diffusion coefficients, and diffusivity selectivity of the binary mixture in the coal ultramicropores. It turns out that the absolute adsorption amount of each species in the mixture decreases as temperature increases, but increases as its own bulk mole fraction increases. The self-, corrected, and transport diffusion coefficients of pure CO2 and pure CH4 all increase as temperature or/and their own bulk mole fractions increase. Compared to CH4, the adsorption and diffusion of CO2 are preferential in the coal ultramicropores. Adsorption selectivity and diffusivity selectivity were simultaneously employed to reveal that the optimal injection depth for CO2-ECBM is 800-1000 m at 308-323 K temperature and 8.0-10.0 MPa.

Temperature and moisture effects on greenhouse gas emissions from deep active-layer boreal soils

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

Bond-Lamberty, Ben; Smith, A. Peyton; Bailey, Vanessa L.

Rapid climatic changes, rising air temperatures, and increased fires are expected to drive permafrost degradation and alter soil carbon (C) cycling in many high-latitude ecosystems. How these soils will respond to changes in their temperature, moisture, and overlying vegetation is uncertain but critical to understand given the large soil C stocks in these regions. We used a laboratory experiment to examine how temperature and moisture control CO 2 and CH 4 emissions from mineral soils sampled from the bottom of the annual active layer, i.e., directly above permafrost, in an Alaskan boreal forest. Gas emissions from 30 cores, subjected tomore » two temperatures and either field moisture conditions or experimental drought, were tracked over a 100-day incubation; we also measured a variety of physical and chemical characteristics of the cores. Gravimetric water content was 0.31 ± 0.12 (unitless) at the beginning of the incubation; cores at field moisture were unchanged at the end, but drought cores had declined to 0.06 ± 0.04. Daily CO 2 fluxes were positively correlated with incubation chamber temperature, core water content, and percent soil nitrogen. They also had a temperature sensitivity ( Q 10) of 1.3 and 1.9 for the field moisture and drought treatments, respectively. Daily CH 4 emissions were most strongly correlated with percent nitrogen, but neither temperature nor water content was a significant first-order predictor of CH 4 fluxes. The cumulative production of C from CO 2 was over 6 orders of magnitude higher than that from CH 4; cumulative CO 2 was correlated with incubation temperature and moisture treatment, with drought cores producing 52–73 % lower C. Cumulative CH 4 production was unaffected by any treatment. These results suggest that deep active-layer soils may be sensitive to changes in soil moisture under aerobic conditions, a critical factor as discontinuous permafrost thaws in interior Alaska. Furthermore, deep but unfrozen high-latitude soils have been shown to be strongly affected by long-term experimental warming, and these results provide insight into their future dynamics and feedback potential with future climate change.« less

Temperature and moisture effects on greenhouse gas emissions from deep active-layer boreal soils

DOE PAGES

Bond-Lamberty, Ben; Smith, A. Peyton; Bailey, Vanessa L.

2016-12-21

Rapid climatic changes, rising air temperatures, and increased fires are expected to drive permafrost degradation and alter soil carbon (C) cycling in many high-latitude ecosystems. How these soils will respond to changes in their temperature, moisture, and overlying vegetation is uncertain but critical to understand given the large soil C stocks in these regions. We used a laboratory experiment to examine how temperature and moisture control CO 2 and CH 4 emissions from mineral soils sampled from the bottom of the annual active layer, i.e., directly above permafrost, in an Alaskan boreal forest. Gas emissions from 30 cores, subjected tomore » two temperatures and either field moisture conditions or experimental drought, were tracked over a 100-day incubation; we also measured a variety of physical and chemical characteristics of the cores. Gravimetric water content was 0.31 ± 0.12 (unitless) at the beginning of the incubation; cores at field moisture were unchanged at the end, but drought cores had declined to 0.06 ± 0.04. Daily CO 2 fluxes were positively correlated with incubation chamber temperature, core water content, and percent soil nitrogen. They also had a temperature sensitivity ( Q 10) of 1.3 and 1.9 for the field moisture and drought treatments, respectively. Daily CH 4 emissions were most strongly correlated with percent nitrogen, but neither temperature nor water content was a significant first-order predictor of CH 4 fluxes. The cumulative production of C from CO 2 was over 6 orders of magnitude higher than that from CH 4; cumulative CO 2 was correlated with incubation temperature and moisture treatment, with drought cores producing 52–73 % lower C. Cumulative CH 4 production was unaffected by any treatment. These results suggest that deep active-layer soils may be sensitive to changes in soil moisture under aerobic conditions, a critical factor as discontinuous permafrost thaws in interior Alaska. Furthermore, deep but unfrozen high-latitude soils have been shown to be strongly affected by long-term experimental warming, and these results provide insight into their future dynamics and feedback potential with future climate change.« less

Temperature and moisture effects on greenhouse gas emissions from deep active-layer boreal soils

NASA Astrophysics Data System (ADS)

Bond-Lamberty, Ben; Smith, A. Peyton; Bailey, Vanessa

2016-12-01

Rapid climatic changes, rising air temperatures, and increased fires are expected to drive permafrost degradation and alter soil carbon (C) cycling in many high-latitude ecosystems. How these soils will respond to changes in their temperature, moisture, and overlying vegetation is uncertain but critical to understand given the large soil C stocks in these regions. We used a laboratory experiment to examine how temperature and moisture control CO2 and CH4 emissions from mineral soils sampled from the bottom of the annual active layer, i.e., directly above permafrost, in an Alaskan boreal forest. Gas emissions from 30 cores, subjected to two temperatures and either field moisture conditions or experimental drought, were tracked over a 100-day incubation; we also measured a variety of physical and chemical characteristics of the cores. Gravimetric water content was 0.31 ± 0.12 (unitless) at the beginning of the incubation; cores at field moisture were unchanged at the end, but drought cores had declined to 0.06 ± 0.04. Daily CO2 fluxes were positively correlated with incubation chamber temperature, core water content, and percent soil nitrogen. They also had a temperature sensitivity (Q10) of 1.3 and 1.9 for the field moisture and drought treatments, respectively. Daily CH4 emissions were most strongly correlated with percent nitrogen, but neither temperature nor water content was a significant first-order predictor of CH4 fluxes. The cumulative production of C from CO2 was over 6 orders of magnitude higher than that from CH4; cumulative CO2 was correlated with incubation temperature and moisture treatment, with drought cores producing 52-73 % lower C. Cumulative CH4 production was unaffected by any treatment. These results suggest that deep active-layer soils may be sensitive to changes in soil moisture under aerobic conditions, a critical factor as discontinuous permafrost thaws in interior Alaska. Deep but unfrozen high-latitude soils have been shown to be strongly affected by long-term experimental warming, and these results provide insight into their future dynamics and feedback potential with future climate change.

Mechanical response of CH3NH3PbI3 nanowires

NASA Astrophysics Data System (ADS)

Ćirić, L.; Ashby, K.; Abadie, T.; Spina, M.; Duchamp, M.; Náfrádi, B.; Kollár, M.; Forró, L.; Horváth, E.

2018-03-01

We report a systematic study of the mechanical response of methylammonium lead triiodide CH3NH3PbI3 nanowires by employing bending measurements using atomic force microscope on suspended wires over photo-lithographically patterned channels. Force-deflection curves measured at room temperature give a Young's modulus between 2 and 14 GPa. This broad range of values is attributed to the variations in the microcrystalline texture of halide perovskite nanowires. The mechanical response of a highly crystalline nanowire is linear with force and has a brittle character. The braking modulus of 48 ± 20 MPa corresponds to 100 μm of radius of curvature of the nanowires, rendering them much better structures for flexible devices than spin coated films. The measured moduli decrease rapidly if the NW is exposed to water vapor.

On the interactions of nitriles and fluoro-substituted pyridines with silicon tetrafluoride: Computations and thin film IR spectroscopy

NASA Astrophysics Data System (ADS)

Hora, Nicholas J.; Wahl, Benjamin M.; Soares, Camilla; Lara, Skylee A.; Lanska, John R.; Phillips, James A.

2018-04-01

The nature of the interactions between silicon tetrafluoride and series of nitrogen bases, including nitriles (RCN, with R > CH3), pyridine, and various fluoro-substituted pyridines, has been investigated via quantum-chemical computations, low-temperature IR spectroscopy, and bulk reactivity experiments. Using (primarily) M06 with the 6-311+G(2df,2pd) basis set, we obtained equilibrium structures, binding energies, harmonic frequencies, and N-Si potentials in the gas-phase and in bulk dielectric media for an extensive series of 1:1 molecular complexes, including: C6H5CH2CN-SiF4, CH3CH2CN-SiF4, (CH3)3CCN-SiF4, C5H5N-SiF4, 4-FC5H4N-SiF4, 3,5-C5F2H3N-SiF4, 2,6-C5F2H3N-SiF4 and 3,4,5-C5F3H2N-SiF4. In addition, for the analogous 2:1 complexes of pyridine and 3,5-difluororpyridine, we obtained equilibrium structures, binding energies, and harmonic frequencies. The N-Si distances in the 1:1 nitrile complexes are fairly long, ranging from 2.84 Å to 2.88 Å, and the binding energies range from 4.0 to 4.2 kcal/mol (16.7-17.6 kJ/mol). Also, computations predict extremely anharmonic N-Si potentials, for which the inner portions of the curve are preferentially stabilized in dielectric media, which predict an enhancement of these interactions in condensed-phases. However, we see no evidence of bulk reactivity between C6H5CH2CN, CH3CH2CN, or (CH3)3CCN and SiF4, nor any significant interaction between (CH3)3CCN and SiF4 in low temperature IR spectra of solid, (CH3)3CCN/SiF4 thin films. Conversely, the interactions in four of the five 1:1, pyridine-SiF4 complexes are generally stronger; binding energies range from 5.7 to 9.6 kcal/mol (23.8-40.2 kJ/mol), and correspondingly the N-Si distances are relatively short (2.12-2.25 Å). The exception is 2,6-C5F2H3N-SiF4, for which the binding energy is only 3.6 kcal/mol (15.1 kJ/mol), and the N-Si distance is quite long (3.12 Å). In addition, both pyridine and 3,5-difluororpyridine were found to form stable reaction products with SiF4; but no analogous product was obtained with 2,6-difluororpyridine and SiF4, nor was any significant interaction indicated in low-temperature IR spectra of 2,6-difluororpyridine/SiF4 films. By contrast, low temperature spectra of pyridine/SiF4 and 3,5-difluororpyridine/SiF4 thin films are consistent with the presence of a distinct 2:1 reaction product. Moreover, the observed frequencies agree reasonably well with those predicted for the cis, octahedral coordination isomers of the 2:1 molecular complexes, in which the N-Si bonds are compressed slightly relative to those in the predicted gas-phase structures.

High-resolution sub-Doppler infrared spectroscopy of atmospherically relevant Criegee precursor CH2I radicals: CH2 stretch vibrations and "charge-sloshing" dynamics

NASA Astrophysics Data System (ADS)

Kortyna, A.; Lesko, D. M. B.; Nesbitt, D. J.

2018-05-01

The combination of a pulsed supersonic slit-discharge source and single-mode difference frequency direct absorption infrared spectroscopy permit first high resolution infrared study of the iodomethyl (CH2I) radical, with the CH2I radical species generated in a slit jet Ne/He discharge and cooled to 16 K in the supersonic expansion. Dual laser beam detection and collisional collimation in the slit expansion yield sub-Doppler linewidths (60 MHz), an absolute frequency calibration of 13 MHz, and absorbance sensitivities within a factor of two of the shot-noise limit. Fully rovibrationally resolved direct absorption spectra of the CH2 symmetric stretch mode (ν2) are obtained and fitted to a Watson asymmetric top Hamiltonian with electron spin-rotation coupling, providing precision rotational constants and spin-rotation tensor elements for the vibrationally excited state. Analysis of the asymmetric top rotational constants confirms a vibrationally averaged planar geometry in both the ground- and first-excited vibrational levels. Sub-Doppler resolution permits additional nuclear spin hyperfine structures to be observed, with splittings in excellent agreement with microwave measurements on the ground state. Spectroscopic data on CH2I facilitate systematic comparison with previous studies of halogen-substituted methyl radicals, with the periodic trends strongly correlated with the electronegativity of the halogen atom. Interestingly, we do not observe any asymmetric CH2 stretch transitions, despite S/N ≈ 25:1 on strongest lines in the corresponding symmetric CH2 stretch manifold. This dramatic reversal of the more typical 3:1 antisymmetric/symmetric CH2 stretch intensity ratio signals a vibrational transition moment poorly described by simple "bond-dipole" models. Instead, the data suggest that this anomalous intensity ratio arises from "charge sloshing" dynamics in the highly polar carbon-iodine bond, as supported by ab initio electron differential density plots and indeed consistent with observations in other halomethyl radicals and protonated cluster ions.

Evidence of spin phonon coupling in magnetoelectric NiFe{sub 2}O{sub 4}/PMN-PT composite

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

Ahlawat, Anju; Satapathy, S., E-mail: srinu73@rrcat.gov.in, E-mail: srinusatapathy@gmail.com; Gupta, P. K.

2013-12-16

The coupling of phonon with spin in strain coupled magnetoelectric NiFe{sub 2}O{sub 4} (NFO)/0.65Pb(Mg{sub 1/3}Nb{sub 2/3})O{sub 3}–0.35PbTiO{sub 3} (PMN-PT) composite was investigated by temperature-dependent Raman spectroscopy and magnetic measurements in the range 30–350 °C. Pure NFO shows usual ferromagnetic behaviour in this temperature range while NFO/PMN-PT composite show dramatic change in magnetic moment across ferroelectric transition temperature (T{sub c} ∼ 180 °C) of PMN-PT. The temperature evolution of the Raman spectra for the composite shows significant phonon anomalies in T-site (Fe-O) and O-site (Ni/Fe-O) phonon modes at ferroelectric transition temperature is attributed to spin phonon coupling in NFO/PMN-PT composite. The strain mediated magnetoelectric couplingmore » mechanism in this composite is apparent from the observed spin phonon interaction.« less

Atmospheric Dynamics and Disequilibrium CO/CH4 Chemistry in the Atmosphere of the Transiting Planet HD 209458b

NASA Astrophysics Data System (ADS)

Cooper, C. S.; Showman, A. P.

2005-08-01

Chemical equilibrium considerations predict that carbon will be present in the atmosphere of HD 209458b as either CO or CH4. Assuming a solar abundance distribution of elements, the concentrations of these species are controlled by temperature and pressure only. In cooler regions, however, vigorous mass transport can occur on time scales shorter than the time scale for interconversion between CO and CH4. This results in excess [CO]/[CH4] relative to the concentrations attained in chemical equilibrium. In this work, we adapt the model of HD 209458b's meteorology used in Cooper & Showman (2005) to treat the disequilibrium chemistry of carbon. Cooper & Showman (2005) show that high-speed winds ( ˜ 4 km s-1) and large temperature contrasts ( ˜ 500 K) are plausible near the photosphere. We model CO and CH4 as passive tracers; i.e., they follow but do not disturb the fluid dynamics of the system. Our simulations will yield maps of the distribution of CO and CH4 to help guide efforts to detect the presence of carbon on this planet. Though CO was not detected on HD 209458b (Deming et al. 2005) by transmission spectroscopy, its presence in the atmosphere cannot be ruled out. For example, CO could be present over much of the dayside hemisphere but depleted near the limbs. The distribution of CO in the atmosphere is diagnostic of temperature at the pressure levels probed by various CO absorption features (Bézard & Lellouch 2002). A positive CO detection would also rule out the hypothesis that the ratio C/O > 1 on this extrasolar planet (e.g., Fortney et al. 2005). This research is supported by NSF grant AST-0307664 and NASA GSRP NGT5-50462.

Low-Temperature Dynamic Nuclear Polarization at 9.4 Tesla With a 30 Milliwatt Microwave Source

PubMed Central

Thurber, Kent R.; Yau, Wai-Ming; Tycko, Robert

2010-01-01

Dynamic nuclear polarization (DNP) can provide large signal enhancements in nuclear magnetic resonance (NMR) by transfer of polarization from electron spins to nuclear spins. We discuss several aspects of DNP experiments at 9.4 Tesla (400 MHz resonant frequency for 1H, 264 GHz for electron spins in organic radicals) in the 7–80 K temperature range, using a 30 mW, frequency-tunable microwave source and a quasi-optical microwave bridge for polarization control and low-loss microwave transmission. In experiments on frozen glycerol/water doped with nitroxide radicals, DNP signal enhancements up to a factor of 80 are observed (relative to 1H NMR signals with thermal equilibrium spin polarization). The largest sensitivity enhancements are observed with a new triradical dopant, DOTOPA-TEMPO. Field modulation with a 10 G root-mean-squared amplitude during DNP increases the nuclear spin polarizations by up to 135%. Dependencies of 1H NMR signal amplitudes, nuclear spin relaxation times, and DNP build-up times on the dopant and its concentration, temperature, microwave power, and modulation frequency are reported and discussed. The benefits of low-temperature DNP can be dramatic: the 1H spin polarization is increased approximately 1000-fold at 7 K with DNP, relative to thermal polarization at 80 K. PMID:20392658

Using a non-spin flip model to rationalize the irregular patterns observed in the activation of the C-H and Si-H bonds of small molecules by CpMCO (M = Co, Rh) complexes.

PubMed

Castro, Guadalupe; Colmenares, Fernando

2017-09-20

The activation of the C-H and Si-H bonds of CH(CH 3 ) 3 and SiH(CH 3 ) 3 molecules by organometallic compounds CpMCO (M = Co, Rh) has been investigated through DFT and CASSCF-MRMP2 calculations. In particular, we have analyzed the pathways joining the lowest-lying triplet and singlet states of the reactants with the products arising from the insertion of the metal atom into the C-H or Si-H bonds of the organic molecules. Channels connecting the reactants with the inserted structure Cp(CO)H-M-C(CH 3 ) 3 through the oxidative addition of the C-H bond of the organic molecule to the metal fragment were found only for the reaction CpRhCO + CH(CH 3 ) 3 . However, inserted structures could also be obtained for the interactions of SiH(CH 3 ) 3 with CpCoCO and CpRhCO by two sequential reactions involving the formation and rebounding of the radical fragments Cp(CO)H-M + Si(CH 3 ) 3 . According to this two-step reaction scheme, the complex CpCoCO is unable to activate the C-H bond of the CH(CH 3 ) 3 molecule due to the high energy at which the radical fragments Cp(CO)H-M + C(CH 3 ) 3 are located. The picture attained for these interactions is consistent with the available experimental data for this kind of reaction and allows rationalization of the differences in the reactivity patterns determined for them without using spin-flip models, as has been proposed in previous studies.

Compact CH{sub 4} sensor system based on a continuous-wave, low power consumption, room temperature interband cascade laser

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

Dong, Lei, E-mail: donglei@sxu.edu.cn; State Key Laboratory of Quantum Optics and Quantum Optics Devices, Institute of Laser Spectroscopy, Shanxi University, Taiyuan 030006; Li, Chunguang

A tunable diode laser absorption spectroscopy-based methane sensor, employing a dense-pattern multi-pass gas cell and a 3.3 μm, CW, DFB, room temperature interband cascade laser (ICL), is reported. The optical integration based on an advanced folded optical path design and an efficient ICL control system with appropriate electrical power management resulted in a CH{sub 4} sensor with a small footprint (32 × 20 × 17 cm{sup 3}) and low-power consumption (6 W). Polynomial and least-squares fit algorithms are employed to remove the baseline of the spectral scan and retrieve CH{sub 4} concentrations, respectively. An Allan-Werle deviation analysis shows that the measurement precision can reach 1.4 ppb for amore » 60 s averaging time. Continuous measurements covering a seven-day period were performed to demonstrate the stability and robustness of the reported CH{sub 4} sensor system.« less

Temperature Effects on Microbial CH4 and CO2 Production in Permafrost-Affected Soils From the Barrow Environmental Observatory

NASA Astrophysics Data System (ADS)

Graham, D. E.; Roy Chowdhury, T.; Zheng, J.; Moon, J. W.; Yang, Z.; Gu, B.; Wullschleger, S. D.

2015-12-01

Warmer Arctic temperatures are increasing the annual soil thaw depth and prolonging the thaw season in Alaskan permafrost zones. This change exposes organic matter buried in the soils and permafrost to microbial degradation and mineralization to form CO2 and CH4. The proportion and fluxes of these greenhouse gases released into the atmosphere control the global feedback on warming. To improve representations of these biogeochemical processes in terrestrial ecosystem models we compared soil properties and microbial activities in core samples of polygonal tundra from the Barrow Environmental Observatory. Measurements of soil water potential through the soil column characterized water binding to the organic and mineral components. This suction combines with temperature to control freezing, gas diffusion and microbial activity. The temperature-dependence of CO2 and CH4 production from anoxic soil incubations at -2, +4 or +8 °C identified a significant lag in methanogenesis relative to CO2 production by anaerobic respiration and fermentation. Changes in the abundance of methanogen signature genes during incubations indicate that microbial population shifts caused by thawing and warmer temperatures drive changes in the mixtures of soil carbon degradation products. Comparisons of samples collected across the microtopographic features of ice-wedge polygons address the impacts of water saturation, iron reduction and organic matter content on CH4 production and oxidation. These combined measurements build process understanding that can be applied across scales to constrain key response factors in models that address Arctic soil warming.

Local spin dynamics at low temperature in the slowly relaxing molecular chain [Dy(hfac)3{NIT(C6H4OPh)}]: A μ+ spin relaxation study

NASA Astrophysics Data System (ADS)

Arosio, Paolo; Corti, Maurizio; Mariani, Manuel; Orsini, Francesco; Bogani, Lapo; Caneschi, Andrea; Lago, Jorge; Lascialfari, Alessandro

2015-05-01

The spin dynamics of the molecular magnetic chain [Dy(hfac)3{NIT(C6H4OPh)}] were investigated by means of the Muon Spin Relaxation (μ+SR) technique. This system consists of a magnetic lattice of alternating Dy(III) ions and radical spins, and exhibits single-chain-magnet behavior. The magnetic properties of [Dy(hfac)3{NIT(C6H4OPh)}] have been studied by measuring the magnetization vs. temperature at different applied magnetic fields (H = 5, 3500, and 16500 Oe) and by performing μ+SR experiments vs. temperature in zero field and in a longitudinal applied magnetic field H = 3500 Oe. The muon asymmetry P(t) was fitted by the sum of three components, two stretched-exponential decays with fast and intermediate relaxation times, and a third slow exponential decay. The temperature dependence of the spin dynamics has been determined by analyzing the muon longitudinal relaxation rate λinterm(T), associated with the intermediate relaxing component. The experimental λinterm(T) data were fitted with a corrected phenomenological Bloembergen-Purcell-Pound law by using a distribution of thermally activated correlation times, which average to τ = τ0 exp(Δ/kBT), corresponding to a distribution of energy barriers Δ. The correlation times can be associated with the spin freezing that occurs when the system condenses in the ground state.

Computation provides chemical insight into the diverse hydride NMR chemical shifts of [Ru(NHC)4(L)H]0/+ species (NHC = N-heterocyclic carbene; L = vacant, H2, N2, CO, MeCN, O2, P4, SO2, H-, F- and Cl-) and their [Ru(R2PCH2CH2PR2)2(L)H]+ congeners.

PubMed

Häller, L Jonas L; Mas-Marzá, Elena; Cybulski, Mateusz K; Sanguramath, Rajashekharayya A; Macgregor, Stuart A; Mahon, Mary F; Raynaud, Christophe; Russell, Christopher A; Whittlesey, Michael K

2017-02-28

Relativistic density functional theory calculations, both with and without the effects of spin-orbit coupling, have been employed to model hydride NMR chemical shifts for a series of [Ru(NHC) 4 (L)H] 0/+ species (NHC = N-heterocyclic carbene; L = vacant, H 2 , N 2 , CO, MeCN, O 2 , P 4 , SO 2 , H - , F - and Cl - ), as well as selected phosphine analogues [Ru(R 2 PCH 2 CH 2 PR 2 ) 2 (L)H] + (R = i Pr, Cy; L = vacant, O 2 ). Inclusion of spin-orbit coupling provides good agreement with the experimental data. For the NHC systems large variations in hydride chemical shift are shown to arise from the paramagnetic term, with high net shielding (L = vacant, Cl - , F - ) being reinforced by the contribution from spin-orbit coupling. Natural chemical shift analysis highlights the major orbital contributions to the paramagnetic term and rationalizes trends via changes in the energies of the occupied Ru d π orbitals and the unoccupied σ* Ru-H orbital. In [Ru(NHC) 4 (η 2 -O 2 )H] + a δ-interaction with the O 2 ligand results in a low-lying LUMO of d π character. As a result this orbital can no longer contribute to the paramagnetic shielding, but instead provides additional deshielding via overlap with the remaining (occupied) d π orbital under the L z angular momentum operator. These two effects account for the unusual hydride chemical shift of +4.8 ppm observed experimentally for this species. Calculations reproduce hydride chemical shift data observed for [Ru( i Pr 2 PCH 2 CH 2 P i Pr 2 ) 2 (η 2 -O 2 )H] + (δ = -6.2 ppm) and [Ru(R 2 PCH 2 CH 2 PR 2 ) 2 H] + (ca. -32 ppm, R = i Pr, Cy). For the latter, the presence of a weak agostic interaction trans to the hydride ligand is significant, as in its absence (R = Me) calculations predict a chemical shift of -41 ppm, similar to the [Ru(NHC) 4 H] + analogues. Depending on the strength of the agostic interaction a variation of up to 18 ppm in hydride chemical shift is possible and this factor (that is not necessarily readily detected experimentally) can aid in the interpretation of hydride chemical shift data for nominally unsaturated hydride-containing species. The synthesis and crystallographic characterization of the BAr F 4 - salts of [Ru(IMe 4 ) 4 (L)H] + (IMe 4 = 1,3,4,5-tetramethylimidazol-2-ylidene; L = P 4 , SO 2 ; Ar F = 3,5-(CF 3 ) 2 C 6 H 3 ) and [Ru(IMe 4 ) 4 (Cl)H] are also reported.

The 12C/13C Isotopic Ratio In Titan's Hydrocarbons

NASA Astrophysics Data System (ADS)

Nixon, Conor A.; Achterberg, R. K.; Vinatier, S.; Bezard, B.; Coustenis, A.; Teanby, N. A.; Irwin, P. G.; Cassini CIRS Team

2007-10-01

Isotopic ratios in planetary atmospheres are of considerable interest, yielding insights both about currently occurring processes, and also the formation and early evolution of the body. Before Cassini, ground-based measurements of Titan's 12C/13C in HCN showed no firm evidence of deviation from the terrestrial inorganic standard (88.9) - albeit with large error bars of 20% - contrasting the enrichment in nitrogen (15N/14N≈4.5 terrestrial). Since 2004, the Composite Infrared Spectrometer (CIRS) instrument on Cassini has recorded spectra of Titan's stratosphere globally, including the emissions of multiple isotopologues for certain hydrocarbons. We selected spectra for analysis from four flybys (T4, T12, T19, T22), covering five latitudes from 65°S to 71°N. By means of a radiative transfer code and inversion scheme, we have first modeled the ν4 band of 12CH4 at 1304 cm-1 to retrieve stratospheric temperatures, and subsequently the emissions of 13CH4, 12C2H2, 13C12CH2, 12C2H6 and 13C12CH6. Our results indicate 12C/13C = 81.2±2.0 for all three species combined over all five latitudes, in excellent agreement with the Huygens GCMS value of 12CH4/13CH4 = 82.3±1.0 (Niemann et al. 2005), some 9% lower than terrestrial inorganic, and lower than in ethane on Saturn (91 (-13) (+26)) and Jupiter (99 (-23) (+43)) (Sada et al. 1996). No latitude variation was detected, however the 12C/13C in the C2 species (83.9±3.1 in acetylene, 89.9±7.2 in ethane) were consistently higher than in methane (78.0±2.7) after considering random errors. Although it is possible that this is a real chemical or physical (condensation) effect, it is more likely due to systematic errors in our temperature profile, as our spectra do not yield independent temperature information at 10 mbar where the emissions of 13C12CH2 and 13C12CH6 originate, and we default to the Huygens probe temperatures. In future, this problem may be resolved by modeling CIRS limb spectra.

Temperature Dependent Rate Coefficients for the Gas-Phase Reaction of the OH Radical with Linear (L2, L3) and Cyclic (D3, D4) Permethylsiloxanes.

PubMed

Bernard, François; Papanastasiou, Dimitrios K; Papadimitriou, Vassileios C; Burkholder, James B

2018-05-03

Permethylsiloxanes are emitted into the atmosphere during production and use as personal care products, lubricants, and cleaning agents. The predominate atmospheric loss process for permethylsiloxanes is expected to be via gas-phase reaction with the OH radical. In this study, rate coefficients, k(T), for the OH radical gas-phase reaction with the two simplest linear and cyclic permethylsiloxanes were measured using a pulsed laser photolysis-laser induced fluorescence technique over the temperature range of 240-370 K and a relative rate method at 294 K: hexamethyldisiloxane ((CH 3 ) 3 SiOSi(CH 3 ) 3 , L 2 ), k 1 ; octamethyltrisiloxane ([(CH 3 ) 3 SiO] 2 Si(CH 3 ) 2 , L 3 ), k 2 ; hexamethylcyclotrisiloxane ([-Si(CH 3 ) 2 O-] 3 , D 3 ), k 3 ; and octamethylcyclotetrasiloxane ([-Si(CH 3 ) 2 O-] 4 , D 4 ), k 4 . The obtained k(294 K) values and temperature-dependence expressions for the 240-370 K temperature range are (cm 3 molecule -1 s -1 , 2σ absolute uncertainties): k 1 (294 K) = (1.28 ± 0.08) × 10 -12 , k 1 ( T) = (1.87 ± 0.18) × 10 -11 exp(-(791 ± 27)/ T); k 2 (294 K) = (1.72 ± 0.10) × 10 -12 , k 2 ( T) = 1.96 × 10 -13 (T/298) 4.34 exp(657/ T); k 3 (294 K) = (0.82 ± 0.05) × 10 -12 , k 3 ( T) = (1.29 ± 0.19) × 10 -11 exp(-(805 ± 43)/ T); and k 4 (294 K) = (1.12 ± 0.10) × 10 -12 , k 4 ( T) = (1.80 ± 0.26) × 10 -11 exp(-(816 ± 43)/ T). The cyclic molecules were found to be less reactive than the analogous linear molecule with the same number of -CH 3 groups, while the linear and cyclic permethylsiloxane reactivity both increase with the increasing number of CH 3 - groups. The present results are compared with previous rate coefficient determinations where available. The permethylsiloxanes included in this study are atmospherically short-lived compounds with estimated atmospheric lifetimes of 11, 8, 17, and 13 days, respectively.

A DFT-Elucidated Comparison of the Solution-Phase and SAM Electrochemical Properties of Short-Chain Mercaptoalkylferrocenes: Synthetic and Spectroscopic Aspects, and the Structure of Fc-CH2CH2-S-S-CH2CH2-Fc.

PubMed

Lewtak, Jan P; Landman, Marilé; Fernández, Israel; Swarts, Jannie C

2016-03-07

Facile synthetic procedures to synthesize a series of difficult-to-obtain mercaptoalkylferrocenes, namely, Fc(CH2)nSH, where n = 1 (1), 2 (2), 3 (3), or 4 (4) and Fc = Fe(η(5)-C5H5)(η(5)-C5H4), are reported. Dimerization of 1-4 to the corresponding disulfides 19-22 was observed in air. Dimer 20 (Z = 2) crystallized in the triclinic space group P1̅. Dimers 20-22 could be reduced back to the original Fc(CH2)nSH derivatives with LiAlH4 in refluxing tetrahydrofuran. Density functional theory (DFT) calculations showed that the highest occupied molecular orbital of 1-4 lies exclusively on the ferrocenyl group implying that the electrochemical oxidation observed at ca. -15 < Epa < 76 mV versus FcH/FcH(+) involves exclusively an Fe(II) to Fe(III) process. Further DFT calculations showed this one-electron oxidation is followed by proton loss on the thiol group to generate a radical, Fc(CH2)nS(•), with spin density mainly located on the sulfur. Rapid exothermic dimerization leads to the observed dimers, Fc(CH2)n-S-S-(CH 2)nFc. Reduction of the ferrocenium groups on the dimer occurs at potentials that still showed the ferrocenyl group ΔE = Epa,monomer - Epc,dimer ≤ 78 mV, indicating that the redox properties of the ferrocenyl group on the mercaptans are very similar to those of the dimer. (1)H NMR measurements showed that, like ferrocenyl oxidation, the resonance position of the sulfhydryl proton, SH, and others, are dependent on -(CH2)n- chain length. Self-assembled monolayers (SAMs) on gold were generated to investigate the electrochemical behavior of 1-4 in the absence of diffusion. Under these conditions, ΔE approached 0 mV for the longer chain derivatives at slow scan rates. The surface-bound ferrocenyl group of the metal-thioether, Fc(CH2)n -S-Au, is oxidized at approximately equal potentials as the equivalent CH2Cl2-dissolved ferrocenyl species 1-4. Surface coverage by the SAMs is dependent on alkyl chain length with the largest coverage obtained for 4, while the rate of heterogeneous electron transfer between SAM substrate and electrode was the fastest for the shortest chain derivative, Fc-CH2-S-Au.

Winter fluxes of CO2 and CH4 from subalpine soils in Rocky Mountain National Park, Colorado

USGS Publications Warehouse

Mast, M. Alisa; Wickland, Kimberly P.; Striegl, Robert G.; Clow, David W.

1998-01-01

Fluxes of CO2 and CH4 through a seasonal snowpack were measured in and adjacent to a subalpine wetland in Rocky Mountain National Park, Colorado. Gas diffusion through the snow was controlled by gas production or consumption in the soil and by physical snowpack properties. The snowpack insulated soils from cold midwinter air temperatures allowing microbial activity to continue through the winter. All soil types studied were net sources of CO2 to the atmosphere through the winter, whereas saturated soils in the wetland center were net emitters of CH4 and soils adjacent to the wetland were net CH4 consumers. Most sites showed similar temporal patterns in winter gas fluxes; the lowest fluxes occurred in early winter, and maximum fluxes occurred at the onset of snowmelt. Temporal changes in fluxes probably were related to changes in soil-moisture conditions and hydrology because soil temperatures were relatively constant under the snowpack. Average winter CO2 fluxes were 42.3, 31.2, and 14.6 mmol m−2 d−1 over dry, moist, and saturated soils, respectively, which accounted for 8 to 23% of the gross annual CO2emissions from these soils. Average winter CH4 fluxes were −0.016, 0.274, and 2.87 mmol m−2 d−1over dry, moist, and saturated soils, respectively. Microbial activity under snow cover accounted for 12% of the annual CH4 consumption in dry soils and 58 and 12% of the annual CH4 emitted from moist and saturated soils, respectively. The observed ranges in CO2 and CH4 flux through snow indicated that winter fluxes are an important part of the annual carbon budget in seasonally snow-covered terrains.

Effects of CO addition on the characteristics of laminar premixed CH{sub 4}/air opposed-jet flames

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

Wu, C.-Y.; Chao, Y.-C.; Chen, C.-P.

2009-02-15

The effects of CO addition on the characteristics of premixed CH{sub 4}/air opposed-jet flames are investigated experimentally and numerically. Experimental measurements and numerical simulations of the flame front position, temperature, and velocity are performed in stoichiometric CH{sub 4}/CO/air opposed-jet flames with various CO contents in the fuel. Thermocouple is used for the determination of flame temperature, velocity measurement is made using particle image velocimetry (PIV), and the flame front position is measured by direct photograph as well as with laser-induced predissociative fluorescence (LIPF) of OH imaging techniques. The laminar burning velocity is calculated using the PREMIX code of Chemkin collectionmore » 3.5. The flame structures of the premixed stoichiometric CH{sub 4}/CO/air opposed-jet flames are simulated using the OPPDIF package with GRI-Mech 3.0 chemical kinetic mechanisms and detailed transport properties. The measured flame front position, temperature, and velocity of the stoichiometric CH{sub 4}/CO/air flames are closely predicted by the numerical calculations. Detailed analysis of the calculated chemical kinetic structures reveals that as the CO content in the fuel is increased from 0% to 80%, CO oxidation (R99) increases significantly and contributes to a significant level of heat-release rate. It is also shown that the laminar burning velocity reaches a maximum value (57.5 cm/s) at the condition of 80% of CO in the fuel. Based on the results of sensitivity analysis, the chemistry of CO consumption shifts to the dry oxidation kinetics when CO content is further increased over 80%. Comparison between the results of computed laminar burning velocity, flame temperature, CO consumption rate, and sensitivity analysis reveals that the effect of CO addition on the laminar burning velocity of the stoichiometric CH{sub 4}/CO/air flames is due mostly to the transition of the dominant chemical kinetic steps. (author)« less

On the multiferroic skyrmion-host GaV4S8

NASA Astrophysics Data System (ADS)

Widmann, S.; Ruff, E.; Günther, A.; Krug von Nidda, H.-A.; Lunkenheimer, P.; Tsurkan, V.; Bordács, S.; Kézsmárki, I.; Loidl, A.

2017-12-01

The lacunar spinel GaV4S8 exhibits orbital ordering at 44 K and shows a complex magnetic phase diagram below 12.7 K, which includes ferromagnetic and cycloidal spin order. At low but finite external magnetic fields, Néel-type skyrmions are formed in this material. Skyrmions are whirl-like spin vortices that have received great theoretical interest because of their non-trivial spin topology and that are also considered as basic entities for new data-storage technologies. Interestingly, we found that the orbitally ordered phase shows sizable ferroelectric polarisation and that excess spin-driven polarisations appear in all magnetic phases, including the skyrmion-lattice phase. Hence, GaV4S8 shows simultaneous magnetic and polar order and belongs to the class of multiferroics materials that attracted enormous attention in recent years. Here, we summarise the existing experimental information on the magnetic, electronic and dielectric properties of GaV4S8. By performing detailed magnetic susceptibility, resistivity, specific heat and dielectric experiments, we complement the low-temperature phase diagram. Specifically, we show that the low-temperature and low-field ground state of GaV4S8 seems to have a more complex spin configuration than purely collinear ferromagnetic spin order. In addition, at the structural Jahn-Teller transition the magnetic exchange interaction changes from antiferromagnetic to ferromagnetic. We also provide experimental evidence that the vanadium V4 clusters in GaV4S8 can be regarded as molecular units with spin 1/2. However, at high temperatures deviations in the susceptibility show up, indicating that either the magnetic moments of the vanadium atoms fluctuate independently or excited states of the V4 molecule become relevant.

Oxidative desulfurization of fuels catalyzed by Fenton-like ionic liquids at room temperature.

PubMed

Jiang, Yunqing; Zhu, Wenshuai; Li, Huaming; Yin, Sheng; Liu, Hua; Xie, Qingjie

2011-03-21

Oxidation of the sulfur-containing compounds benzothiophene (BT), dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT) has been studied in a desulfurization system composed of model oil, hydrogen peroxide, and different types of ionic liquids [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3), [(C(8)H(17))(3)CH(3)N]Cl/CuCl(2), [(C(8)H(17))(3)CH(3)N]Cl/ZnCl(2), [(C(8)H(17))(3)CH(3)N]Cl/SnCl(2), [(C(4)H(9))(3)CH(3)N]Cl/FeCl(3), [C(10)H(21)(CH(3))(3)N]Cl/FeCl(3), [(C(10)H(21))(2)(CH(3))(2)N]Cl/FeCl(3). Deep desulfurization is achieved in the Fenton-like ionic liquid [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3) at 25 °C for 1 h. The desulfurization of DBT reaches 97.9%, in consuming very low amount of [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3) (only 0.702 mmol). The reaction conditions, for example, the amount of [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3) or H(2)O(2), the temperature, and the molar ratio of FeCl(3) to [(C(8)H(17))(3)CH(3)N]Cl, are investigated for this system. The oxidation reactivity of the different sulfur-containing compounds is found to decrease in the order of DBT>BT>4,6-DMDBT. The desulfurization system can be recycled six times without significant decrease in activity. The sulfur level of FCC gasoline could be reduced from 360 ppm to 110 ppm. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

{sup 1}H and {sup 19}F spin-lattice relaxation and CH{sub 3} or CF{sub 3} reorientation in molecular solids containing both H and F atoms

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

Beckmann, Peter A., E-mail: pbeckman@brynmawr.edu; Rheingold, Arnold L.

2016-04-21

The dynamics of methyl (CH{sub 3}) and fluoromethyl (CF{sub 3}) groups in organic molecular (van der Waals) solids can be exploited to survey their local environments. We report solid state {sup 1}H and {sup 19}F spin-lattice relaxation experiments in polycrystalline 3-trifluoromethoxycinnamic acid, along with an X-ray diffraction determination of the molecular and crystal structure, to investigate the intramolecular and intermolecular interactions that determine the properties that characterize the CF{sub 3} reorientation. The molecule is of no particular interest; it simply provides a motionless backbone (on the nuclear magnetic resonance (NMR) time scale) to investigate CF{sub 3} reorientation occurring on themore » NMR time scale. The effects of {sup 19}F–{sup 19}F and {sup 19}F–{sup 1}H spin-spin dipolar interactions on the complicated nonexponential NMR relaxation provide independent inputs into determining a model for CF{sub 3} reorientation. As such, these experiments provide much more information than when only one spin species (usually {sup 1}H) is present. In Sec. IV, which can be read immediately after the Introduction without reading the rest of the paper, we compare the barrier to CH{sub 3} and CF{sub 3} reorientation in seven organic solids and separate this barrier into intramolecular and intermolecular components.« less

Mechanistic Processes Controlling Gas Sorption in Shale Reservoirs

NASA Astrophysics Data System (ADS)

Schaef, T.; Loring, J.; Ilton, E. S.; Davidson, C. L.; Owen, T.; Hoyt, D.; Glezakou, V. A.; McGrail, B. P.; Thompson, C.

2014-12-01

Utilization of CO2 to stimulate natural gas production in previously fractured shale-dominated reservoirs where CO2 remains in place for long-term storage may be an attractive new strategy for reducing the cost of managing anthropogenic CO2. A preliminary analysis of capacities and potential revenues in US shale plays suggests nearly 390 tcf in additional gas recovery may be possible via CO2 driven enhanced gas recovery. However, reservoir transmissivity properties, optimum gas recovery rates, and ultimate fate of CO2 vary among reservoirs, potentially increasing operational costs and environmental risks. In this paper, we identify key mechanisms controlling the sorption of CH4 and CO2 onto phyllosilicates and processes occurring in mixed gas systems that have the potential of impacting fluid transfer and CO2 storage in shale dominated formations. Through a unique set of in situ experimental techniques coupled with molecular-level simulations, we identify structural transformations occurring to clay minerals, optimal CO2/CH4 gas exchange conditions, and distinguish between adsorbed and intercalated gases in a mixed gas system. For example, based on in situ measurements with magic angle spinning NMR, intercalation of CO2 within the montmorillonite structure occurs in CH4/CO2 gas mixtures containing low concentrations (<5 mol%) of CO2. A stable montmorillonite structure dominates during exposure to pure CH4 (90 bar), but expands upon titration of small fractions (1-3 mol%) of CO2. Density functional theory was used to quantify the difference in sorption behavior between CO2 and CH4 and indicates complex interactions occurring between hydrated cations, CH4, and CO2. The authors will discuss potential impacts of these experimental results on CO2-based hydrocarbon recovery processes.

Effect of shell thickness on the exchange bias blocking temperature and coercivity in Co-CoO core-shell nanoparticles

NASA Astrophysics Data System (ADS)

Thomas, S.; Reethu, K.; Thanveer, T.; Myint, M. T. Z.; Al-Harthi, S. H.

2017-08-01

The exchange bias blocking temperature distribution of naturally oxidized Co-CoO core-shell nanoparticles exhibits two distinct signatures. These are associated with the existence of two magnetic entities which are responsible for the temperature dependence of an exchange bias field. One is from the CoO grains which undergo thermally activated magnetization reversal. The other is from the disordered spins at the Co-CoO interface which exhibits spin-glass-like behavior. We investigated the oxide shell thickness dependence of the exchange bias effect. For particles with a 3 nm thick CoO shell, the predominant contribution to the temperature dependence of exchange bias is the interfacial spin-glass layer. On increasing the shell thickness to 4 nm, the contribution from the spin-glass layer decreases, while upholding the antiferromagnetic grain contribution. For samples with a 4 nm CoO shell, the exchange bias training was minimal. On the other hand, 3 nm samples exhibited both the training effect and a peak in coercivity at an intermediate set temperature Ta. This is explained using a magnetic core-shell model including disordered spins at the interface.

A theoretical study of the hydrogen-storage potential of (H2)4CH4 in metal organic framework materials and carbon nanotubes.

PubMed

Li, Q; Thonhauser, T

2012-10-24

The hydrogen-methane compound (H(2))(4)CH(4)-or for short H4M-is one of the most promising hydrogen-storage materials. This van der Waals compound is extremely rich in molecular hydrogen: 33.3 mass%, not including the hydrogen bound in CH(4); including it, we reach even 50.2 mass%. Unfortunately, H4M is not stable under ambient pressure and temperature, requiring either low temperature or high pressure. In this paper, we investigate the properties and structure of the molecular and crystalline forms of H4M, using ab initio methods based on van der Waals DFT (vdW-DF). We further investigate the possibility of creating the pressures required to stabilize H4M through external agents such as metal organic framework (MOF) materials and carbon nanotubes, with very encouraging results. In particular, we find that certain MOFs can create considerable pressure for H4M in their cavities, but not enough to stabilize it at room temperature, and moderate cooling is still necessary. On the other hand, we find that all the investigated carbon nanotubes can create the high pressures required for H4M to be stable at room temperature, with direct implications for new and exciting hydrogen-storage applications.

Eutrophication effects on greenhouse gas fluxes from shallow-lake mesocosms override those of climate warming.

PubMed

Davidson, Thomas A; Audet, Joachim; Svenning, Jens-Christian; Lauridsen, Torben L; Søndergaard, Martin; Landkildehus, Frank; Larsen, Søren E; Jeppesen, Erik

2015-12-01

Fresh waters make a disproportionately large contribution to greenhouse gas (GHG) emissions, with shallow lakes being particular hot spots. Given their global prevalence, how GHG fluxes from shallow lakes are altered by climate change may have profound implications for the global carbon cycle. Empirical evidence for the temperature dependence of the processes controlling GHG production in natural systems is largely based on the correlation between seasonal temperature variation and seasonal change in GHG fluxes. However, ecosystem-level GHG fluxes could be influenced by factors, which while varying seasonally with temperature are actually either indirectly related (e.g. primary producer biomass) or largely unrelated to temperature, for instance nutrient loading. Here, we present results from the longest running shallow-lake mesocosm experiment which demonstrate that nutrient concentrations override temperature as a control of both the total and individual GHG flux. Furthermore, testing for temperature treatment effects at low and high nutrient levels separately showed only one, rather weak, positive effect of temperature (CH4 flux at high nutrients). In contrast, at low nutrients, the CO2 efflux was lower in the elevated temperature treatments, with no significant effect on CH4 or N2 O fluxes. Further analysis identified possible indirect effects of temperature treatment. For example, at low nutrient levels, increased macrophyte abundance was associated with significantly reduced fluxes of both CH4 and CO2 for both total annual flux and monthly observation data. As macrophyte abundance was positively related to temperature treatment, this suggests the possibility of indirect temperature effects, via macrophyte abundance, on CH4 and CO2 flux. These findings indicate that fluxes of GHGs from shallow lakes may be controlled more by factors indirectly related to temperature, in this case nutrient concentration and the abundance of primary producers. Thus, at ecosystem scale, response to climate change may not follow predictions based on the temperature dependence of metabolic processes. © 2015 John Wiley & Sons Ltd.

Spectral Fingerprints of Earth-like Planets Around FGK Stars

PubMed Central

Kaltenegger, Lisa; Zsom, Andras; Segura, Antígona; Sasselov, Dimitar

2013-01-01

Abstract We present model atmospheres for an Earth-like planet orbiting the entire grid of main sequence FGK stars with effective temperatures ranging from Teff=4250 K to Teff=7000 K in 250 K intervals. We have modeled the remotely detectable spectra of Earth-like planets for clear and cloudy atmospheres at the 1 AU equivalent distance from the VIS to IR (0.4 to 20 μm) to compare detectability of features in different wavelength ranges in accordance with the James Webb Space Telescope and future design concepts to characterize exo-Earths. We have also explored the effect of the stellar UV levels as well as spectral energy distribution on a terrestrial atmosphere, concentrating on detectable atmospheric features that indicate habitability on Earth, namely, H2O, O3, CH4, N2O, and CH3Cl. The increase in UV dominates changes of O3, OH, CH4, N2O, and CH3Cl, whereas the increase in stellar temperature dominates changes in H2O. The overall effect as stellar effective temperatures and corresponding UV increase is a lower surface temperature of the planet due to a bigger part of the stellar flux being reflected at short wavelengths, as well as increased photolysis. Earth-like atmosphere models show more O3 and OH but less stratospheric CH4, N2O, CH3Cl, and tropospheric H2O (but more stratospheric H2O) with increasing effective temperature of main sequence stars. The corresponding detectable spectral features, on the other hand, show different detectability depending on the wavelength observed. We concentrate on directly imaged planets here as a framework to interpret future light curves, direct imaging, and secondary eclipse measurements of atmospheres of terrestrial planets in the habitable zone at varying orbital positions. Key Words: Habitability—Planetary atmospheres—Extrasolar terrestrial planets—Spectroscopic biosignatures. Astrobiology 13, 251–269. PMID:23537136

Role of spin polarization in FM/Al/FM trilayer film at low temperature

NASA Astrophysics Data System (ADS)

Lu, Ning; Webb, Richard

2014-03-01

Measurements of electronic transport in diffusive FM/normal metal/FM trilayer film are performed at temperature ranging from 2K to 300K to determine the behavior of the spin polarized current in normal metal under the influence of quantum phase coherence and spin-orbital interaction. Ten samples of Hall bar with length of 200 micron and width of 20 micron are fabricated through e-beam lithography followed by e-gun evaporation of Ni0.8Fe0.2, aluminum and Ni0.8Fe0.2 with different thickness (5nm to 45nm) in vacuum. At low temperature of 4.2K, coherent backscattering, Rashba spin-orbital interaction and spin flip scattering of conduction electrons contribute to magnetoresistance at low field. Quantitative analysis of magnetoresistance shows transition between weak localization and weak anti-localization for samples with different thickness ratio, which indicates the spin polarization actually affects the phase coherence length and spin-orbital scattering length. However, at temperature between 50K and 300K, only the spin polarization dominates the magnetoresistance.

Methane Feedbacks to the Global Climate System in a Warmer World

NASA Astrophysics Data System (ADS)

Dean, Joshua F.; Middelburg, Jack J.; Röckmann, Thomas; Aerts, Rien; Blauw, Luke G.; Egger, Matthias; Jetten, Mike S. M.; de Jong, Anniek E. E.; Meisel, Ove H.; Rasigraf, Olivia; Slomp, Caroline P.; in't Zandt, Michiel H.; Dolman, A. J.

2018-03-01

Methane (CH4) is produced in many natural systems that are vulnerable to change under a warming climate, yet current CH4 budgets, as well as future shifts in CH4 emissions, have high uncertainties. Climate change has the potential to increase CH4 emissions from critical systems such as wetlands, marine and freshwater systems, permafrost, and methane hydrates, through shifts in temperature, hydrology, vegetation, landscape disturbance, and sea level rise. Increased CH4 emissions from these systems would in turn induce further climate change, resulting in a positive climate feedback. Here we synthesize biological, geochemical, and physically focused CH4 climate feedback literature, bringing together the key findings of these disciplines. We discuss environment-specific feedback processes, including the microbial, physical, and geochemical interlinkages and the timescales on which they operate, and present the current state of knowledge of CH4 climate feedbacks in the immediate and distant future. The important linkages between microbial activity and climate warming are discussed with the aim to better constrain the sensitivity of the CH4 cycle to future climate predictions. We determine that wetlands will form the majority of the CH4 climate feedback up to 2100. Beyond this timescale, CH4 emissions from marine and freshwater systems and permafrost environments could become more important. Significant CH4 emissions to the atmosphere from the dissociation of methane hydrates are not expected in the near future. Our key findings highlight the importance of quantifying whether CH4 consumption can counterbalance CH4 production under future climate scenarios.

Comparison of CH4 Emission from Rice Paddy Soils between Coastal Zone and Inland Regions

NASA Astrophysics Data System (ADS)

Sun, M.; Li, X.

2016-12-01

Numerous measurements of methane (CH4) emission fluxes have been carried out in rice paddy soil between coastal zone and inland regions. However, the differences of CH4 emission from rice paddy soils in these two locations were unavailable. A database of CH4 emission in paddy rice was compiled from previous published references and field observations with major parameters including water regimes, fertilizer application, CH4 fluxes, and environmental variables. Results showed that CH4 emission from inland paddy fields was significantly higher than that in the coastal zone (p < 0.05). Fertilizer application and water management played an important role in CH4 emission. The application of organic fertilizer and continuous flooding significantly promoted CH4 emission from paddy fields. CH4 fluxes showed significantly positive correlations with organic matter, total nitrogen, available potassium and annual temperature (R2 = 0.39, 0.53, 0.27 and 0.23, p < 0.05), and negative correlations with pH and available phosphorus (R2 = 0.29 and 0.37, p < 0.05). Significant differences occurred in available potassium between inland and coastal rice paddy (p < 0.05), which might account for the difference of CH4 emission between inland and coastal rice paddy. The contrasting of CH4 fluxes between inland and coastal wetlands could improve our understanding of the roles of rice paddies in the regional CH4 regulation. Our results also have implications for informing rice paddy management and climate change policy making the efforts being made by agricultural organizations and enterprises to restore coastal rice paddies for mitigating CH4 emissions.

Generation of Hydrogen and Methane during Experimental Low-Temperature Reaction of Ultramafic Rocks with Water.

PubMed

McCollom, Thomas M; Donaldson, Christopher

2016-06-01

Serpentinization of ultramafic rocks is widely recognized as a source of molecular hydrogen (H2) and methane (CH4) to support microbial activity, but the extent and rates of formation of these compounds in low-temperature, near-surface environments are poorly understood. Laboratory experiments were conducted to examine the production of H2 and CH4 during low-temperature reaction of water with ultramafic rocks and minerals. Experiments were performed by heating olivine or harzburgite with aqueous solutions at 90°C for up to 213 days in glass bottles sealed with butyl rubber stoppers. Although H2 and CH4 increased steadily throughout the experiments, the levels were very similar to those found in mineral-free controls, indicating that the rubber stoppers were the predominant source of these compounds. Levels of H2 above background were observed only during the first few days of reaction of harzburgite when CO2 was added to the headspace, with no detectable production of H2 or CH4 above background during further heating of the harzburgite or in experiments with other mineral reactants. Consequently, our results indicate that production of H2 and CH4 during low-temperature alteration of ultramafic rocks may be much more limited than some recent experimental studies have suggested. We also found no evidence to support a recent report suggesting that spinels in ultramafic rocks may stimulate H2 production. While secondary silicates were observed to precipitate during the experiments, formation of these deposits was dominated by Si released by dissolution of the glass bottles, and reaction of the primary silicate minerals appeared to be very limited. While use of glass bottles and rubber stoppers has become commonplace in experiments intended to study processes that occur during serpentinization of ultramafic rocks at low temperatures, the high levels of H2, CH4, and SiO2 released during heating indicate that these reactor materials are unsuitable for this purpose. Serpentinization-Hydrogen generation-Abiotic methane synthesis. Astrobiology 16, 389-406.

Variable (Tg, Ts) Measurements of Alkane Dissociative Sticking Coefficients

NASA Astrophysics Data System (ADS)

Valadez, Leticia; Dewitt, Kristy; Abbott, Heather; Kolasinski, Kurt; Harrision, Ian

2006-03-01

Dissociative sticking coefficients S(Tg, Ts) for CH4 and C2H6 on Pt(111) have been measured as a function of gas temperature (Tg) and surface temperature (Ts) using an effusive molecular beam. Microcanonical unimolecular rate theory (MURT) was employed to extract transition state characteristics [e.g., E0(CH4) = 52.5±3.5 kJ/mol-1 and E0(C2H6) = 26.5±3 kJ/mol-1]. MURT allows our S(Tg, Ts) values to be directly compared to other supersonic molecular beam and thermal equilibrium sticking measurements. The S(Tg, Ts) depend strongly on Ts, however, only for CH4 is a strong Tg dependence observed. The fairly weak Tg dependence for C2H6 suggests that vibrational mode specific behavior and/or molecular rotations play stronger roles in the dissociative chemisorption of C2H6 than they do for CH4. Interestingly, thermal S(Tg=Ts) predictions based on MURT modeling of our CH4/Pt(111) data are three orders of magnitude higher than recent thermal equilibrium measurements on supported Pt nanocrystallite catalysts [J. M. Wei, E. Iglesia, J. Phys. Chem. B 108, 4094 (2004)].

Raman and X-Ray Investigation of High-Temperature Methane in the Diamond Anvil Cell

NASA Astrophysics Data System (ADS)

Spaulding, D.; Weck, G.; Loubeyre, P.; Mezouar, M.

2016-12-01

The chemistry and equations of state of simple molecular systems are of extreme importance to planetary astrophysics and for accurate characterization of reaction products and pathways at high pressures and temperatures. Simple molecules such as H2O, CO2 and CH4 are model systems for understanding the effects of pressure on chemical bonding. Here we present recent work to conduct fine-scale studies of the vibrational, chemical and structural properties of CH4 at pressures and temperatures up to 12 GPa and 1000K, with particular attention to behavior in the vicinity of the melting curve. We present results from resistive and laser-heating experiments, coupled with Raman spectroscopy. In addition, high P/T synchrotron powder x-ray diffraction provides tight constraints on melting and solid structure. Our results favor a somewhat higher melting curve and lower dissociative stability limit for the CH4 molecule than other recent work.

Trimethylamine stimulated and dissolved organic matter inhibited methane production in sediment from the Poyang Lake, China.

PubMed

Wang, Jiajia; Liu, Chunying; Gong, Xiaofeng; Liu, Yuanmu; Chen, Chunli

2016-10-01

Methane (CH4) emitted from wetlands contributes significantly to the greenhouse effect. The Poyang Lake, the largest freshwater lake in China, is fed by five rivers and connects to the Yangtze River. The area of the lake fluctuates dramatically between drawdown and flood periods with large areas of wetlands. In order to understand the CH4 production capacity and factors that influence CH4 production in the wetland, a static closed chamber combined with a gas chromatograph technique was used to investigate the influence of substrates and electron acceptors on methanogenesis. The results showed that CH4 production capacity of sediments from the Poyang Lake was [Formula: see text] and it was stimulated by trimethylamine (TMA) to a great extent. Incubation temperature played a vital role on CH4 production in sediments and the optimum temperature for methanogenesis was 35°C. Minimum CH4 production capacity occurred with the addition of FeCl3, and the inhibitory effects of electron acceptors decreased in the sequence: FeCl3 > MnO2 > DOM > Fe2O3. In this study, DOM was demonstrated as one of the inhibitors to methanogenesis and TMA was the main substrate of methanogens in the sediments of the Poyang Lake whose pH value is 7.83.

The H2/CH4 ratio during serpentinization cannot reliably identify biological signatures

NASA Astrophysics Data System (ADS)

Huang, Ruifang; Sun, Weidong; Liu, Jinzhong; Ding, Xing; Peng, Shaobang; Zhan, Wenhuan

2016-09-01

Serpentinization potentially contributes to the origin and evolution of life during early history of the Earth. Serpentinization produces molecular hydrogen (H2) that can be utilized by microorganisms to gain metabolic energy. Methane can be formed through reactions between molecular hydrogen and oxidized carbon (e.g., carbon dioxide) or through biotic processes. A simple criterion, the H2/CH4 ratio, has been proposed to differentiate abiotic from biotic methane, with values approximately larger than 40 for abiotic methane and values of <40 for biotic methane. The definition of the criterion was based on two serpentinization experiments at 200 °C and 0.3 kbar. However, it is not clear whether the criterion is applicable at a wider range of temperatures. In this study, we performed sixteen experiments at 311-500 °C and 3.0 kbar using natural ground peridotite. Our results demonstrate that the H2/CH4 ratios strongly depend on temperature. At 311 °C and 3.0 kbar, the H2/CH4 ratios ranged from 58 to 2,120, much greater than the critical value of 40. By contrast, at 400-500 °C, the H2/CH4 ratios were much lower, ranging from 0.1 to 8.2. The results of this study suggest that the H2/CH4 ratios cannot reliably discriminate abiotic from biotic methane.

The H2/CH4 ratio during serpentinization cannot reliably identify biological signatures.

PubMed

Huang, Ruifang; Sun, Weidong; Liu, Jinzhong; Ding, Xing; Peng, Shaobang; Zhan, Wenhuan

2016-09-26

Serpentinization potentially contributes to the origin and evolution of life during early history of the Earth. Serpentinization produces molecular hydrogen (H 2 ) that can be utilized by microorganisms to gain metabolic energy. Methane can be formed through reactions between molecular hydrogen and oxidized carbon (e.g., carbon dioxide) or through biotic processes. A simple criterion, the H 2 /CH 4 ratio, has been proposed to differentiate abiotic from biotic methane, with values approximately larger than 40 for abiotic methane and values of <40 for biotic methane. The definition of the criterion was based on two serpentinization experiments at 200 °C and 0.3 kbar. However, it is not clear whether the criterion is applicable at a wider range of temperatures. In this study, we performed sixteen experiments at 311-500 °C and 3.0 kbar using natural ground peridotite. Our results demonstrate that the H 2 /CH 4 ratios strongly depend on temperature. At 311 °C and 3.0 kbar, the H 2 /CH 4 ratios ranged from 58 to 2,120, much greater than the critical value of 40. By contrast, at 400-500 °C, the H 2 /CH 4 ratios were much lower, ranging from 0.1 to 8.2. The results of this study suggest that the H 2 /CH 4 ratios cannot reliably discriminate abiotic from biotic methane.

Density functional theory study of acetaldehyde hydrodeoxygenation on MoO3

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

Mei, Donghai; Karim, Ayman M.; Wang, Yong

2011-04-06

Periodic spin-polarized density functional theory calculations were performed to investigate acetaldehyde (CH3CHO) hydrodeoxygenation on the reduced molybdenum trioxide (MoO3) surface. The perfect O-terminated α-MoO3(010) surface is reduced to generate an oxygen defect site in the presence of H2. H2 dissociatively adsorbs at the surface oxygen sites forming two surface hydroxyls, which can recombine into a water molecule weakly bound at the Mo site. A terminal oxygen (Ot) defect site thus forms after water desorption. CH3CHO adsorbs at the O-deficient Mo site via either the sole O-Mo bond or the O-Mo and the C-O double bonds. The possible reaction pathways ofmore » the adsorbed CH3CHO with these two configurations were thoroughly examined using the dimer searching method. Our results show that the ideal deoxygenation of CH3CHO leading to ethylene (C2H4) on the reduced MoO3(010) surface is feasible. The adsorbed CH3CHO first dehydrogenate into CH2CHO by reacting with a neighboring terminal Ot. The hydroxyl (OtH) then hydrogenates CH2CHO into CH2CH2O to complete the hydrogen transfer cycle with an activation barrier of 1.39 eV. The direct hydrogen transfer from CH3CHO to CH2CH2O is unlikely due to the high barrier of 2.00 eV. The produced CH2CH2O readily decomposes into C2H4 that directly releases to the gas phase, and regenerates the Ot atom on the Mo site. As a result, the reduced MoO3(010) surface is reoxidized to the perfect MoO3(010) surface after CH3CHO deoxygenation. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.« less

Spin and orbital magnetic moments of Fe and Co in Co/Fe and Fe/Co multilayers on Si from L2,3 edge X-ray Magnetic Circular Dichroism Spectroscopy

NASA Astrophysics Data System (ADS)

Vemuru, Krishnamurthy; Rosenberg, Richard; Mankey, Gary

Nanostructured FeCo thin films are interesting for magnetic recording applications due to their high saturation magnetization, high Curie temperature and low magnetocrystalline anisotropy. It is desirable to know how the magnetism is modified by the nanostructrure. We report Fe L 2 , 3 edge and Co L2 , 3 edge x-ray magnetic circular dichroism (XMCD) investigations of element specific spin and orbital magnetism of Fe and Co in two multilayer samples: (S1) Si/SiO2/[Co 0.8 nm/Fe 1.6 nm]x32/W (2nm) and (S2) Si/SiO2/[Co 1.6 nm/Fe 0.8 nm]x32/W (2nm) thin films at room temperature. Sum rule analysis of XMCD at Fe L2 , 3 edge in sample S1 shows that the orbital moment of Fe is strongly enhanced and the spin moment is strongly reduced as compared to the values found in bulk Fe. Details of sum rule analysis will be presented to compare and contrast spin magnetic moments and orbital magnetic moments of Fe and Co in the two multilayer samples. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.

Warming Early Mars With CH4

NASA Astrophysics Data System (ADS)

Justh, H. L.; Kasting, J. F.

2002-12-01

The nature of the ancient climate of Mars remains one of the fundamental unresolved problems in martian research. While the present environment is hostile to life, images from the Mariner, Viking and Mars Global Surveyor missions, have shown geologic features on the martian surface that seem to indicate an earlier period of hydrologic activity. The fact that ancient valley networks and degraded craters have been seen on the martian surface indicates that the early martian climate may have been more Earth-like, with a warmer surface temperature. The presence of liquid water would require a greenhouse effect much larger than needed at present, as the solar constant, S0, was 25% lower 3.8 billion years ago when the channels are thought to have formed (1,2). Previous calculations have shown that gaseous CO2 and H2O alone could not have warmed the martian surface to the temperature needed to account for the presence of liquid water (3). It has been hypothesized that a CO2-H2O atmosphere could keep early Mars warm if it was filled with CO2 ice clouds in the upper martian troposphere (4). Obtaining mean martian surface temperatures above 273 K would require nearly 100% cloud cover, a condition that is unrealistic for condensation clouds on early Mars. Any reduction in cloud cover makes it difficult to achieve warm martian surface temperatures except at high pressures and CO2 clouds could cool the martian surface if they were low and optically thick (5). CO2 and CH4 have been suggested as important greenhouse gases on the early Earth. Our research focuses on the effects of increased concentrations of atmospheric greenhouse gases on the surface temperature of early Mars, with emphasis on the reduced greenhouse gas, CH4. To investigate the possible warming effect of CH4, we modified a one-dimensional, radiative-convective climate model used in previous studies of the early martian climate (5). New cloud-free temperature profiles for various surface pressures and CH4 mixing ratios will be presented. This use of climate modeling is important since it is the fundamental way that the magnitude of possible geochemical and biological CH4 sources can be related to predicted CH4 concentrations in the early martian atmosphere. References: 1) Gough, D. O. Solar Physics 74, 21-34 (1981). 2) Carr, M. H. Water on Mars (1996). 3) Kasting, J. F. Icarus 94, 1-13 (1991). 4) Forget, F., and Pierrehumbert R. T. Science 278, 1273-1276 (1997). 5) Mischna, M. A., Kasting J. F., Pavlov A., and Freedman R. Icarus 145, 546-554 (2000).

Selectivity for CO2 over CH4 on a functionalized periodic mesoporous phenylene-silica explained by transition state theory

NASA Astrophysics Data System (ADS)

Kunkel, Christian; Viñes, Francesc; Lourenço, Mirtha A. O.; Ferreira, Paula; Gomes, José R. B.; Illas, Francesc

2017-03-01

Efficient separation of CO2/CH4 is critical in biogas upgrading, requiring highly selective adsorbents. Based on the adsorption energies of -0.30 and -0.14 eV, previously calculated by dispersion corrected density functional theory for adsorption/desorption of CO2 and CH4 on the functionalized periodic mesoporous phenylene-silica material APTMS@Ph-PMO, respectively, transition state theory rates were derived and used to simulate the adsorption/desorption rates of these two gases on APTMS@Ph-PMO. The latter yielded an estimation of initial CO2/CH4 selectivity at various temperatures. At T = 298 K, selectivity of 32.2 agrees to an experimental value of 26.1, which validates the method used for evaluating CO2/CH4 adsorption selectivities.

High-performance planar green light-emitting diodes based on a PEDOT:PSS/CH3NH3PbBr3/ZnO sandwich structure

NASA Astrophysics Data System (ADS)

Shi, Zhi-Feng; Sun, Xu-Guang; Wu, Di; Xu, Ting-Ting; Zhuang, Shi-Wei; Tian, Yong-Tao; Li, Xin-Jian; Du, Guo-Tong

2016-05-01

Recently, perovskite-based light-emitting diodes based on organometal halide emitters have attracted much attention because of their excellent properties of high color purity, tunable emission wavelength and a low-temperature processing technique. As is well-known, organic light-emitting diodes have shown powerful capabilities in this field; however, the fabrication of these devices typically relies on high-temperature and high-vacuum processes, which increases the final cost of the product and renders them uneconomical for use in large-area displays. Organic/inorganic hybrid halide perovskites match with these material requirements, as it is possible to prepare such materials with high crystallinity through solution processing at low temperature. Herein, we demonstrated a high-brightness green light-emitting diode based on PEDOT:PSS/CH3NH3PbBr3/ZnO sandwich structures by a spin-coating method combined with a sputtering system. Under forward bias, a dominant emission peak at ~530 nm with a low full width of half-maximum (FWHM) of 30 nm can be achieved at room temperature. Owing to the high surface coverage of the CH3NH3PbBr3 layer and a device design based on carrier injection and a confinement configuration, the proposed diode exhibits good electroluminescence performance, with an external quantum efficiency of 0.0645%. More importantly, we investigated the working stability of the studied diode under continuous operation to verify the sensitivity of the electroluminescence performance to ambient atmosphere and to assess the suitability of the diode for practical applications. Moreover, the underlying reasons for the undesirable emission decay are tentatively discussed. This demonstration of an effective green electroluminescence based on CH3NH3PbBr3 provides valuable information for the design and development of perovskites as efficient emitters, thus facilitating their use in existing applications and suggesting new potential applications.

Underlying Ecosystem Methane Emissions Exceed Cattle-Derived Methane from Subtropical Lowland Pastures.

NASA Astrophysics Data System (ADS)

Chamberlain, S. D.; Sparks, J. P.

2014-12-01

Grazing cattle are a major methane (CH4) source from pasture ecosystems, however the underlying landscape is a potentially significant CH4 source that has received far less attention. Ecosystem surface emissions of CH4 are poorly quantified, vary widely across time and space, and are easily underestimated if emission hotspots or episodic fluxes are overlooked. We used static chambers, eddy covariance, and mobile cavity-ringdown spectrometry surveys to quantify spatially and temporally variable CH4 emissions from subtropical lowland pastures. We conclude emissions from soil and standing water are the dominant CH4 source, and cattle were responsible for only 13% of annual CH4emissions. The ecosystem emit 33.8 ± 2.2 g CH4 m-2 yr-1, however surface CH4 emissions were highly variable in both time and space. Seasonal flooding of pastures and low-lying landforms (canals, ditches, wetlands) drove high magnitude CH4 emissions. We observed large CH4 emissions from wetlands and, to a lesser extent, the entire landscape during the wet season. In contrast, during the dry season there was no appreciable CH4 accumulation in pastures when cattle were not present, and canals, which comprise 1.7% of the total land area, were responsible 97.7 % of dry season emissions. Ecosystem CH4 fluxes, measured by eddy covariance, varied seasonally and positively correlated to soil and air temperature, topsoil water content, and water table depth. Our work is the first to use mobile spectrometers to map biogenic CH4 emissions at the landscape scale, and demonstrates that soils and water are a strong pasture CH4 source that must be considered in addition to cattle emissions.

Potassium doped methylammonium lead iodide (MAPbI3) thin films as a potential absorber for perovskite solar cells; structural, morphological, electronic and optoelectric properties

NASA Astrophysics Data System (ADS)

Muzammal uz Zaman, Muhammad; Imran, Muhammad; Saleem, Abida; Kamboh, Afzal Hussain; Arshad, Muhammad; Khan, Nawazish Ali; Akhter, Parvez

2017-10-01

In this article, we have demonstrated the doping of K in the light absorbing CH3NH3PbI3 perovskite i.e. (M = CH3, A = NH3; x = 0-1). One of the major merits of methylammonium lead iodide (CH3NH3PbI3) perovskites is that they act as efficient absorbing material of light in photovoltaic cell imparting long carrier lifetime and optimum band gap. The structural, morphological, electronic and optoelectric properties of potassium (K) doped light absorber methylammonium lead iodide (CH3NH3PbI3) perovskites are reported here i.e. Kx(MA)1-xPbI3 (M = CH3, A =NH3; x = 0-1). The thin films of perovskites (x = 0-1) were deposited by spin coating on cleaned FTO substrates and characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), current-voltage (IV), X-ray photoelectron spectroscopy (XPS) and Diffused reflectance spectroscopy (DRS) analysis. The organic constituents i.e. MA = CH3NH3, in perovskites solar cells induce instability even at the room temperature. To overcome such instabilities we have replaced the organic constituents by K because both of them have electropositive nature. Potassium successfully replaces the CH3NH3. Initially, this compound grows in a tetragonal crystal structure, however, beyond 30% doping of potassium orthorhombic distortions are induced in the parent tetragonal unit cell. Such phase transformation is microscopically visible in the electron micrographs of doped samples; cubic grains for MAPbI3 begin to transform into strip like structures in K-doped samples. The resistance of the samples is decreased for partial K-doping, which we suggested to be arising due to the electropositive nature of K. It is observed that the binding energy difference between Pb4f and I3d core levels are very similar in all the investigated systems and show formal oxidation states. Also, the partially doped samples showed increased absorption and bandgaps around 1.5 eV which is an optimum value for solar absorption.

Oxidation of ethane to ethanol by N2O in a metal-organic framework with coordinatively unsaturated iron(II) sites.

PubMed

Xiao, Dianne J; Bloch, Eric D; Mason, Jarad A; Queen, Wendy L; Hudson, Matthew R; Planas, Nora; Borycz, Joshua; Dzubak, Allison L; Verma, Pragya; Lee, Kyuho; Bonino, Francesca; Crocellà, Valentina; Yano, Junko; Bordiga, Silvia; Truhlar, Donald G; Gagliardi, Laura; Brown, Craig M; Long, Jeffrey R

2014-07-01

Enzymatic haem and non-haem high-valent iron-oxo species are known to activate strong C-H bonds, yet duplicating this reactivity in a synthetic system remains a formidable challenge. Although instability of the terminal iron-oxo moiety is perhaps the foremost obstacle, steric and electronic factors also limit the activity of previously reported mononuclear iron(IV)-oxo compounds. In particular, although nature's non-haem iron(IV)-oxo compounds possess high-spin S = 2 ground states, this electronic configuration has proved difficult to achieve in a molecular species. These challenges may be mitigated within metal-organic frameworks that feature site-isolated iron centres in a constrained, weak-field ligand environment. Here, we show that the metal-organic framework Fe2(dobdc) (dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate) and its magnesium-diluted analogue, Fe0.1Mg1.9(dobdc), are able to activate the C-H bonds of ethane and convert it into ethanol and acetaldehyde using nitrous oxide as the terminal oxidant. Electronic structure calculations indicate that the active oxidant is likely to be a high-spin S = 2 iron(IV)-oxo species.

A Pilot Study of Ion - Molecule Reactions at Temperatures Relevant to the Atmosphere of Titan.

PubMed

Zymak, Illia; Žabka, Ján; Polášek, Miroslav; Španěl, Patrik; Smith, David

2016-11-01

Reliable theoretical models of the chemical kinetics of the ionosphere of Saturn's moon, Titan, is highly dependent on the precision of the rates of the reactions of ambient ions with hydrocarbon molecules at relevant temperatures. A Variable Temperature Selected Ions Flow Tube technique, which has been developed primarily to study these reactions at temperatures within the range of 200-330 K, is briefly described. The flow tube temperature regulation system and the thermalisation of ions are also discussed. Preliminary studies of two reactions have been carried out to check the reliability and efficacy of kinetics measurements: (i) Rate constants of the reaction of CH 3 + ions with molecular oxygen were measured at different temperatures, which indicate values in agreement with previous ion cyclotron resonance measurements ostensibly made at 300 K. (ii) Formation of CH 3 + ions in the reaction of N 2 + ions with CH 4 molecules were studied at temperatures within the range 240-310 K which showed a small but statistically significant decrease of the ratio of product CH 3 + ions to reactant N 2 + ions with reaction temperature.

Two solvent and temperature dependent copper(II) compounds formed by a flexible ligand: syntheses, structures and SC-SC transformation.

PubMed

Sun, Haixia; Xie, Wenli; Lv, Shenghong; Xu, Yan; Wu, Yong; Zhou, Yaoming; Ma, Zhenmao; Fang, Min; Liu, Hong-Ke

2012-07-07

A nonporous neutral framework [CuCl(2)(m-bttmb)(2)](n) (1) was changed into a porous ionic {[Cu(m-bttmb)(2)(H(2)O)Cl]Cl(CH(3)CN)(0.5)(H(2)O)(2.75)}(n) (2) by simply increasing the amount of CH(3)CN in the mixed solvent (CH(3)CN and H(2)O) or temperature in the reactions of CuCl(2)·2H(2)O with 1,3-bis(triazol-1-ylmethyl)-2,4,6-trimethylbenzene (m-bttmb). 1 undergoes transformation into 2 when treated with CH(3)CN. Both 1 and 2 have 2D 4-connected (4,4) network architectures but in different packing arrangements. These compounds have been characterized by single-crystal X-ray diffraction analysis, elemental analysis, IR spectra and thermogravimetric analysis. This work may provide a way to control the formation of neutral or ionic frameworks, as well as porosities by adjusting the polarity and components of the solvents.

Discovery of room-temperature spin-glass behaviors in two-dimensional oriented attached single crystals

NASA Astrophysics Data System (ADS)

Ma, Ji; Chen, Kezheng

2016-05-01

In this study, room-temperature spin-glass behaviors were observed in flake-like oriented attached hematite (α-Fe2O3) and iron phosphate hydroxide hydrate (Fe5(PO4)4(OH)3·2H2O) single crystals. Remarkably, their coercivity (HC) values were found to be almost invariable at various given temperatures from 5 to 300 K. The spin topographic map in these flakes was assumed as superparamagnetic (SPM) "islands" isolated by spin glass (SG)-like "bridges". A spin-glass model was then proposed to demonstrate the spin frustration within these "bridges", which were formed by the staggered atomic planes in the uneven surfaces belonging to different attached nanoparticles. Under the spatial limitation and coupling shield of these "bridges", the SPM "islands" were found to be collectively frozen to form a superspin glass (SSG) state below 80 K in weak applied magnetic fields; whereas, when strong magnetic fields were applied, the magnetic coupling of these "islands" would become superferromagnetic (SFM) through tunneling superexchange, so that, these SFM spins could antiferromagnetically couple with the SG-like "bridges" to yield pronounced exchange bias (EB) effect.

Aerobic Methane Oxidation in Alaskan Lakes Along a Latitudinal Transect

NASA Astrophysics Data System (ADS)

Martinez-Cruz, K. C.; Sepulveda-Jauregui, A.; Walter Anthony, K. M.; Anthony, P.; Thalasso, F.

2013-12-01

Karla Martinez-Cruz* **, Armando Sepulveda-Jauregui*, Katey M. Walter Anthony*, Peter Anthony*, and Frederic Thalasso**. * Water and Environmental Research Center, Institute of Northern Engineering, University of Alaska Fairbanks, Fairbanks, Alaska. ** Biotechnology and Bioengineering Department, Cinvestav, Mexico city, D. F., Mexico. Methane (CH4) is the third most important greenhouse gas in the atmosphere, after carbon dioxide and water vapor. Boreal lakes play an important role in the current global warming by contributing as much as 6% of global atmospheric CH4 sources annually. On the other hand, aerobic methane oxidation (methanotrophy) in lake water is a fundamental process in global methane cycling that reduces the amount of CH4 emissions to the atmosphere. Several environmental factors affect aerobic methane oxidation in the water column both directly and indirectly, including concentration of CH4 and O2, temperature and carbon budgets of lakes. We analyzed the potential of aerobic methane oxidation (PMO) rates in incubations of water collected from 30 Alaskan lakes along a north-south transect during winter and summer 2011. Our findings showed an effect of CH4 and O2 concentrations, temperature and yedoma thawing permafrost on PMO activity in the lake water. The highest PMO rates were observed in summer by lakes situated on thawing yedoma permafrost, most of them located in the interior of Alaska. We also estimated that 60-80% of all CH4 produced in Alaskan lakes could be taken up by methanotrophs in the lake water column, showing the significant influence of aerobic methane oxidation of boreal lakes to the global CH4 budget.

Seasonal and diel variations of ammonia and methane emissions from a naturally ventilated dairy building and the associated factors influencing emissions.

PubMed

Saha, C K; Ammon, C; Berg, W; Fiedler, M; Loebsin, C; Sanftleben, P; Brunsch, R; Amon, T

2014-01-15

Understanding seasonal and diel variations of ammonia (NH3) and methane (CH4) emissions from a naturally ventilated dairy (NVD) building may lead to develop successful control strategies for reducing emissions throughout the year. The main objective of this study was to quantify seasonal and diel variations of NH3 and CH4 emissions together with associated factors influencing emissions. Measurements were carried out with identical experimental set-up to cover three winter, spring and summer seasons, and two autumn seasons in the years 2010, 2011, and 2012. The data from 2010 and 2011 were used for developing emission prediction models and the data from 2012 were used for model validation. The results showed that NH3 emission varied seasonally following outside temperature whereas CH4 emission did not show clear seasonal trend. Diel variation of CH4 emission was less pronounced than NH3. The average NH3 and CH4 emissions between 6a.m. and 6p.m. were 66% and 33% higher than the average NH3 and CH4 emissions between 6p.m. and 6a.m., respectively for all seasons. The significant relationships (P<0.0001) between NH3 and influencing factors were found including outside temperature, humidity, wind speed and direction, hour of the day and day of the year. The significant effect (P<0.0001) of climate factors, hours of the day and days of the year on CH4 emission might be directly related to activities of the cows. © 2013.

[Short-term effects of fire disturbance on greenhouse gases emission from Betula platyphylla-forested wetland in Xiaoxing'an Mountains, Northeast China].

PubMed

Mu, Chang-cheng; Zhang, Bo-wen; Han, Li-dong; Yu, Li-li; Gu, Han

2011-04-01

By the methods of static chamber and gas chromatography, this paper studied the effects of fire disturbance on the seasonal dynamics and source/sink functions of CH4, CO2 and N2O emissions from Betula platyphylla-forested wetland as well as their relations with environmental factors in Xiaoxing' an Mountains of China. In growth season, slight fire disturbance on the wetland induced an increase of air temperature and ground surface temperature by 1.8-3.9 degrees C and a decrease of water table by 6.3 cm; while heavy fire disturbance led to an increase of air temperature and 0-40 cm soil temperature by 1.4-3.8 degrees C and a decrease of water table by 33.9 cm. Under slight or no fire disturbance, the CH4 was absorbed by the wetland soil in spring but emitted in summer and autumn; under heavy fire disturbance, the CH4 was absorbed in spring and summer but emitted in autumn. The CO2 flux had a seasonal variation of summer > spring = autumn under no fire disturbance, but of summer > autumn > spring under fire disturbance; and the N2O flux varied in the order of spring > summer > autumn under no fire disturbance, but of autumn > spring > summer under slight fire disturbance, and of summer > spring = autumn under heavy fire disturbance. At unburned site, the CO2 flux was significantly positively correlated with air temperature and ground surface temperature; at slightly burned site, the CO2 flux had significant positive correlations with air temperature, 5-10 cm soil temperature, and water table; at heavily burned sites, there was a significant positive correlation between CO2 flux and 5-40 cm soil temperature. Fire disturbance made the CH4 emission increased by 169.5% at lightly burned site or turned into weak CH4 sink at heavily burned site, and made the CO2 and N2O emissions and the global warming potential (GWP) at burned sites decreased by 21.2% -34.7%, 65.6% -95.8%, and 22.9% -36.6% respectively, compared with those at unburned site. Therefore, fire disturbance could decrease the greenhouse gases emission from Betula platyphylla-forested wetland, and planned firing could be properly implemented in wetland management.

An Octanuclear Metallosupramolecular Cage Designed To Exhibit Spin-Crossover Behavior.

PubMed

Struch, Niklas; Bannwarth, Christoph; Ronson, Tanya K; Lorenz, Yvonne; Mienert, Bernd; Wagner, Norbert; Engeser, Marianne; Bill, Eckhard; Puttreddy, Rakesh; Rissanen, Kari; Beck, Johannes; Grimme, Stefan; Nitschke, Jonathan R; Lützen, Arne

2017-04-24

By employing the subcomponent self-assembly approach utilizing 5,10,15,20-tetrakis(4-aminophenyl)porphyrin or its zinc(II) complex, 1H-4-imidazolecarbaldehyde, and either zinc(II) or iron(II) salts, we were able to prepare O-symmetric cages having a confined volume of ca. 1300 Å 3 . The use of iron(II) salts yielded coordination cages in the high-spin state at room temperature, manifesting spin-crossover in solution at low temperatures, whereas corresponding zinc(II) salts led to the corresponding diamagnetic analogues. The new cages were characterized by synchrotron X-ray crystallography, high-resolution mass spectrometry, and NMR, Mössbauer, IR, and UV/Vis spectroscopy. The cage structures and UV/Vis spectra were independently confirmed by state-of-the-art DFT calculations. A remarkably high-spin-stabilizing effect through encapsulation of C 70 was observed. The spin-transition temperature T 1/2 is lowered by 20 K in the host-guest complex. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Influence of preadsorbed oxygen on activated chemisorption of methane on Pd(110)

NASA Astrophysics Data System (ADS)

Valden, M.; Pere, J.; Xiang, N.; Pessa, M.

1996-07-01

Dissociative chemisorption of methane on clean and oxygen modified Pd(110) has been studied by using molecular beam surface scattering. The absolute dissociation probability of CH 4 ( Stot) is found to increase exponentially with the incident normal energy ( En) of CH 4 and with surface temperature ( TS) on clean Pd(110). The kinetic isotope effect is also found; namely, Stot of CD 4 is 4 to 5 times smaller than Stot of CH 4 throughout the entire range of En studied. These results are consistent with a direct dissociation mechanism. Measurements on preadsorbed oxygen on Pd(110) show that Stot of CH 4 decreases linearly, as oxygen coverage is increased from 0 to 0.4 ML in good agreement with the first-order Langmuir kinetics when approximately two active sites are blocked by one oxygen atom. No influence of the oxygen induced surface reconstructions on the dissociative adsorption kinetics of CH 4 is observed.

Specific features of spin-variable properties of [Fe(acen)pic2]BPh4 · nH2O

NASA Astrophysics Data System (ADS)

Ivanova, T. A.; Ovchinnikov, I. V.; Gil'mutdinov, I. F.; Mingalieva, L. V.; Turanova, O. A.; Ivanova, G. I.

2016-02-01

The [Fe(acen)pic2]BPh4 · nH2O compound has been synthesized and studied in the temperature interval of 5-300 K by the methods of EPR and magnetic susceptibility. The existence of ferromagnetic interactions between Fe(III) complexes in this compound has been revealed, in contrast to unhydrated [Fe(acen)pic2]BPh4. The reduction in the integrated intensity of the magnetic resonance signal as the temperature decreases below 80 K has been explained by the transition of high-spin ions to the low-spin state. It has been shown that the phase transition temperature in the presence of intermolecular (ferromagnetic) interactions is lower than that in the case of noninteracting centers.

Spin crossover behaviour in Hofmann-like coordination polymer Fe(py)2[Pd(CN)4] with 57Fe Mössbauer spectra

NASA Astrophysics Data System (ADS)

Kitazawa, Takafumi; Kishida, Takanori; Kawasaki, Takeshi; Takahashi, Masashi

2017-11-01

We have prepared the 2D spin crossover complexes Fe(L)2Pd(CN)4 (L = py : 1a; py-D5 : 1b and py-15N : 1c). 1a has been characterised by 57Fe Mossbauer spectroscopic measurements, single crystal X-ray determination and SQUID measurements. The Mössbauer spectra for 1a indicate that the iron(II) spin states are in high spin states at 298 K and are in low spin states at 77 K. The crystal structures of 1a at 298 K and 90 K also show the high spin state and the low spin state respectively, associated with the Fe(II)-N distances. The spin transition temperature range of 1a is higher than that of Fe(py)2Ni(CN)4 since Pd(II) ions are larger and heavier than Ni(II) ions. SQUID data indicate isotope effects among 1a, 1b and 1c are observed in very small shifts of the transition temperatures probably due to larger and heavier Pd(II) ions. The delicate shifts would be associated with subtle balances between different vibrations around Fe(II) atoms and electronic factors.

Comparison of CH4 Emission and CO2 Exchange Between 2013 and 2014 in a Subarctic Peatland

NASA Astrophysics Data System (ADS)

Clarizia, P. E.; Verbeke, B. A.; McCalley, C. K.; Werner, S. L.; Malhotra, A.; Burke, S. A.; Crill, P. M.; Varner, R. K.

2014-12-01

One of the major concerns with climate change is the potential feedback from the emission of greenhouse gases, carbon dioxide (CO2) and methane (CH4), from high latitude thawing organic soils. With increasing temperatures in Arctic regions, thawing permafrost palsas transition to wetter sedge-dominated wetlands, which account for 20-39% of global atmospheric CH4 burden. This rapid change in habitat raises the following question: how do CO2 exchange rates and CH4 emissions change along a gradient of permafrost thaw and what is the interannual variability in these fluxes? To address this question, we measured CO2 exchange, CH4 flux, vegetative type and vascular green area (VGA) along a thaw gradient during July of 2013 and 2014 in Stordalen Mire, Sweden. Environmental variables showed that 2013 and 2014 were climatically different; higher photosynthetically active radiation (PAR) and measurements of water table level and temperature showed that 2014 was warmer and drier than 2013. Warmer conditions led to higher rates of respiration and gross primary productivity (GPP), with the largest increases observed in the palsa sites, likely due to an increase in mean temperature. Methane fluxes showed a less consistent response to climate differences between years, fluxes were higher in 2014 in the mostly inundated Eriophorum angustifolium dominated site and lower in the drier Sphagnum and Eriophorum vaginatum dominated sites. Results of this study highlight the need for accounting for interannual variability when predicting greenhouse gas emissions during permafrost thaw.

Beyond the Methanogenic Black-Box: Greenhouse Gas Fluxes (CO2, CH4, N2O) as Evidence for Wetlands as Dynamic Redox Systems

NASA Astrophysics Data System (ADS)

Mcnicol, G.; Knox, S. H.; Sturtevant, C. S.; Baldocchi, D. D.; Silver, W. L.

2015-12-01

Seminal wetland research in the 1990s demonstrated that annual methane (CH4) fluxes scaled positively with ecosystem production across distinctive wetlands globally. This relationship implies a model of flooded wetland ecosystems as 'methanogenic black-boxes'; poised at a low redox state, and tending to release a fixed fraction of incoming annual productivity as CH4. In contrast, recent studies have reported high ratios of carbon dioxide (CO2) to CH4 emissions, and are adding to a body of evidence suggesting wetlands can vary more widely in their redox state. To explore this apparent incongruence we used principles of redox thermodynamics and laboratory experiments to develop predictions of wetland greenhouse gas (GHG) fluxes under different redox regimes. We then used a field study to test the hypothesis that ecosystem seasonality in gross primary productivity (GPP) and temperature would drive changes in GHG emissions, mediated by a dynamic - as opposed to static - redox regime. We estimated wetland GHG emissions from an emergent marsh in the Sacramento Delta, CA from March 2014-2015. We measured CO2, CH4 and N2O emissions via diffusion and ebullition with manual sampling, and whole-ecosystem fluxes of CO2 and CH4 using eddy-covariance. Ebullition and diffusive CH4 fluxes were strongly seasonal, with minimum rates (0.86 and 0.35 mg C-CH­­4 m-2 yr-1, respectively) during winter, and maximum rates (1.3 and 1.8 g C-CH­­4 m-2 yr-1, respectively) during the summer growing season. In contrast, winter diffusive CO2 fluxes (494 g C-CO2 m-2 yr-1) and fall bubble CO2 concentrations (1.49%) were highest, despite being seasons of lower GPP, temperature, and CH4 flux. Further, diffusive and ebullition fluxes of N2O showed zero net flux only during spring and summer months, whereas the wetland was a significant source of N2O during winter (81.2 ± 24.4 mg N-N2O m-2 yr-1). These seasonal flux dynamics contradict a 'methanogenic black box' model of wetland redox, which predicts carbon limitation of, and concurrent maxima in, heterotrophic CO2 and CH4 emissions, and no significant N2O emissions. Rather these results suggest that wetlands can function as dynamic redox environments where GHG emission rate and composition varies predictably in time with seasonal changes in GPP and temperature.

Highly Efficient Room Temperature Spin Injection Using Spin Filtering in MgO

NASA Astrophysics Data System (ADS)

Jiang, Xin

2007-03-01

Efficient electrical spin injection into GaAs/AlGaAs quantum well structures was demonstrated using CoFe/MgO tunnel spin injectors at room temperature. The spin polarization of the injected electron current was inferred from the circular polarization of electroluminescence from the quantum well. Polarization values as high as 57% at 100 K and 47% at 290 K were obtained in a perpendicular magnetic field of 5 Tesla. The interface between the tunnel spin injector and the GaAs interface remained stable even after thermal annealing at 400 ^oC. The temperature dependence of the electron-hole recombination time and the electron spin relaxation time in the quantum well was measured using time-resolved optical techniques. By taking into account of these properties of the quantum well, the intrinsic spin injection efficiency can be deduced. We conclude that the efficiency of spin injection from a CoFe/MgO spin injector is nearly independent of temperature and, moreover, is highly efficient with an efficiency of ˜ 70% for the temperature range studied (10 K to room temperature). Tunnel spin injectors are thus highly promising components of future semiconductor spintronic devices. Collaborators: Roger Wang^1, 3, Gian Salis^2, Robert Shelby^1, Roger Macfarlane^1, Seth Bank^3, Glenn Solomon^3, James Harris^3, Stuart S. P. Parkin^1 ^1 IBM Almaden Research Center, San Jose, CA 95120 ^2 IBM Zurich Research Laboratory, S"aumerstrasse 4, 8803 R"uschlikon, Switzerland ^3 Solid States and Photonics Laboratory, Stanford University, Stanford, CA 94305

Evidence for a spinon Fermi surface in a triangular-lattice quantum-spin-liquid candidate

DOE PAGES

Shen, Yao; Li, Yao-Dong; Wo, Hongliang; ...

2016-12-05

A quantum spin liquid is an exotic quantum state of matter in which spins are highly entangled and remain disordered down to zero temperature. Such a state of matter is potentially relevant to high-temperature superconductivity and quantum-information applications, and experimental identification of a quantum spin liquid state is of fundamental importance for our understanding of quantum matter. Theoretical studies have proposed various quantum-spin-liquid ground states, most of which are characterized by exotic spin excitations with fractional quantum numbers (termed ‘spinons’). In this paper, we report neutron scattering measurements of the triangular-lattice antiferromagnet YbMgGaO 4 that reveal broad spin excitations coveringmore » a wide region of the Brillouin zone. The observed diffusive spin excitation persists at the lowest measured energy and shows a clear upper excitation edge, consistent with the particle–hole excitation of a spinon Fermi surface. Finally, our results therefore point to the existence of a quantum spin liquid state with a spinon Fermi surface in YbMgGaO 4, which has a perfect spin-1/2 triangular lattice as in the original proposal of quantum spin liquids.« less

Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br

NASA Technical Reports Server (NTRS)

Hsu, K.-J.; Demore, W. B.

1994-01-01

Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br have been measured by a relative rate technique in which the reaction rate of each compound was compared to that of HFC-152a (CH3CHF2) and (for CH2Cl2) HFC-161 (CH3CH2F). Using absolute rate constants for HFC-152a and HFC-161, which we have determined relative to those for CH4, CH3CCl3, and C2H6, temperature dependent rate constants of both compounds were derived. The derived rate constant for CH3Br is in good agreement with recent absolute measurements. However, for the chloromethanes all the rate constants are lower at atmospheric temperatures than previously reported, especially for CH2Cl2 where the present rate constant is about a factor of 1.6 below the JPL 92-20 value. The new rate constant appears to resolve a discrepancy between the observed atmospheric concentrations and those calculated from the previous rate constant and estimated release rates.

3D Spin-Liquid State in an Organic Hyperkagome Lattice of Mott Dimers

NASA Astrophysics Data System (ADS)

Mizuno, Asato; Shuku, Yoshiaki; Matsushita, Michio M.; Tsuchiizu, Masahisa; Hara, Yuuki; Wada, Nobuo; Shimizu, Yasuhiro; Awaga, Kunio

2017-08-01

We report the first 3D spin liquid state of isotropic organic spins. Structural analysis, and magnetic and heat-capacity measurements were carried out for a chiral organic radical salt, (TBA) 1.5[(-)-NDI -Δ ] (TBA denotes tetrabutylammonium and NDI denotes naphthalene diimide), in which (-)-NDI -Δ forms a K4 structure due to its triangular molecular structure and an intermolecular π -π overlap between the NDI moieties. This lattice was identical to the hyperkagome lattice of S =1 /2 Mott dimers, and should exhibit 3D spin frustration. In fact, even though the high-temperature magnetic susceptibility followed the Curie-Weiss law with a negative Weiss constant of θ =-15 K , the low-temperature magnetic measurements revealed no long-range magnetic ordering down to 70 mK, and suggested the presence of a spin liquid state with a large residual paramagnetism χ0 of 8.5 ×10-6 emu g-1 at the absolute zero temperature. This was supported by the N 14 NMR measurements down to 0.38 K. Further, the low-temperature heat capacities cp down to 68 mK clearly indicated the presence of cp for the spin liquid state, which can be fitted to the power law of T0.62 in the wide temperature range 0.07-4.5 K.

Interannual, seasonal, and retrospective analysis of the methane and carbon dioxide budgets of a temperate peatland

NASA Astrophysics Data System (ADS)

Olson, D. M.; Griffis, T. J.; Noormets, A.; Kolka, R.; Chen, J.

2013-03-01

Three years (2009-2011) of near-continuous methane (CH4) and carbon dioxide (CO2) fluxes were measured with the eddy covariance (EC) technique at a temperate peatland located within the Marcell Experimental Forest, in northern Minnesota, USA. The peatland was a net source of CH4 and a net sink of CO2 in each year with annual carbon budgets of -26.8 (±18.7), -15.5 (±14.8), and -14.6 (±21.5) g C m-2 yr-1 for 2009-2011, respectively. Differences in the seasonal hydrometeorological conditions among the three study years were most pronounced during 2011, which was considerably warmer (+1.3°C) and wetter (+40 mm) than the 30 year average. The annual CH4 budget was +11.8 (±3.1), +12.2 (±3.0), and +24.9 (±5.6) g C m-2 yr-1 for the respective years and accounted for 23%-39% of the annual carbon budget. The larger CH4 emission in 2011 is attributed to significant warming of the peat column coupled with a high water table position throughout the entire growing season. Historical (1991-2011) CH4 emissions were estimated based on long-term hydrometeorological records and functional relationships derived from our 3 year field study. The predicted historical annual CH4 budget ranged from +7.8 to +15.2 (±2.7) g CH4-C m-2 yr-1. Recent (2007-2011) increases in temperature, precipitation, and rising water table at this site suggest that CH4 emissions have been increasing, but were generally greater from 1991 to 1999 when average soil temperature and precipitation were higher than in recent years. The global warming potential (considering CO2 and CH4) for this peatland was calculated based on a 100 year time horizon. In all three study years, the peatland had a net positive radiative forcing on climate and was greatest (+187 g C m-2) in 2011. The interannual variability in CH4 exchange at this site suggests high sensitivity to variations in hydrometeorological conditions.

Magnetic Ordering in Gold Nanoclusters

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

Agrachev, Mikhail; Antonello, Sabrina; Dainese, Tiziano

Here, several research groups have observed magnetism in monolayer-protected gold-cluster samples, but the results were often contradictory and thus a clear understanding of this phenomenon is still missing. We used Au 25(SCH 2CH 2Ph) 18 0, which is a paramagnetic cluster that can be prepared with atomic precision and whose structure is known precisely. Previous magnetometry studies only detected paramagnetism. We used samples representing a range of crystallographic orders and studied their magnetic behaviors by electron paramagnetic resonance (EPR). As a film, Au 25(SCH 2CH 2Ph) 18 0 displays paramagnetic behavior but, at low temperature, ferromagnetic interactions are detectable. Onemore » or few single crystals undergo physical reorientation with the applied field and display ferromagnetism, as detected through hysteresis experiments. A large collection of microcrystals is magnetic even at room temperature and shows distinct paramagnetic, superparamagnetic, and ferromagnetic behaviors. Simulation of the EPR spectra shows that both spin-orbit coupling and crystal distortion are important to determine the observed magnetic behaviors. DFT calculations carried out on single cluster and periodic models predict values of spin6orbit coupling and crystal6splitting effects in agreement with the EPR derived quantities. Magnetism in gold nanoclusters is thus demonstrated to be the outcome of a very delicate balance of factors. To obtain reproducible results, the samples must be (i) controlled for composition and thus be monodispersed with atomic precision, (ii) of known charge state, and (iii) well defined also in terms of crystallinity and experimental conditions. This study highlights the efficacy of EPR spectroscopy to provide a molecular understanding of these phenomena« less

Magnetic Ordering in Gold Nanoclusters

DOE PAGES

Agrachev, Mikhail; Antonello, Sabrina; Dainese, Tiziano; ...

2017-06-12

Here, several research groups have observed magnetism in monolayer-protected gold-cluster samples, but the results were often contradictory and thus a clear understanding of this phenomenon is still missing. We used Au 25(SCH 2CH 2Ph) 18 0, which is a paramagnetic cluster that can be prepared with atomic precision and whose structure is known precisely. Previous magnetometry studies only detected paramagnetism. We used samples representing a range of crystallographic orders and studied their magnetic behaviors by electron paramagnetic resonance (EPR). As a film, Au 25(SCH 2CH 2Ph) 18 0 displays paramagnetic behavior but, at low temperature, ferromagnetic interactions are detectable. Onemore » or few single crystals undergo physical reorientation with the applied field and display ferromagnetism, as detected through hysteresis experiments. A large collection of microcrystals is magnetic even at room temperature and shows distinct paramagnetic, superparamagnetic, and ferromagnetic behaviors. Simulation of the EPR spectra shows that both spin-orbit coupling and crystal distortion are important to determine the observed magnetic behaviors. DFT calculations carried out on single cluster and periodic models predict values of spin6orbit coupling and crystal6splitting effects in agreement with the EPR derived quantities. Magnetism in gold nanoclusters is thus demonstrated to be the outcome of a very delicate balance of factors. To obtain reproducible results, the samples must be (i) controlled for composition and thus be monodispersed with atomic precision, (ii) of known charge state, and (iii) well defined also in terms of crystallinity and experimental conditions. This study highlights the efficacy of EPR spectroscopy to provide a molecular understanding of these phenomena« less

Estimating wetland methane emissions from the northern high latitudes from 1990 to 2009 using artificial neural networks

NASA Astrophysics Data System (ADS)

Zhu, Xudong; Zhuang, Qianlai; Qin, Zhangcai; Glagolev, Mikhail; Song, Lulu

2013-04-01

Methane (CH4) emissions from wetland ecosystems in nothern high latitudes provide a potentially positive feedback to global climate warming. Large uncertainties still remain in estimating wetland CH4 emisions at regional scales. Here we develop a statistical model of CH4 emissions using an artificial neural network (ANN) approach and field observations of CH4 fluxes. Six explanatory variables (air temperature, precipitation, water table depth, soil organic carbon, soil total porosity, and soil pH) are included in the development of ANN models, which are then extrapolated to the northern high latitudes to estimate monthly CH4 emissions from 1990 to 2009. We estimate that the annual wetland CH4 source from the northern high latitudes (north of 45°N) is 48.7 Tg CH4 yr-1 (1 Tg = 1012 g) with an uncertainty range of 44.0 53.7 Tg CH4 yr-1. The estimated wetland CH4 emissions show a large spatial variability over the northern high latitudes, due to variations in hydrology, climate, and soil conditions. Significant interannual and seasonal variations of wetland CH4 emissions exist in the past 2 decades, and the emissions in this period are most sensitive to variations in water table position. To improve future assessment of wetland CH4 dynamics in this region, research priorities should be directed to better characterizing hydrological processes of wetlands, including temporal dynamics of water table position and spatial dynamics of wetland areas.

Experimental investigation and computational modeling of hot filament diamond chemical vapor deposition

NASA Astrophysics Data System (ADS)

Zumbach, Volker; Schäfer, Jörg; Tobai, Jens; Ridder, Michael; Dreier, Thomas; Schaich, Thomas; Wolfrum, Jürgen; Ruf, Bernhard; Behrendt, Frank; Deutschman, Olaf; Warnatz, Jürgen

1997-10-01

A joint investigation has been undertaken of the gas-phase chemistry taking place in a hot-filament chemical vapor-deposition (HFCVD) process for diamond synthesis on silica surfaces by a detailed comparison of numerical modeling and experimental results. Molecular beam sampling using quadrupole mass spectroscopy and resonance-enhanced multiphoton ionization time of flight mass spectroscopy (REMPI-TOF-MS) has been used to determine absolute concentrations of stable hydrocarbons and radicals. Resulting species of a CH4/H2, a CH4/D2 (both 0.5%/99.5%) and a C2H2/H2 (0.25%/99.75%) feedgas mixture were investigated for varying filament and substrate temperatures. Spatially resolved temperature profiles at various substrate temperatures, obtained from coherent anti-Stokes Raman spectroscopy (CARS) of hydrogen, are used as input parameters for the numerical code to reproduce hydrogen atom, methyl radical, methane, acetylene, and ethylene concentration profiles in the boundary layer of the substrate. In addition, the concentration of vibrationally excited hydrogen is determined by CARS. Results reveal only qualitative agreement between measured data and simulations, concerning concentrations of stable species and radicals probed near the surface, on filament and substrate temperature dependence, respectively. Hydrogen and deuterium experiments show similar behaviour for all species. In the case of CH4 as feedgas the model describes measured concentration profiles of CH3, CH4, and C2H2 qualitatively well. Large differences between model and experiment occur for hydrogen atoms (factor of 2) and C2H4 (factor of 3). For acetylene as feedgas the model is not able to give any predictions because no conversion of C2H2 is seen in the model in contrast to the experiment.

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

Raston, Paul L., E-mail: paul.raston@adelaide.edu.au; Douberly, Gary E.; Jäger, Wolfgang

Methanol is one of the simplest molecules that undergo torsional oscillations, and so it has been extensively studied in the gas phase by various spectroscopic techniques. At 300 K, a large number of rotational, torsional, and vibrational energy levels is populated, and this makes for a rather complicated spectrum, which is still not fully understood. It is expected that in going from 300 K to 0.4 K (the temperature of helium nanodroplets) the population distribution of methanol will mainly collapse into two states; the J{sub K} = 0{sub 0} state for the A{sub 1} nuclear spin symmetry species (with I{submore » CH{sub 3}} = 3/2), and the J{sub K} = 1{sub −1} state for the E species (I{sub CH{sub 3}} = 1/2). This results in a simplified spectrum that consists of narrow a-type (ΔK = 0) lines and broader b- and c-type (ΔK = ±1) lines. We have recorded the rotovibrational spectrum of CH{sub 3}OH in the OH stretching, CH{sub 3} stretching and bending, CH{sub 3} rocking, and CO stretching regions, and have firmly assigned five bands (v{sub 1}, v{sub 2}, v{sub 3}, v{sub 7}, and v{sub 8}), and tentatively assigned five others (v{sub 9}, 2v{sub 4}, v{sub 4} + v{sub 10}, 2v{sub 10}, and v{sub 4} + v{sub 5}). To our knowledge, the transitions we have assigned within the v{sub 4} + v{sub 10}, 2v{sub 10}, and v{sub 4} + v{sub 5} bands have not yet been assigned in the gas phase, and we hope that considering the very small “matrix” shift in helium nanodroplets (<1 cm{sup −1} for most subband origins of CH{sub 3}OH), those made here can aid in their gas phase identification. Microwave-infrared double resonance spectroscopy was used to confirm the initially tentative a-type infrared assignments in the OH stretching (v{sub 1}) band of A{sub 1} species methanol, in addition to revealing “warm” b-type lines. From a rotovibrational analysis, the B rotational constant is found to be reduced quite significantly (56%) with respect to the gas phase, and the torsional tunneling splittings are relatively unaffected and are at most reduced by 16%. While most rovibrational peaks are Lorentzian shaped, and those which are significantly perturbed by vibrational coupling in the gas phase are additionally broadened, the narrowest ΔJ = +1 peaks are asymmetric, and a skew-type analysis suggests that the response time of the helium solvent upon excitation is of the order of 1 ns.« less

Low-temperature dynamic nuclear polarization at 9.4 T with a 30 mW microwave source.

PubMed

Thurber, Kent R; Yau, Wai-Ming; Tycko, Robert

2010-06-01

Dynamic nuclear polarization (DNP) can provide large signal enhancements in nuclear magnetic resonance (NMR) by transfer of polarization from electron spins to nuclear spins. We discuss several aspects of DNP experiments at 9.4 T (400 MHz resonant frequency for (1)H, 264 GHz for electron spins in organic radicals) in the 7-80K temperature range, using a 30 mW, frequency-tunable microwave source and a quasi-optical microwave bridge for polarization control and low-loss microwave transmission. In experiments on frozen glycerol/water doped with nitroxide radicals, DNP signal enhancements up to a factor of 80 are observed (relative to (1)H NMR signals with thermal equilibrium spin polarization). The largest sensitivity enhancements are observed with a new triradical dopant, DOTOPA-TEMPO. Field modulation with a 10 G root-mean-squared amplitude during DNP increases the nuclear spin polarizations by up to 135%. Dependencies of (1)H NMR signal amplitudes, nuclear spin relaxation times, and DNP build-up times on the dopant and its concentration, temperature, microwave power, and modulation frequency are reported and discussed. The benefits of low-temperature DNP can be dramatic: the (1)H spin polarization is increased approximately 1000-fold at 7 K with DNP, relative to thermal polarization at 80K. (c) 2010 Elsevier Inc. All rights reserved.

Messengers from the Early Solar System - Comets as Carriers of Cosmic Information

NASA Technical Reports Server (NTRS)

Mumma, Michael J.

2011-01-01

Viewed from a cosmic perspective, Earth is a dry planet yet its oceans are enriched in deuterium by a large factor relative to nebular hydrogen. Can comets have delivered Earth s water? The question of exogenous delivery of water and organics to Earth and other young planets is of critical importance for understanding the origin of Earth s water, and for assessing the possible existence of exo-planets similar to Earth. Strong gradients in temperature and chemistry in the proto-planetary disk, coupled with dynamical models, imply that comets from the Oort Cloud and Kuiper Disk reservoirs should have diverse composition. The primary volatiles in comets (ices native to the nucleus) provide the preferred metric, and taxonomies based on them are now beginning to emerge [1, 2, 3]. The measurement of cosmic parameters such as the nuclear spin temperatures for H2O, NH3, and CH4, and of enrichment factors for isotopologues (D/H in water and hydrogen cyanide, N-14/N-15 in CN and hydrogen cyanide) provide additional important tests for the origin of cometary material.

A cool-temperate young larch plantation as a net methane source - A 4-year continuous hyperbolic relaxed eddy accumulation and chamber measurements

NASA Astrophysics Data System (ADS)

Ueyama, Masahito; Yoshikawa, Kota; Takagi, Kentaro

2018-07-01

Upland forests are thought to be methane (CH4) sinks due to oxidation by methanotrophs in aerobic soils. However, CH4 budget for upland forests are not well quantified at the ecosystem scale, when possible CH4 sources, such as small wet areas, exists in the ecosystem. Here, we quantified CH4 fluxes in a cool-temperate larch plantation based on four-year continuous measurements using the hyperbolic relaxed eddy accumulation (HREA) method and dynamic closed chambers with a laser-based analyzer. After filling data gaps for half-hourly data using machine-learning-based regressions, we found that the forest acted as a net CH4 source at the canopy scale: 30 ± 11 mg CH4 m-2 yr-1 in 2014, 56 ± 8 mg CH4 m-2 yr-1 in 2015, 154 ± 5 mg CH4 m-2 yr-1 in 2016, and 132 ± 6 mg CH4 m-2 yr-1 in 2017. Hotspot emissions from the edge of the pond could strongly contribute to the canopy-scale emissions. The magnitude of the hotspot emissions was 10-100 times greater than the order of the canopy-scale and chamber-based CH4 fluxes at the dry soils. The high temperatures with wet conditions stimulated the hotspot emissions, and thus induced canopy-scale CH4 emissions in the summer. Understanding and modeling the dynamics of hotspot emissions are important for quantifying CH4 budgets of upland forests. Micrometeorological measurements at various forests are required for revisiting CH4 budget of upland forests.

Local spin dynamics at low temperature in the slowly relaxing molecular chain [Dy(hfac)3(NIT(C6H4OPh))]: A μ{sup +} spin relaxation study

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

Arosio, Paolo, E-mail: paolo.arosio@guest.unimi.it; Orsini, Francesco; Corti, Maurizio

2015-05-07

The spin dynamics of the molecular magnetic chain [Dy(hfac){sub 3}(NIT(C{sub 6}H{sub 4}OPh))] were investigated by means of the Muon Spin Relaxation (μ{sup +}SR) technique. This system consists of a magnetic lattice of alternating Dy(III) ions and radical spins, and exhibits single-chain-magnet behavior. The magnetic properties of [Dy(hfac){sub 3}(NIT(C{sub 6}H{sub 4}OPh))] have been studied by measuring the magnetization vs. temperature at different applied magnetic fields (H = 5, 3500, and 16500 Oe) and by performing μ{sup +}SR experiments vs. temperature in zero field and in a longitudinal applied magnetic field H = 3500 Oe. The muon asymmetry P(t) was fitted by the sum of three components, twomore » stretched-exponential decays with fast and intermediate relaxation times, and a third slow exponential decay. The temperature dependence of the spin dynamics has been determined by analyzing the muon longitudinal relaxation rate λ{sub interm}(T), associated with the intermediate relaxing component. The experimental λ{sub interm}(T) data were fitted with a corrected phenomenological Bloembergen-Purcell-Pound law by using a distribution of thermally activated correlation times, which average to τ = τ{sub 0} exp(Δ/k{sub B}T), corresponding to a distribution of energy barriers Δ. The correlation times can be associated with the spin freezing that occurs when the system condenses in the ground state.« less

Flow Reactor Studies with Nanosecond Pulsed Discharges at Atmospheric Pressure and Higher

DTIC Science & Technology

2013-10-01

Experiment and model analysis of low temperature C2H4/N2/O2/Ar mixtures suggest intermediate formation of nitromethane . Formation of such nitro and...Large amount of nitromethane (CH3NO2) forms within the plasma region, by CH3+NO2(+M)=CH3NO2(+M). Downstream, CH3NO2 then decomposes. • Current model

Effect of grazing on methane uptake from Eurasian steppe of China.

PubMed

Tang, Shiming; Zhang, Yujuan; Zhai, Xiajie; Wilkes, Andreas; Wang, Chengjie; Wang, Kun

2018-03-20

The effects of grazing on soil methane (CH 4 ) uptake in steppe ecosystems are important for understanding carbon sequestration and cycling because the role of grassland soil for CH 4 uptake can have major impacts at the global level. Here, a meta-analysis of 27 individual studies was carried out to assess the response patterns of soil CH 4 uptake to grazing in steppe ecosystems of China. The weighted log response ratio was used to assess the effect size. We found that heavy grazing significantly depressed soil CH 4 uptake by 36.47%, but light and moderate grazing had no significant effects in grassland ecosystem. The response of grassland soil CH 4 uptake to grazing also was found to depend upon grazing intensity, grazing duration and climatic types. The increase in soil temperature and reduced aboveground biomass and soil moisture induced by heavy grazing may be the major regulators of the soil CH 4 uptake. These findings imply that grazing effects on soil CH 4 uptake are highly context-specific and that grazing in different grasslands might be managed differently to help mitigate greenhouse gas emissions.

More CH4 is emitted during the fallow than during the growing season in a Mediterranean rice agrosystems

NASA Astrophysics Data System (ADS)

Martínez-Eixarch, Maite; Ibàñez, Carles; Alcaraz, Carles; Viñas, Marc; Aranda, Xavier; Saldaña, J. Antonio

2017-04-01

Paddy rice fields are an important source of greenhouse gas emissions (GHG) as they contribute 5 to 20 % of the global anthropogenic CH4 emissions. The Ebre Delta (Catalonia, NE Spain) is one of the most important wetland complexes in the Western Mediterranean with 65 % of its area covered by rice fields. The results herein presented assess the annual pattern of CH4 emissions from paddy rice in Ebre Delta, including the growing and fallow seasons as well as the major environmental variables modulating such emissions. Fifteen rice fields covering the geo-physical variability of the Ebre Delta were selected for GHG monitoring. Common agronomic management was practiced: water direct-seeding, permanent flooding and moderate mineral fertilization during the growing season and straw incorporation, progressive drainage of the fields after the harvest. Fields are left fallow during the winter. GHG were monthly sampled, from May to December in 2015. In each field, three closed chambers were used; from each of these, four gas samples were taken over a 30-minute period. Simultaneously, hydrological regime, soil physic-chemical parameters and plant cover were measured. GHG were analysed by gas chromatography. A Generalized linear model analysis (GLM) was performed to assess the most important influencing factors on CH4 emissions. An information-theoretic approach was used to find the best approximating models. Overall, the CH4 emissions showed a bi-modal pattern, with peaks in July-August and in October. Emissions rates ranged from 2.1 ± 0.5 to 7.5 ± 1.4 mg C-CH4 m-2 h-1 in the growing season (May to September) and from 25.0 ± 5.7 to 20.1 ± 3.3 mg C-CH4 m-2 h-1 at post-harvest (October to December). In total, 314 kg C-CH4 ha-1 were emitted from Ebre Delta rice fields, of which 70 % during post-harvest. Larger off-season emissions were likely induced by straw incorporation. The results of the GLM-IT analysis revealed that during the growing season, soil Eh and water level were the most important factors influencing CH4 emissions, followed by soil temperature and plant cover, with similar degree of importance. During the fallow season, soil redox and water level were also the most important factors, along with air temperature. Throughout the growing and fallow seasons, soil Eh was negatively related to CH4 emissions whereas temperature and plant cover positively. Interestingly, water level showed a contrasting effect on CH4 emissions: positive during the growing season and negative the fallow. Traditionally, most of the research on GHG mitigation options in paddy rice has been focused on the rice growing period and less attention has been paid to the post-harvest season. The higher contribution of the fallow season to the total annual CH4 emissions evidenced in our study suggests that more effort should be made on this season when aiming at mitigating CH4 emissions, being water and straw management the key factors. Accordingly, we also recommend the inclusion of the fallow season for GHG inventories from paddy rice, usually neglected, to avoid CH4 emissions underestimations.

Assessing the impact of electronic and steric tuning of the ligand in the spin state and catalytic oxidation ability of the Fe(II)(Pytacn) family of complexes.

PubMed

Prat, Irene; Company, Anna; Corona, Teresa; Parella, Teodor; Ribas, Xavi; Costas, Miquel

2013-08-19

A family of iron complexes with the general formula [Fe(II)((R,R)'Pytacn)(X)2](n+) is described, where (R,R)'Pytacn is the tetradentate ligand 1-[(4-R'-6-R-2-pyridyl)methyl]-4,7-dimethyl-1,4,7-triazacyclononane, R refers to the group at the α-position of the pyridine, R' corresponds to the group at the γ-position, and X denotes CH3CN or CF3SO3. Herein, we study the influence of the pyridine substituents R and R' on the electronic properties of the coordinated iron center by a combination of structural and spectroscopic characterization using X-ray diffraction, (1)H NMR and UV-vis spectroscopies, and magnetic susceptibility measurements. The electronic properties of the substituent in the γ-position of the pyridine ring (R') modulate the strength of the ligand field, as shown by magnetic susceptibility measurements in CD3CN solution, which provide a direct indication of the population of the magnetically active high-spin S = 2 ferrous state. Indeed, a series of complexes [Fe(II)((H,R)'Pytacn)(CD3CN)2](2+) exist as mixtures of high-spin (S = 2) and low-spin (S = 0) complexes, and their effective magnetic moment directly correlates with the electron-releasing ability of R'. On the other hand, the substitution of the hydrogen atom in the α-position of the pyridine by a methyl, chlorine, or fluorine group favors the high-spin state. The whole family of complexes has been assayed in catalytic C-H and C═C oxidation reactions with H2O2. These catalysts exhibit excellent efficiency in the stereospecific hydroxylation of alkanes and in the oxidation of olefins. Remarkably, R'-substituents have little influence on the efficiency and chemoselectivity of the catalytic activity of the complexes, but the selectivity toward olefin cis-dihydroxylation is enhanced for complexes with R = Me, F, or Cl. Isotopic labeling studies in the epoxidation and cis-dihydroxylation reactions show that R has a definitive role in dictating the origin of the oxygen atom that is transferred in the epoxidation reaction.

Cesium lead iodide solar cells controlled by annealing temperature.

PubMed

Kim, Yu Geun; Kim, Tae-Yoon; Oh, Jeong Hyeon; Choi, Kyoung Soon; Kim, Youn-Jea; Kim, Soo Young

2017-02-22

An inorganic lead halide perovskite film, CsPbI 3 , used as an absorber in perovskite solar cells (PSCs) was optimized by controlling the annealing temperature and the layer thickness. The CsPbI 3 layer was synthesized by one-step coating of CsI mixed with PbI 2 and a HI additive in N,N-dimethylformamide. The annealing temperature of the CsPbI 3 film was varied from 80 to 120 °C for different durations and the thickness was controlled by changing the spin-coating rpm. After annealing the CsPbI 3 layer at 100 °C under dark conditions for 10 min, a black phase of CsPbI 3 was formed and the band gap was 1.69 eV. Most of the yellow spots disappeared, the surface coverage was almost 100%, and the rms roughness was minimized to 3.03 nm after annealing at 100 °C. The power conversion efficiency (PCE) of the CsPbI 3 based PSC annealed at 100 °C was 4.88%. This high PCE value is attributed to the low yellow phase ratio, high surface coverage, low rms roughness, lower charge transport resistance, and lower charge accumulation. The loss ratio of the PCE of the CH 3 NH 3 PbI x Cl 3-x and CsPbI 3 based PSCs after keeping in air was 47 and 26%, respectively, indicating that the stability of the CsPbI 3 based PSC is better than that of the CH 3 NH 3 PbI x Cl 3-x based PSC. From these results, it is evident that CsPbI 3 is a potential candidate for solar cell applications.

Effects of Nickel Doping on the Multiferroic and Magnetic Phases of MnWO 4

DOE PAGES

Poudel, N.; Lorenz, B.; Lv, B.; ...

2015-12-15

There are various orders in multiferroic materials with a frustrated spiral spin modulation inducing a ferroelectric state are extremely sensitive to small perturbations such as magnetic and electric fields, external pressure, or chemical substitutions. A classical multiferroic, the mineral Hubnerite with chemical formula MnWO 4, shows three different magnetic phases at low temperature. The intermediate phase between 7.5K < T < 12.7K is multiferroic and ferroelectricity is induced by an inversion symmetry breaking spiral Mn-spin order and strong spin-lattice interactions. Furthermore, the substitution of Ni 2+ (spin 1) for Mn 2+ (spin 5/2) in MnWO 4 and its effects onmore » the magnetic and multiferroic phases are studied. The ferroelectric phase is stabilized for low Ni content (up to 10%). Upon further Ni doping, the polarization in the ferroelectric phase is quickly suppressed while a collinear and commensurate magnetic phase, characteristic of the magnetic structure in NiWO 4, appears first at higher temperature, gradually extends to lower temperature, and becomes the ground state above 30% doping. Between 10% and 30%, the multiferroic phase coexists with the collinear commensurate phase. In this concentration region, the spin spiral plane is close to the a-b plane which explains the drop of the ferroelectric polarization. Finally, the phase diagram of Mn 1-xNi xWO 4 is derived by a combination of magnetic susceptibility, specific heat, electric polarization, and neutron scattering measurements.« less

Two-dimensional magneto-optical light modulation in EuTiO3

NASA Astrophysics Data System (ADS)

Bussmann-Holder, Annette; Roleder, Krystian; Stuhlhofer, Benjamin; Logvenov, Gennady; Simon, Arndt; KöHler, Jürgen

EuTiO3 is antiferromagnetic at low temperature, namely below TN = 5.7K. In the high temperature paramagnetic phase the strongly nonlinear coupling between the lattice and the nomnially silent Eu 4f7 spins induces magnetic correlations which become apparent in muon spin rotation experiments and more recently in birefringence measurments in an external magnetic field. It is shown here, that high quality films of insulating EuTiO3 deposited on a thin SrTiO3 substrate are versatile tools for light modulation. The operating temperature is close to room temperature and admits multiple device engineering. By using small magnetic fields the birefringence of the samples can be switched off and on. Similarly, rotation of the sample in the field can modify its birefringence Δn. In addition, Δn can be increased by a factor of 4 in very modest fields with simultaneously enhancing the operating temperature by almost 100K. The results can be understood in terms of paramagnon phonon interaction where spin activity is achieved via the local spin-phonon double-well potential.

CO2, CH4, and DOC Flux During Long Term Thaw of High Arctic Tundra

NASA Astrophysics Data System (ADS)

Stackhouse, B. T.; Vishnivetskaya, T. A.; Layton, A.; Bennett, P.; Mykytczuk, N.; Lau, C. M.; Whyte, L.; Onstott, T. C.

2013-12-01

Arctic regions are expected to experience temperature increases of >4° C by the end of this century. This warming is projected to cause a drastic reduction in the extent of permafrost at high northern latitudes, affecting an estimated 1000 Pg of SOC in the top 3 m. Determining the effects of this temperature change on CO2 and CH4 emissions is critical for defining source constraints to global climate models. To investigate this problem, 18 cores of 1 m length were collected in late spring 2011 before the thawing of the seasonal active layer from an ice-wedge polygon near the McGill Arctic Research Station (MARS) on Axel Heiberg Island, Nunavut, Canada (N79°24, W90°45). Cores were collected from acidic soil (pH 5.5) with low SOC (~1%), summertime active layer depth between 40-70 cm (2010-2013), and sparse vegetation consisting primarily of small shrubs and sedges. Cores were progressively thawed from the surface over the course of 14 weeks to a final temperature of 4.5° C and held at that temperature for 15 months under the following conditions: in situ water saturation conditions versus fully water saturated conditions using artificial rain fall, surface light versus no surface light, cores from the polygon edge, and control cores with a permafrost table maintained at 70 cm depth. Core headspaces were measured weekly for CO2, CH4, H2, CO, and O2 flux during the 18 month thaw experiment. After ~20 weeks of thawing maximum, CO2 flux for the polygon edge and dark treatment cores were 3.0×0.7 and 1.7×0.4 mmol CO2 m-2 hr-1, respectively. The CO2 flux for the control, saturated, and in situ saturation cores reached maximums of 0.6×0.2, 0.9×0.5, and 0.9×0.1 mmol CO2 m-2 hr-1, respectively. Field measurements of CO2 flux from an adjacent polygon during the mid-summer of 2011 to 2013 ranged from 0.3 to 3.7 mmol CO2 m-2 hr-1. Cores from all treatments except water saturated were found to consistently oxidize CH4 at ~atmospheric concentrations (2 ppmv) with a maximum rate of -196×12 (dark) nmol CH4 m-2 hr-1. Saturated cores occasionally acted as slight CH4 sources (17×17 nmol CH4 m-2 hr-1) but were generally found to still behave as CH4 sinks (maximum rate -93×56 nmol CH4 m-2 hr-1). Dissolved CH4 in the permafrost pore water immediately upon thaw was ~0.5 μM in all treatments, and remained at this concentration in the saturated cores. In in situ water saturation treatments, however, pore water CH4 concentrations decreased from 0.6×0.3 μM to 0.2×0.1 μM over the course of three weeks without release into the core headspace. This is likely due to aerobic methanotrophy, as the concentration of genomic sequences associated with methanotrophic bacteria was found to be 30 times greater in the upper 60 cm than in the permafrost. Sustained concentrations of CH4 in the deeper portion of saturated cores indicated that methanogenesis is occurring at depths near and below the permafrost table. Measurements of in situ DOC were 0.22×0.05 mmol L-1, whereas core DOC values increased to a maximum of >1.7 mmol L-1 (primarily acetate) during the course of the thawing experiment. These findings indicate that in a warming Arctic, even under various hydrological regimes, these soil types will be able to act as a sink of atmospheric CH4, a moderate source of CO2 and a potential source for DOC.

A high level computational study of the CH4/CF4 dimer: how does it compare with the CH4/CH4 and CF4/CF4 dimers?

NASA Astrophysics Data System (ADS)

Biller, Matthew J.; Mecozzi, Sandro

2012-04-01

The interaction within the methane-methane (CH4/CH4), perfluoromethane-perfluoromethane (CF4/CF4) methane-perfluoromethane dimers (CH4/CF4) was calculated using the Hartree-Fock (HF) method, multiple orders of Møller-Plesset perturbation theory [MP2, MP3, MP4(DQ), MP4(SDQ), MP4(SDTQ)], and coupled cluster theory [CCSD, CCSD(T)], as well as the PW91, B97D, and M06-2X density functional theory (DFT) functionals. The basis sets of Dunning and coworkers (aug-cc-pVxZ, x = D, T, Q), Krishnan and coworkers [6-311++G(d,p), 6-311++G(2d,2p)], and Tsuzuki and coworkers [aug(df, pd)-6-311G(d,p)] were used. Basis set superposition error (BSSE) was corrected via the counterpoise method in all cases. Interaction energies obtained with the MP2 method do not fit with the experimental finding that the methane-perfluoromethane system phase separates at 94.5 K. It was not until the CCSD(T) method was considered that the interaction energy of the methane-perfluoromethane dimer (-0.69 kcal mol-1) was found to be intermediate between the methane (-0.51 kcal mol-1) and perfluoromethane (-0.78 kcal mol-1) dimers. This suggests that a perfluoromethane molecule interacts preferentially with another perfluoromethane (by about 0.09 kcal mol-1) than with a methane molecule. At temperatures much lower than the CH4/CF4 critical solution temperature of 94.5 K, this energy difference becomes significant and leads perfluoromethane molecules to associate with themselves, forming a phase separation. The DFT functionals yielded erratic results for the three dimers. Further development of DFT is needed in order to model dispersion interactions in hydrocarbon/perfluorocarbon systems.

The magnetic structure of Co(NCNH)₂ as determined by (spin-polarized) neutron diffraction

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

Jacobs, Philipp; Houben, Andreas; Senyshyn, Anatoliy

The magnetic structure of Co(NCNH)₂ has been studied by neutron diffraction data below 10 K using the SPODI and DNS instruments at FRM II, Munich. There is an intensity change in the (1 1 0) and (0 2 0) reflections around 4 K, to be attributed to the onset of a magnetic ordering of the Co²⁺ spins. Four different spin orientations have been evaluated on the basis of Rietveld refinements, comprising antiferromagnetic as well as ferromagnetic ordering along all three crystallographic axes. Both residual values and supplementary susceptibility measurements evidence that only a ferromagnetic ordering with all Co²⁺ spins parallelmore » to the c axis is a suitable description of the low-temperature magnetic ground state of Co(NCNH)₂. The deviation of the magnetic moment derived by the Rietveld refinement from the expectancy value may be explained either by an incomplete saturation of the moment at temperatures slightly below the Curie temperature or by a small Jahn–Teller distortion. - Graphical abstract: The magnetic ground state of Co(NCNH)₂ has been clarified by (spin-polarized) neutron diffraction data at low temperatures. Intensity changes below 4 K arise due to the onset of ferromagnetic ordering of the Co²⁺ spins parallel to the c axis, corroborated by various (magnetic) Rietveld refinements. Highlights: • Powderous Co(NCNH)₂ has been subjected to (spin-polarized) neutron diffraction. • Magnetic susceptibility data of Co(NCNH)₂ have been collected. • Below 4 K, the magnetic moments align ferromagnetically with all Co²⁺ spins parallel to the c axis. • The magnetic susceptibility data yield an effective magnetic moment of 4.68 and a Weiss constant of -13(2) K. • The ferromagnetic Rietveld refinement leads to a magnetic moment of 2.6 which is close to the expectancy value of 3.« less

Spin-lattice relaxation and the calculation of gain, pump power, and noise temperature in ruby

NASA Technical Reports Server (NTRS)

Lyons, J. R.

1989-01-01

The use of a quantitative analysis of the dominant source of relaxation in ruby spin systems to make predictions of key maser amplifier parameters is described. The spin-lattice Hamiltonian which describes the interaction of the electron spins with the thermal vibrations of the surrounding lattice is obtained from the literature. Taking into account the vibrational anisotropy of ruby, Fermi's rule is used to calculate the spin transition rates between the maser energy levels. The spin population rate equations are solved for the spin transition relaxation times, and a comparison with previous calculations is made. Predictions of ruby gain, inversion ratio, and noise temperature as a function of physical temperature are made for 8.4-GHz and 32-GHz maser pumping schemes. The theory predicts that ruby oriented at 90 deg will have approximately 50 percent higher gain in dB and slightly lower noise temperature than a 54.7-deg ruby at 32 GHz (assuming pump saturation). A specific calculation relating pump power to inversion ratio is given for a single channel of the 32-GHz reflected wave maser.

Single crystal growth, magnetic and thermal properties of perovskite YFe0.6Mn0.4O3 single crystal

NASA Astrophysics Data System (ADS)

Xie, Tao; Shen, Hui; Zhao, Xiangyang; Man, Peiwen; Wu, Anhua; Su, Liangbi; Xu, Jiayue

2016-11-01

High quality YFe0.6Mn0.4O3 single crystal was grown by floating zone technique using a four-mirror-image-furnace under flowing air. Powder X-ray diffraction gives well evidence that the specimen has an orthorhombic structure, with space group Pbnm. Temperature dependence of the magnetizations of YFe0.6Mn0.4O3 single crystal were studied under ZFC and FC modes in the temperature range from 5 K to 400 K. A clear spin reorientation transition behavior (Γ4→Γ1) is observed in the temperature range of 322-316 K, due to the substitution of Mn at the Fe site of YFeO3. Its Néel temperature is around 385 K. Moreover, the spin reorientation is verified by the change of magnetic hysteresis loops of the sample along [001] axis in the temperature range of 50-385 K. The thermal properties of the sample were measured by the differential scanning calorimeter (DSC) from 300 K to 500 K, which also clearly appear anomaly in the spin reorientation region.

Non-LTE models of Titan's upper atmosphere

NASA Technical Reports Server (NTRS)

Yelle, Roger V.

1991-01-01

Models for the thermal structure of Titan's upper atmosphere, between 0.1 mbar and 0.01 nbar are presented. The calculations include non-LTE heating/cooling in the rotation-vibration bands of CH4, C2H2, and C2H6, absorption of solar IR radiation in the near-IR bands of CH4 and subsequent cascading to the nu-4 band of CH4, absorption of solar EUV and UV radiation, thermal conduction and cooling by HCN rotational lines. Unlike earlier models, the calculated exospheric temperature agrees well with observations, because of the importance of HCN cooling. The calculations predict a well-developed mesopause with a temperature of 135-140 K at an altitude of approximately 600 km and pressure of about 0.1 microbar. The mesopause is at a higher pressure than predicted by earlier calculations because non-LTE radiative transfer in the rotation-vibration bands of CH4, C2H2, and C2H6 is treated in an accurate manner. The accuracy of the LTE approximation for source functions and heating rates is discussed.

Halogen Substitution Effects on N2 O Schiff Base Ligands in Unprecedented Abrupt FeII Spin Crossover Complexes.

PubMed

Phonsri, Wasinee; Macedo, David S; Vignesh, Kuduva R; Rajaraman, Gopalan; Davies, Casey G; Jameson, Guy N L; Moubaraki, Boujemaa; Ward, Jas S; Kruger, Paul E; Chastanet, Guillaume; Murray, Keith S

2017-05-23

A family of halogen-substituted Schiff base iron(II) complexes, [Fe II (qsal-X) 2 ], (qsal-X=5-X-N-(8-quinolyl)salicylaldimines)) in which X=F (1), Cl (2), Br (3) or I (4) has been investigated in detail. Compound 1 shows a temperature invariant high spin state, whereas the others all show abrupt spin transitions, at or above room temperature, namely, 295 K (X=I) up to 342 K (X=Br), these being some of the highest T 1/2 values obtained, to date, for Fe II N/O species. We have recently reported subtle symmetry breaking in [Fe II (qsal-Cl) 2 ] 2 with two spin transition steps occurring at 308 and 316 K. A photomagnetic study reveals almost full HS conversion of [Fe II (qsal-I) 2 ] 4 at low temperature (T(LIESST)=54 °K). The halogen substitution effects on the magnetic properties, as well as the crystal packing of the [Fe II (qsal-X) 2 ] compounds and theoretical calculations, are discussed in depth, giving important knowledge for the design of new spin crossover materials. In comparison to the well known iron(III) analogues, [Fe III (qsal-X) 2 ] + , the two extra π-π and P4AE interactions found in [Fe II (qsal-X) 2 ] compounds, are believed to be accountable for the spin transitions occurring at ambient temperatures. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spin Transport in Nondegenerate Si with a Spin MOSFET Structure at Room Temperature

NASA Astrophysics Data System (ADS)

Sasaki, Tomoyuki; Ando, Yuichiro; Kameno, Makoto; Tahara, Takayuki; Koike, Hayato; Oikawa, Tohru; Suzuki, Toshio; Shiraishi, Masashi

2014-09-01

Spin transport in nondegenerate semiconductors is expected to pave the way to the creation of spin transistors, spin logic devices, and reconfigurable logic circuits, because room-temperature (RT) spin transport in Si has already been achieved. However, RT spin transport has been limited to degenerate Si, which makes it difficult to produce spin-based signals because a gate electric field cannot be used to manipulate such signals. Here, we report the experimental demonstration of spin transport in nondegenerate Si with a spin metal-oxide-semiconductor field-effect transistor (MOSFET) structure. We successfully observe the modulation of the Hanle-type spin-precession signals, which is a characteristic spin dynamics in nondegenerate semiconductors. We obtain long spin transport of more than 20 μm and spin rotation greater than 4π at RT. We also observe gate-induced modulation of spin-transport signals at RT. The modulation of the spin diffusion length as a function of a gate voltage is successfully observed, which we attribute to the Elliott-Yafet spin relaxation mechanism. These achievements are expected to lead to the creation of practical Si-based spin MOSFETs.

Dipolar Spin Ice States with a Fast Monopole Hopping Rate in CdEr2X4 (X =Se , S)

NASA Astrophysics Data System (ADS)

Gao, Shang; Zaharko, O.; Tsurkan, V.; Prodan, L.; Riordan, E.; Lago, J.; Fâk, B.; Wildes, A. R.; Koza, M. M.; Ritter, C.; Fouquet, P.; Keller, L.; Canévet, E.; Medarde, M.; Blomgren, J.; Johansson, C.; Giblin, S. R.; Vrtnik, S.; Luzar, J.; Loidl, A.; Rüegg, Ch.; Fennell, T.

2018-03-01

Excitations in a spin ice behave as magnetic monopoles, and their population and mobility control the dynamics of a spin ice at low temperature. CdEr2 Se4 is reported to have the Pauling entropy characteristic of a spin ice, but its dynamics are three orders of magnitude faster than the canonical spin ice Dy2 Ti2 O7 . In this Letter we use diffuse neutron scattering to show that both CdEr2 Se4 and CdEr2 S4 support a dipolar spin ice state—the host phase for a Coulomb gas of emergent magnetic monopoles. These Coulomb gases have similar parameters to those in Dy2 Ti2 O7 , i.e., dilute and uncorrelated, and so cannot provide three orders faster dynamics through a larger monopole population alone. We investigate the monopole dynamics using ac susceptometry and neutron spin echo spectroscopy, and verify the crystal electric field Hamiltonian of the Er3 + ions using inelastic neutron scattering. A quantitative calculation of the monopole hopping rate using our Coulomb gas and crystal electric field parameters shows that the fast dynamics in CdEr2X4 (X =Se , S) are primarily due to much faster monopole hopping. Our work suggests that CdEr2X4 offer the possibility to study alternative spin ice ground states and dynamics, with equilibration possible at much lower temperatures than the rare earth pyrochlore examples.

Line Mixing in Water Vapor and Methane

NASA Technical Reports Server (NTRS)

Smith, M. A. H.; Brown, L. R.; Toth, R. A.; Devi, V. Malathy; Benner, Chris

2006-01-01

A multispectrum fitting algorithm has been used to identify line mixing and determine mixing parameters for infrared transitions of H2O and CH4 in the 5-9 micrometer region. Line mixing parameters at room temperature were determined for two pairs of transitions in the v2 fundamental band of H2O-16, for self-broadening and for broadening by H2, He, CO2, N2, O2 and air. Line mixing parameters have been determined from air-broadened CH4 spectra, recorded at temperatures between 210 K and 314 K, in selected R-branch manifolds of the v4 band. For both H2O and CH4, the inclusion of line mixing was seen to have a greater effect on the retrieved values of the line shifts than on the retrieved values of other parameters

Intermediate-scale community-level flux of CO 2 and CH 4 in a Minnesota peatland: Putting the SPRUCE project in a global context

DOE PAGES

Hanson, Paul J.; Gill, Allison; Xu, Xiaofeng; ...

2016-08-20

Peatland measurements of CO 2 and CH 4 flux were obtained at scales appropriate to the in situ biological community below the tree layer to demonstrate representativeness of the spruce and peatland responses under climatic and environmental change (SPRUCE) experiment. Surface flux measurements were made using dual open-path analyzers over an area of 1.13 m 2 in daylight and dark conditions along with associated peat temperatures, water table height, hummock moisture, atmospheric pressure and incident radiation data. Observations from August 2011 through December 2014 demonstrated seasonal trends correlated with temperature as the dominant apparent driving variable. The S1-Bog for themore » SPRUCE study was found to be representative of temperate peatlands in terms of CO 2 and CH 4 flux. Maximum net CO 2 flux in midsummer showed similar rates of C uptake and loss: daytime surface uptake was -5 to -6 µmol m -2 s -1 and dark period loss rates were 4–5 µmol m -2 s -1 (positive values are carbon lost to the atmosphere). Maximum midsummer CH4-C flux ranged from 0.4 to 0.5 µmol m -2 s -1 and was a factor of 10 lower than dark CO 2–C efflux rates. Midwinter conditions produced near-zero flux for both CO 2 and CH 4 with frozen surfaces. Integrating temperature-dependent models across annual periods showed dark CO 2–C and CH 4–C flux to be 894 ± 34 and 16 ± 2 gC m -2 y -1, respectively. Net ecosystem exchange of carbon from the shrub-forb-Sphagnum-microbial community (excluding tree contributions) ranged from -3.1 gCO2–C m -2 y -1 in 2013, to C losses from 21 to 65 gCO 2–C m -2 y -1 for the other years.« less

Experimental Determination of Carbon Isotope Fractionation in C-O-H-Fluids and the Carbonate-melt - Graphite System at High Temperatures

NASA Astrophysics Data System (ADS)

Kueter, N.; Schmidt, M. W.; Lilley, M. D.; Bernasconi, S. M.

2017-12-01

The understanding of deep-earth carbon fluxes depends greatly on the investigation of carbon isotope systematics in C-O-H-fluids and carbon minerals, such as graphite and diamond (C0). The isotope fractionation factors between the different C-phases and species (in e.g. a fluid) thus govern the observed isotope fractionation patterns. C-isotope fractionation factors relevant for high temperatures are mainly derived from theoretical calculations [e.g. 1,2,3] and, with few exceptions, lack experimental determinations [e.g. 4]. Hundreds of own experiments aimed at equilibrating elemental carbon (C0, graphite/diamond) with C-O-H-fluids demonstrate that kinetics reigns as no system would be closed for H on time scales and temperatures allowing for graphite to equilibrate. To overcome this problem, we performed two studies to determine the C-isotope fractionation in 1) the CO2-CO-CH4 system and 2) the carbonate-melt - graphite system. Equilibrium C-isotope fractionation factors were obtained for CO2 - CO and CH4 - CO pairs (600 - 1200°C) and graphite - Na2CO3/CaCO3melt (900 - 1500°C). Combined with the already available fractionation data for the CaCO3-CO2 pair (400-950°C) from Chacko et al. [4], we determined experimentally based C-isotope fractionation factors for C0 - CH4 and CO2 - C0 pairs by 1) Δ13CCO2-graphite = Δ13CCO2-carbonate + Δ13CCarbonate-graphite and 2) Δ13Cgraphite-CH4 = Δ13CCO2-CH4 - Δ13CCO2-graphite . Current calculated fractionation factors relevant for mantle temperatures (1100 - 1500°C) suggest C-isotope partitioning in the CO2 - C0 pair on the order of 4.2 to 2.4‰, about 2‰ less than predicted by theoretically derived factors [3]. In contrast, our calculations suggest fractionation of about 1.4 to 1.1‰ for the C0 - CH4 pair, about 1‰ higher than expected by theory [3]. [1] Richet et al. (1977) Ann. Rev. Earth Planet. Sci.; [2] Polyakov & Kharlashina (1995) GCA; [3] Bottinga (1969) GCA; [4] Chacko et al. (2001) Rev Mineral Geochem

Limits and dynamics of methane oxidation in landfill cover soils

USDA-ARS?s Scientific Manuscript database

In order to understand the limits and dynamics of methane (CH4) oxidation in landfill cover soils, we investigated CH4 oxidation in daily, intermediate, and final cover soils from two California landfills as a function of temperature, soil moisture and CO2 concentration. The results indicate a signi...

Sub-arctic Wetland Greenhouse Gases (CO2, CH4 & N2O) Emissions are Driven by Interactions of Environmental Controls and Herbivore Grazers

NASA Astrophysics Data System (ADS)

Kelsey, K.; Leffler, A. J.; Beard, K. H.; Choi, R. T.; Welker, J. M.

2015-12-01

Climate change is increasing temperatures, altering precipitation regimes and causing earlier growing seasons, particularly at northern latitudes. Such changes in local environmental conditions have the potential to affect biogeochemical cycling including the exchange of greenhouses gases between the atmosphere and the terrestrial biosphere. In addition to the effects of these environmental controls, animals such as migratory geese also influence biogeochemical cycles through grazing, trampling and delivering nutrient-rich fecal matter. In this work we aimed to quantify how local environmental conditions and the presence of grazing interact as drivers of emissions of three key greenhouse gases, CO2, CH4 and N2O, in coastal wetlands of the Yukon Kuskokwim Delta. We explored the magnitude of emissions across gradients of soil temperature and water table depth, and across vegetation types related to the presence of grazing, ranging from no vegetation through grazed and ungrazed vegetation. We also investigated emissions from grazed areas using experimental manipulations of the timing of grazing and advancement of the growing season. We found that local environmental conditions and use by grazers exert interacting controls on emissions of CO2, CH4 and N2O. Emissions of CO2 and CH4 were positively related to soil temperature and CH4 emissions were inversely related to water table depth, but the relationship varied by vegetation type. Net emissions of CO2 were greatest in ungrazed vegetation types (6.62 umols CO2 m-2 sec-1; p=0.0007) whereas CH4 emissions were greatest in the grazed vegetation (122.56 nmols CH4 m-2 sec-1; p=0.037). Flux of N2O was less than 1 nmol N2O m-2 sec-1 across all landscape positions under typical grazing and temperature conditions, but emissions were stimulated to over 10 nmols m-2 sec-1 when grazing occurred early relative to a typical season. Our results indicate that environmental conditions and the presence of migratory herbivores are both important controls on gas fluxes. Future climate change may alter regional gas flux and biosphere-atmosphere feedbacks both via direct environmental drivers and through climate-driven changes to populations or habits of grazers that also exert important controls on biogeochemical cycling in this region.

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.

Tunable diode-laser absorption measurements of methane at elevated temperatures

NASA Astrophysics Data System (ADS)

Nagali, V.; Chou, S. I.; Baer, D. S.; Hanson, R. K.; Segall, J.

1996-07-01

A diode-laser sensor system based on absorption spectroscopy techniques has been developed to monitor CH4 nonintrusively in high-temperature environments. Fundamental spectroscopic parameters, including the line strengths of the transitions in the R(6) manifold of the 2 nu 3 band near 1.646 mu m, have been determined from high-resolution absorption measurements in a heated static cell. In addition, a corrected expression for the CH 4 partition function has been validated experimentally over the temperature range from 400 to 915 K. Potential applications of the diode-laser sensor system include process control, combustion measurements, and atmospheric monitoring.

Experimental measurements of vapor-liquid equilibria of the H2O + CO2 + CH4 ternary system

USGS Publications Warehouse

Qin, J.; Rosenbauer, R.J.; Duan, Zhenhao

2008-01-01

Reported are the experimental measurements on vapor-liquid equilibria in the H2O + CO2 + CH4 ternary system at temperatures from (324 to 375) K and pressures from (10 to 50) MPa. The results indicate that the CH4 solubility in the ternary mixture is about 10 % to 40 % more than that calculated by interpolation from the Henry's law constants of the binary system, H2O + CH4, and the solubility of CO2 is 6 % to 20 % more than what is calculated by the interpolation from the Henry's law constants of the binary mixture, H 2O + CO2. ?? 2008 American Chemical Society.

Activated adsorption of methane on clean and oxygen-modified Pt?111? and Pd?110?

NASA Astrophysics Data System (ADS)

Valden, M.; Pere, J.; Hirsimäki, M.; Suhonen, S.; Pessa, M.

1997-04-01

Activated adsorption of CH 4 on clean and oxygen modified Pt{111} and Pd{110} has been studied using molecular beam surface scattering. The absolute dissociation probability of CH 4 was measured as a function of the incident normal energy ( E) and the surface temperature ( Ts). The results from clean Pt{111} and Pd{110} are consistent with a direct dissociation mechanism. The dissociative chemisorption dynamics of CH 4 is addressed by using quantum mechanical and statistical models. The influence of adsorbed oxygen on the dissociative adsorption of CH 4 on both Pt{111} and Pd{110} shows that the dissociation probability decreases linearly with increasing oxygen coverage.

Spectroscopic studies of Cr{sup 3+} ions doped in poly(vinylalcohol) complexed polyethylene glycol polymer films

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

Rao, T. Rajavardhana; Raju, Ch. Linga, E-mail: drchlraj-phy@yahoo.com; Brahmam, K. Veera

2015-05-15

Polymer films of Poly(vinylalcohol) (PVA) complexed with Polyethylene glycol (PEG) with different dopant concentrations of Cr{sup 3+} ions are prepared by solution cast technique. Electron paramagnetic resonance (EPR), Optical absorption and FT-IR studies have been carried out on the polymer films. The EPR spectra of the entire samples exhibit resonance signal at g ≈1.97 which is attributed to the isolated Cr{sup 3+} pairs. The temperature variation EPR studies show that the population of spin-levels participating in the resonance decreases with an increase in temperature, which is in accordance with the Boltzmann Law. The paramagnetic susceptibilities (X) have been calculated frommore » the EPR data at different temperatures. The linewidth of the g ≈1.97 resonance signal has been found to be decreasing with an increase in temperature, which confirms the pairing mechanism between Cr{sup 3+} ions. The Optical absorption spectrum of chromium ions in (PVA+PEG) polymer films exhibits three bands, corresponding to the d-d transitions {sup 4}A{sub 2g}(F)→{sup 4}T{sub 1g}(F), {sup 4}A{sub 2g}(F)→{sup 4}T{sub 2g}(F) and {sup 4}A{sub 2g}(F)→{sup 2}T{sub 1g}(G), in the order of decreasing energy. The crystal field parameter Dq and the Racah interelectronic repulsion parameters B and C have been evaluated. From the ultraviolet absorption edges, Optical band gap (E{sub opt}) and Urbach (ΔE) energies are evaluated. FT-IR spectrum exhibits few bands which are attributed to O-H, CH, C=C and C=O groups of stretching and bending vibrations.« less

On the Vertical Thermal Structure of Pluto's Atmosphere

NASA Astrophysics Data System (ADS)

Strobel, Darrell F.; Zhu, Xun; Summers, Michael E.; Stevens, Michael H.

1996-04-01

A radiative-conductive model for the vertical thermal structure of Pluto's atmosphere is developed with a non-LTE treatment of solar heating in the CH43.3 μm and 2.3 μm bands, non-LTE radiative exchange and cooling in the CH47.6 μm band, and LTE cooling by CO rotational line emission. The model includes the effects of opacity and vibrational energy transfer in the CH4molecule. Partial thermalization of absorbed solar radiation in the CH43.3 and 2.3 μm bands by rapid vibrational energy transfer from the stretch modes to the bending modes generates high altitude heating at sub-microbar pressures. Heating in the 2.3 μm bands exceeds heating in 3.3 μm bands by approximately a factor of 6 and occurs predominantly at microbar pressures to generate steep temperature gradients ∼10-20 K km-1forp> 2 μbar when the surface or tropopause pressure is ∼3 μbar and the CH4mixing ratio is a constant 3%. This calculated structure may account for the "knee" in the stellar occultation lightcurve. The vertical temperature structure in the first 100 km above the surface is similar for atmospheres with Ar, CO, and N2individually as the major constituent. If a steep temperature gradient ∼20 K km-1is required near the surface or above the tropopause, then the preferred major constituent is Ar with 3% CH4mixing ratio to attain a calculated ratio ofT/M(= 3.5 K amu-1) in agreement with inferred values from stellar occultation data. However, pure Ar and N2ices at the same temperature yield an Ar vapor pressure of only ∼0.04 times the N2vapor pressure. Alternative scenarios are discussed that may yield acceptable fits with N2as the dominant constituent. One possibility is a 3 μbar N2atmosphere with 0.3% CH4that has 106 K isothermal region (T/M= 3.8 K amu-1) and ∼8 K km-1surface/tropopause temperature gradient. Another possibility would be a higher surface pressure ∼10 μbar with a scattering haze forp> 2 μbar. Our model with appropriate adjustments in the CH4density profile to Triton's inferred profile yields a temperature profile consistent with the UVS solar occultation data (Krasnopolsky, V. A., B. R. Sandel, and F. Herbert 1992.J. Geophys. Res.98, 3065-3078.) and ground-based stellar occultation data (Elliot, J. L., E. W. Dunham, and C. B. Olkin 1993.Bull. Am. Astron. Soc.25, 1106.).

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

Chen, S. L., E-mail: shuch@ist.hokudai.ac.jp; Takayama, J.; Murayama, A.

Time-resolved optical spin orientation spectroscopy was employed to investigate the temperature-dependent electron spin injection in In{sub 0.1}Ga{sub 0.9}As quantum well (QW) and In{sub 0.5}Ga{sub 0.5}As quantum dots (QDs) tunnel-coupled nanostructures with 4, 6, and 8 nm-thick GaAs barriers. The fast picosecond-ranged spin injection from QW to QD excited states (ES) was observed to speed up with temperature, as induced by pronounced longitudinal-optical (LO)-phonon-involved multiple scattering process, which contributes to a thermally stable and almost fully spin-conserving injection within 5–180 K. The LO-phonon coupling was also found to cause accelerated electron spin relaxation of QD ES at elevated temperature, mainly via hyperfine interactionmore » with random nuclear field.« less

Spin relaxation in n-type GaAs quantum wells from a fully microscopic approach

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

Zhou, J.; Wu, M. W.; Department of Physics, University of Science and Technology of China, Hefei, Anhui 230026

2007-01-15

We perform a full microscopic investigation on the spin relaxation in n-type (001) GaAs quantum wells with an Al{sub 0.4}Ga{sub 0.6}As barrier due to the D'yakonov-Perel' mechanism from nearly 20 K to room temperature by constructing and numerically solving the kinetic spin Bloch equations. We consider all the relevant scattering such as the electron-acoustic-phonon, the electron-longitudinal-optical-phonon, the electron-nonmagnetic-impurity, and the electron-electron Coulomb scattering to the spin relaxation. The spin relaxation times calculated from our theory with a fitting spin splitting parameter are in good agreement with the experimental data by Ohno et al. [Physica E (Amsterdam) 6, 817 (2000)] overmore » the whole temperature regime (from 20 to 300 K). The value of the fitted spin splitting parameter agrees with many experiments and theoretical calculations. We further show the temperature dependence of the spin relaxation time under various conditions such as electron density, impurity density, and well width. We predict a peak solely due to the Coulomb scattering in the spin relaxation time at low temperature (<50 K) in samples with low electron density (e.g., density less than 1x10{sup 11} cm{sup -2}) but high mobility. This peak disappears in samples with high electron density (e.g., 2x10{sup 11} cm{sup -2}) and/or low mobility. The hot-electron spin kinetics at low temperature is also addressed with many features quite different from the high-temperature case predicted.« less

Suzaku observations of 4U 1957+11: The most rapidly spinning black hole in the galaxy?

NASA Astrophysics Data System (ADS)

Nowak, Michael A.; Wilms, Jörn; Pottschmidt, Katja; Schulz, Norbert; Miller, Jon; Maitra, Dipankar

2012-03-01

We present three Suzaku observations of the black hole candidate 4U 1957+11-a source that exhibits some of the simplest and cleanest examples of soft, disk-dominated spectra. 4U 1957+11 also presents among the highest peak temperatures found fromdisk-dominated spectra. Such temperatures may be associated with rapid black hole spin. The 4U 1957+11 spectra also require a very low normalization, which can be explained by a combination of small inner disk radius and a large distance (> 10 kpc) which places 4U 1957+11 well into the Galactic halo. We perform joint fits to the Suzaku spectra with relativistic disk models. Assuming a low mass black hole and the nearest distance (3Msolar, 10 kpc), the dimensionless spin parameter a*≡Jc/GM2>~0.9. Higher masses and farther distances yield a* ~1. Low spin cannot be recovered unless 4U 1957+11 is a low mass black hole that is at the unusually large distance of >~ 40 kpc.

The H2/CH4 ratio during serpentinization cannot reliably identify biological signatures

PubMed Central

Huang, Ruifang; Sun, Weidong; Liu, Jinzhong; Ding, Xing; Peng, Shaobang; Zhan, Wenhuan

2016-01-01

Serpentinization potentially contributes to the origin and evolution of life during early history of the Earth. Serpentinization produces molecular hydrogen (H2) that can be utilized by microorganisms to gain metabolic energy. Methane can be formed through reactions between molecular hydrogen and oxidized carbon (e.g., carbon dioxide) or through biotic processes. A simple criterion, the H2/CH4 ratio, has been proposed to differentiate abiotic from biotic methane, with values approximately larger than 40 for abiotic methane and values of <40 for biotic methane. The definition of the criterion was based on two serpentinization experiments at 200 °C and 0.3 kbar. However, it is not clear whether the criterion is applicable at a wider range of temperatures. In this study, we performed sixteen experiments at 311–500 °C and 3.0 kbar using natural ground peridotite. Our results demonstrate that the H2/CH4 ratios strongly depend on temperature. At 311 °C and 3.0 kbar, the H2/CH4 ratios ranged from 58 to 2,120, much greater than the critical value of 40. By contrast, at 400–500 °C, the H2/CH4 ratios were much lower, ranging from 0.1 to 8.2. The results of this study suggest that the H2/CH4 ratios cannot reliably discriminate abiotic from biotic methane. PMID:27666288

Orphan Spins in the S=5/2 Antiferromagnet CaFe_{2}O_{4}.

PubMed

Stock, C; Rodriguez, E E; Lee, N; Demmel, F; Fouquet, P; Laver, M; Niedermayer, Ch; Su, Y; Nemkovski, K; Green, M A; Rodriguez-Rivera, J A; Kim, J W; Zhang, L; Cheong, S-W

2017-12-22

CaFe_{2}O_{4} is an anisotropic S=5/2 antiferromagnet with two competing A (↑↑↓↓) and B (↑↓↑↓) magnetic order parameters separated by static antiphase boundaries at low temperatures. Neutron diffraction and bulk susceptibility measurements, show that the spins near these boundaries are weakly correlated and a carry an uncompensated ferromagnetic moment that can be tuned with a magnetic field. Spectroscopic measurements find these spins are bound with excitation energies less than the bulk magnetic spin waves and resemble the spectra from isolated spin clusters. Localized bound orphaned spins separate the two competing magnetic order parameters in CaFe_{2}O_{4}.

Orphan Spins in the S =5/2 Antiferromagnet CaFe2O4

NASA Astrophysics Data System (ADS)

Stock, C.; Rodriguez, E. E.; Lee, N.; Demmel, F.; Fouquet, P.; Laver, M.; Niedermayer, Ch.; Su, Y.; Nemkovski, K.; Green, M. A.; Rodriguez-Rivera, J. A.; Kim, J. W.; Zhang, L.; Cheong, S.-W.

2017-12-01

CaFe2O4 is an anisotropic S =5/2 antiferromagnet with two competing A (↑↑↓↓) and B (↑↓↑↓) magnetic order parameters separated by static antiphase boundaries at low temperatures. Neutron diffraction and bulk susceptibility measurements, show that the spins near these boundaries are weakly correlated and a carry an uncompensated ferromagnetic moment that can be tuned with a magnetic field. Spectroscopic measurements find these spins are bound with excitation energies less than the bulk magnetic spin waves and resemble the spectra from isolated spin clusters. Localized bound orphaned spins separate the two competing magnetic order parameters in CaFe2 O4 .

Infrared spectroscopy and tunneling dynamics of the vinyl radical in 4He nanodroplets

DOE PAGES

Raston, Paul L.; Liang, Tao; Douberly, Gary E.

2013-05-01

Here, the vinyl radical has been trapped in 4He nanodroplets and probed with infrared laser spectroscopy in the CH stretch region between 2850 and 3200 cm -1. The assigned band origins for the CH 2 symmetric (ν 3), CH 2 antisymmetric (ν 2), and lone α-CH stretch (ν 1) vibrations are in good agreement with previously reported full-dimensional vibrational configuration interaction computations. For all three bands, a-type and b-type transitions are observed from the lowest symmetry allowed roconvibrational state of each nuclear spin isomer, which allows for a determination of the tunneling splittings in both the ground and excited vibrationalmore » levels. Comparisons to gas phase millimeter-wave rotation-tunneling and high-resolution jet-cooled infrared spectra reveal that the He solvent effect is to reduce the ground and ν 3 excited state tunneling splittings by ≈20%. This solvent-induced modification of the tunneling dynamics can be reasonably accounted for by assuming either a ≈2.5% increase in the effective barrier height along the tunneling coordinate or a ≈5% increase in the effective reduced mass of the tunneling particles.« less

Magnetocrystalline two-fold symmetry in CaFe2O4 single crystal

NASA Astrophysics Data System (ADS)

Chhaganlal Gandhi, Ashish; Das, Rajasree; Chou, Fang-Cheng; Lin, Jauyn Grace

2017-05-01

Understanding of magnetocrystalline anisotropy in CaFe2O4 is a matter of importance for its future applications. A high quality single crystal CaFe2O4 sample is studied by using synchrotron x-ray diffraction, a magnetometer and the electron spin resonance (ESR) technique. A broad feature of the susceptibility curve around room temperature is observed, indicating the development of 1D spin interactions above the on-set of antiferromagnetic transition. The angular dependency of ESR reveals an in-plane two-fold symmetry, suggesting a strong correlation between the room temperature spin structure and magnetocrystalline anisotropy. This finding opens an opportunity for the device utilizing the anisotropy field of CaFe2O4.

Magnetization of La2-xSrxNiO4+δ (0⩽x⩽0.5) : Spin-glass and memory effects

NASA Astrophysics Data System (ADS)

Freeman, P. G.; Boothroyd, A. T.; Prabhakaran, D.; Lorenzana, J.

2006-01-01

We have studied the magnetization of a series of spin-charge-ordered La2-xSrxNiO4+δ single crystals with 0⩽x⩽0.5 . For fields applied parallel to the ab plane there is a large irreversibility below a temperature TF1˜50K and a smaller irreversibility that persists up to near the charge-ordering temperature. We observed memory effects in the thermoremnant magnetization across the entire doping range. We found that these materials retain a memory of the temperature at which an external field was removed and that there is a pronounced increase in the thermoremnant magnetization when the system is warmed through a spin reorientation transition.

A new method for speciated CH3O2 radical detection and HIRAC (Highly Instrumented Reactor for Atmospheric Chemistry) studies of the CH3O2 self-reaction

NASA Astrophysics Data System (ADS)

Onel, Lavinia; Brennan, Alexander; Seakins, Paul W.; Whalley, Lisa; Heard, Dwayne

2016-04-01

A new method has been developed for the speciated detection of CH3O2 radicals by FAGE (Fluorescence Assay by Gas Expansion) by titrating CH3O2 to CH3O by reaction with added NO and then detecting the resultant CH3O by LIF (laser induced fluorescence). The limit of detection of the technique is ˜108 cm-3 CH3O2 for a unity signal-to-noise ratio and 5 min averaging time. The method has been used for time monitoring of CH3O2 during its self-reaction within HIRAC at 1 bar and room temperature to determine a preliminary value of the rate coefficient of 4.2 × 10-13 cm3 s-1, which lies in the range of the previous results, (2.7 - 5.2) × 10-13 cm3 s-1.1 In addition to detection of CH3O2, products of the CH3O2 self-reaction were also observed for the two reaction channels over a range of temperatures from 260 - 320 K: (a) 2CH3O2 → CH2O + CH3OH; (b) 2CH3O2 → 2CH3O + O2, namely HO2 radicals (from reaction of CH3O + O2) and formaldehyde monitored by FAGE and formaldehyde and methanol observed by FTIR. A good agreement has been obtained between the FTIR and FAGE measurements of CH2O which increased to ˜ 2 ppmv over the experiments. Using the concentrations of CH3OH and CH2O, the branching ratio for channel (a) at room temperature has been determined as ra = 0.66 ± 0.06. The result is in very good agreement with the value recommended in the review of Tyndall et al.2 of ra = 0.63 ± 0.06. No temperature dependence of ra has been observed from 296 K to 321 K. 1. http://iupac.pole-ether.fr/ 2. G. S. Tyndall et al., J. Geophys. Res. 106, 12157 (2001).

Tunable room-temperature spin-selective optical Stark effect in solution-processed layered halide perovskites.

PubMed

Giovanni, David; Chong, Wee Kiang; Dewi, Herlina Arianita; Thirumal, Krishnamoorthy; Neogi, Ishita; Ramesh, Ramamoorthy; Mhaisalkar, Subodh; Mathews, Nripan; Sum, Tze Chien

2016-06-01

Ultrafast spin manipulation for opto-spin logic applications requires material systems that have strong spin-selective light-matter interaction. Conventional inorganic semiconductor nanostructures [for example, epitaxial II to VI quantum dots and III to V multiple quantum wells (MQWs)] are considered forerunners but encounter challenges such as lattice matching and cryogenic cooling requirements. Two-dimensional halide perovskite semiconductors, combining intrinsic tunable MQW structures and large oscillator strengths with facile solution processability, can offer breakthroughs in this area. We demonstrate novel room-temperature, strong ultrafast spin-selective optical Stark effect in solution-processed (C6H4FC2H4NH3)2PbI4 perovskite thin films. Exciton spin states are selectively tuned by ~6.3 meV using circularly polarized optical pulses without any external photonic cavity (that is, corresponding to a Rabi energy of ~55 meV and equivalent to applying a 70 T magnetic field), which is much larger than any conventional system. The facile halide and organic replacement in these perovskites affords control of the dielectric confinement and thus presents a straightforward strategy for tuning light-matter coupling strength.

Methane emissions from a landfill in north-east India: Performance of various landfill gas emission models.

PubMed

Gollapalli, Muralidhar; Kota, Sri Harsha

2018-03-01

Rapid urbanization and economic growth has led to significant increase in municipal solid waste generation in India during the last few decades and its management has become a major issue because of poor waste management practices. Solid waste generated is deposited into open dumping sites with hardly any segregation and processing. Carbon dioxide (CO 2 ), methane (CH 4 ) and nitrous oxide (N 2 O) are the major greenhouse gases that are released from the landfill sites due to the biodegradation of organic matter. In this present study, CH 4 and CO 2 emissions from a landfill in north-east India are estimated using a flux chamber during September, 2015 to August, 2016. The average emission rates of CH 4 and CO 2 are 68 and 92 mg/min/m 2 , respectively. The emissions are highest in the summer whilst being lowest in winter. The diurnal variation of emissions indicated that the emissions follow a trend similar to temperature in all the seasons. Correlation coefficients of CH 4 and temperature in summer, monsoon and winter are 0.99, 0.87 and 0.97, respectively. The measured CH 4 in this study is in the range of other studies around the world. Modified Triangular Method (MTM), IPCC model and the USEPA Landfill gas emissions model (LandGEM) were used to predict the CH 4 emissions during the study year. The consequent simulation results indicate that the MTM, LandGEM-Clean Air Act, LandGEM-Inventory and IPCC models predict 1.9, 3.3, 1.6 and 1.4 times of the measured CH 4 emission flux in this study. Assuming that this higher prediction of CH 4 levels observed in this study holds well for other landfills in this region, a new CH 4 emission inventory (Units: Tonnes/year), with a resolution of 0.1 0  × 0.1 0 has been developed. This study stresses the importance of biodegradable composition of waste and meteorology, and also points out the drawbacks of the widely used landfill emission models. Copyright © 2017 Elsevier Ltd. All rights reserved.

All-spinel oxide Josephson junctions for high-efficiency spin filtering.

PubMed

Mesoraca, S; Knudde, S; Leitao, D C; Cardoso, S; Blamire, M G

2018-01-10

Obtaining high efficiency spin filtering at room temperature using spinel ferromagnetic tunnel barriers has been hampered by the formation of antiphase boundaries due to their difference in lattice parameters between barrier and electrodes. In this work we demonstrate the use of LiTi 2 O 4 thin films as electrodes in an all-spinel oxide CoFe 2 O 4 -based spin filter devices. These structures show nearly perfect epitaxy maintained throughout the structure and so minimise the potential for APBs formation. The LiTi 2 O 4 in these devices is superconducting and so measurements at low temperature have been used to explore details of the tunnelling and Josephson junction behaviour.

Factors affecting methane production and mitigation in ruminants.

PubMed

Shibata, Masaki; Terada, Fuminori

2010-02-01

Methane (CH(4)) is the second most important greenhouse gas (GHG) and that emitted from enteric fermentation in livestock is the single largest source of emissions in Japan. Many factors influence ruminant CH(4) production, including level of intake, type and quality of feeds and environmental temperature. The objectives of this review are to identify the factors affecting CH(4) production in ruminants, to examine technologies for the mitigation of CH(4) emissions from ruminants, and to identify areas requiring further research. The following equation for CH(4) prediction was formulated using only dry matter intake (DMI) and has been adopted in Japan to estimate emissions from ruminant livestock for the National GHG Inventory Report: Y = -17.766 + 42.793X - 0.849X(2), where Y is CH(4) production (L/day) and X is DMI (kg/day). Technologies for the mitigation of CH(4) emissions from ruminants include increasing productivity by improving nutritional management, the manipulation of ruminal fermentation by changing feed composition, the addition of CH(4) inhibitors, and defaunation. Considering the importance of ruminant livestock, it is essential to establish economically feasible ways of reducing ruminant CH(4) production while improving productivity; it is therefore critical to conduct a full system analysis to select the best combination of approaches or new technologies to be applied under long-term field conditions.

Temperature dependence of the Cl atom reaction with deuterated methanes.

PubMed

Sauer, Frank; Portmann, Robert W; Ravishankara, A R; Burkholder, James B

2015-05-14

Kinetic isotope effect (KIE) and reaction rate coefficients, k1-k4, for the gas-phase reaction of Cl atoms with (12)CH3D (k1), (12)CH2D2 (k2), (12)CHD3 (k3), and (12)CD4 (k4) over the temperature range 223-343 K in 630 Torr of synthetic air are reported. Rate coefficients were measured using a relative rate technique with (12)CH4 as the primary reference compound. Fourier transform infrared spectroscopy was used to monitor the methane isotopologue loss. The obtained KIE values were (12)CH3D: KIE1(T) = (1.227 ± 0.004) exp((43 ± 5)/T); (12)CH2D2: KIE2(T) = (1.14 ± 0.20) exp((191 ± 60)/T); (12)CHD3: KIE3(T) = (1.73 ± 0.34) exp((229 ± 60)/T); and (12)CD4: KIE4(T) = (1.01 ± 0.3) exp((724 ± 19)/T), where KIEx(T) = kCl+(12)CH4(T)/kx(T). The quoted uncertainties are at the 2σ (95% confidence) level and represent the precision of our data. The following Arrhenius expressions and 295 K rate coefficient values (in units of cm(3) molecule(-1) s(-1)) were derived from the above KIE using a rate coefficient of 7.3 × 10(-12) exp(-1280/T) cm(3) molecule(-1) s(-1) for the reaction of Cl with (12)CH4: k1(T) = (5.95 ± 0.70) × 10(-12) exp(-(1323 ± 50)/T), k1(295 K) = (6.7 ± 0.8) × 10(-14); k2(T) = (6.4 ± 1.3) × 10(-12) exp(-(1471 ± 60)/T), k2(295 K) = (4.4 ± 0.9) × 10(-14); k3(T) = (4.2 ± 1.0) × 10(-12) exp(-(1509 ± 60)/T), k3(295 K) = (2.53 ± 0.6) × 10(-14); and k4(T) = (7.13 ± 2.3) × 10(-12) exp(-(2000 ± 120)/T), k4(295 K) = (0.81 ± 0.26) × 10(-14). The reported uncertainties in the pre-exponential factors are 2σ and include estimated systematic errors in our measurements and the uncertainty in the reference reaction rate coefficient. The results from this study are compared with previously reported room-temperature rate coefficients for each of the deuterated methanes as well as the available temperature dependent data for the Cl atom reactions with CH3D and CD4. A two-dimensional atmospheric chemistry model was used to examine the implications of the present results to the atmospheric lifetime and vertical variation in the loss of the deuterated methane isotopologues. The relative contributions of the reactions of OH, Cl, and O((1)D) to the loss of the isotopologues in the stratosphere were also examined. The results of the calculations are described and discussed.

The microwave spectrum of a triplet carbene: HCCN in the X 3Sigma - state

NASA Astrophysics Data System (ADS)

Saito, Shuji; Endo, Yasuki; Hirota, Eizi

1984-02-01

A simple carbene, the HCCN radical, has been identified in the gas phase using a microwave spectroscopic method. The HCCN molecule was generated in a free space absorption cell by the reaction of CH3CN with the microwave discharge products of CF4. Five rotational transitions, each split into three fine structure components, were observed in the region of 110 to 198 GHz. No hyperfine structure was resolved, although some of the observed lines showed broadening. The rotational constant, the centrifugal distortion constant, the spin-spin coupling constant, and the spin-rotation coupling constant were determined with good precision. The observed spectrum is completely consistent with that expected for a linear molecule in a 3Σ state, in agreement with an earlier matrix EPR study of Bernheim et al. [J. Chem. Phys. 43, 196 (1965)].

Chemical Properties of Dialkyl Halonium Ions (R2Hal+) and Their Neutral Analogues, Methyl Carboranes, CH3-(CHB11Hal11), Where Hal = F, Cl.

PubMed

Stoyanov, Evgenii S

2017-04-20

Chloronium cations in their salts (C n H 2n+1 ) 2 Cl + {CHB 11 Cl 11 - }, with n = 1 to 3 and exceptionally stable carborane anions, are stable at ambient and elevated temperatures. The temperature at which they decompose to carbocations with HCl elimination (below 150 °C) decreases with the increasing n from 1 to 3 because of increasing ionicity of C-Cl bonds in the C-Cl + -C bridge. At room temperature, the salts of cations with n ≥ 4 [starting from t-Bu 2 Cl + or (cyclo-C 5 H 11 ) 2 Cl + ] are unstable and decompose. With decreasing chloronium ion stability, their ability to interact with chloroalkanes to form oligomeric cations increases. It was shown indirectly that unstable salt of fluoronium ions (CH 3 ) 2 F + (CHB 11 F 11 - ) must exist at low temperatures. The proposed (CH 3 ) 2 F + cation is much more reactive than the corresponding chloronium, showing at room temperature chemical properties expected of (CH 3 ) 2 Cl + at elevated temperatures.

Effects of the η(5)-C5H4(i)Pr Ligand on the Properties Exhibited by Its Tungsten Nitrosyl Complexes.

PubMed

Fabulyak, Diana; Baillie, Rhett A; Patrick, Brian O; Legzdins, Peter; Rosenfeld, Devon C

2016-02-15

Reaction of Na[η(5)-C5H4(i)Pr] with W(CO)6 in refluxing THF for 4 days generates a solution of Na[(η(5)-C5H4(i)Pr)W(CO)3] that when treated with N-methyl-N-nitroso-p-toluenesulfonamide at ambient temperatures affords (η(5)-C5H4(i)Pr)W(NO)(CO)2 (1) that is isolable in good yield as an analytically pure orange oil. Treatment of 1 with an equimolar amount of I2 in Et2O at ambient temperatures affords (η(5)-C5H4(i)Pr)W(NO)I2 (2) as a dark brown solid in excellent yield. Sequential treatment at low temperatures of 2 with 0.5 equiv of Mg(CH2CMe3)2 and Mg(CH2CH═CMe2)2 in Et2O produces the alkyl allyl complex, (η(5)-C5H4(i)Pr)W(NO)(CH2CMe3)(η(3)-CH2CHCMe2) (3), as a thermally sensitive yellow liquid. Complex 3 may also be synthesized, albeit in low yield, in one vessel at low temperatures by reacting 1 first with 1 equiv of PCl5 and then with the binary magnesium reagents specified above. Interestingly, similar treatment of 1 in Et2O with PCl5 and only 0.5 equiv of Mg(CH2CH═CMe2)2 results in the formation of the unusual complex (η(5)-C5H4(i)Pr)W(NO)(PCl2CMe2CH═CH2)Cl2 (4), which probably is formed via a metathesis reaction of the binary magnesium reagent with (η(5)-C5H4(i)Pr)W(NO)(PCl3)Cl2. The C-D activation of C6D6 by complex 3 has been investigated and compared to that exhibited by its η(5)-C5Me5, η(5)-C5Me4H, and η(5)-C5Me4(n)Pr analogues. Kinetic analyses of the various activations have established that the presence of the η(5)-C5H4(i)Pr ligand significantly increases the rate of the reaction, an outcome that can be attributed to a combination of steric and electronic factors. In addition, mechanistic studies have established that in solution 3 loses neopentane under ambient conditions to generate exclusively the 16e η(2)-diene intermediate complex (η(5)-C5H4(i)Pr)W(NO)(η(2)-CH2═CMeCH═CH2), which then effects the subsequent C-D activations. This behavior contrasts with that exhibited by the η(5)-C5Me5 analogue of 3 which forms both η(2)-diene and η(2)-allene intermediates upon thermolysis. Sixteen-electron (η(5)-C5H4(i)Pr)W(NO)(η(2)-CH2═CMeCH═CH2) has been isolated as its 18e PMe3 adduct. All new organometallic complexes have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of two of them have been established by single-crystal X-ray crystallographic analyses.

A high-spin and durable polyradical: poly(4-diphenylaminium-1,2-phenylenevinylene).

PubMed

Murata, Hidenori; Takahashi, Masahiro; Namba, Kazuaki; Takahashi, Naoki; Nishide, Hiroyuki

2004-02-06

A purely organic, high-spin, and durable polyradical molecule was synthesized: It is based on the non-Kekulé- and non-disjoint design of a pi-conjugated poly(1,2-phenylenevinylene) backbone pendantly 4-substituted with multiple robust arylaminium radicals. 4-N,N-Bis(4-methoxy- and -tert-butylphenyl)amino-2-bromostyrene 5 were synthesized and polymerized with a palladium-phosphine catalyst to afford the head-to-tail-linked polyradical precursors (1). Oxidation of 1 with the nitrosonium ion solubilized with a crown ether gave the aminium polyradicals (1(+)()) which were durable (half-life > 1 month) at room temperature in air. A high-spin ground state with an average S = (4.5)/2 for 1a(+) was proved even at room temperature by magnetic susceptibility, magnetization, ESR, and NMR measurements.

Empirical determination of low J values of 13CH4 transitions from jet cooled and 80 K cell spectra in the icosad region (7170-7367 cm-1)

NASA Astrophysics Data System (ADS)

Votava, O.; Mašát, M.; Pracna, P.; Mondelain, D.; Kassi, S.; Liu, A. W.; Hu, S. M.; Campargue, A.

2014-12-01

The absorption spectrum of 13CH4 was recorded at two low temperatures in the icosad region near 1.38 μm, using direct absorption tunable diode lasers. Spectra were obtained using a cryogenic cell cooled at liquid nitrogen temperature (80 K) and a supersonic jet providing a 32 K rotational temperature in the 7173-7367 cm-1 and 7200-7354 cm-1 spectral intervals, respectively. Two lists of 4498 and 339 lines, including absolute line intensities, were constructed from the 80 K and jet spectra, respectively. All the transitions observed in jet conditions were observed at 80 K. From the temperature variation of their line intensities, the corresponding lower state energy values were determined. The 339 derived empirical values of the J rotational quantum number are found close to integer values and are all smaller than 4, as a consequence of the efficient rotational cooling. Six R(0) transitions have been identified providing key information on the origins of the vibrational bands which contribute to the very congested and not yet assigned 13CH4 spectrum in the considered region of the icosad.

Structural and energetic properties of acetonitrile-Group IV (A & B) halide complexes.

PubMed

Helminiak, Heather M; Knauf, Robin R; Danforth, Samuel J; Phillips, James A

2014-06-19

We have conducted an extensive computational study of the structural and energetic properties of select acetonitrile-Group IV (A & B) tetrahalide complexes, both CH3CN-MX4 and (CH3CN)2-MX4 (M = Si, Ge, Ti; X = F, Cl). We have also examined the reactivity of CH3CN with SiF4, SiCl4, GeCl4, and TiCl4, and measured low-temperature IR spectra of thin films containing CH3CN with SiF4, GeCl4, or TiCl4. The six 1:1 complexes fall into two general structural classes. CH3CN-TiCl4, CH3CN-TiF4, and CH3CN-GeF4, exhibit relatively short M-N bonds (~2.3 Å), an intermediate degree of distortion in the MX4 subunit, and binding energies ranging from 11.0 to 13.0 kcal/mol. Conversely, CH3CN-GeCl4, CH3CN-SiF4, and CH3CN-SiCl4, are weakly bonded systems, with long M-N distances (>3.0 Å), little distortion in the MX4 subunit, and binding energies ranging from 3.0 to 4.4 kcal/mol. The structural features of analogous 2:1 systems resemble those of their 1:1 counterparts, whereas the binding energies (relative to three isolated fragments) are roughly twice as large. Calculated M-N potential curves in the gas phase and bulk, dielectric media are reported for all 1:1 complexes, and for two systems, CH3CN-GeF4 and CH3CN-SiF4, these data predict significant condensed-phase structural changes. The effect on the CH3CN-SiF4 potential is extreme; the curve becomes quite flat over a broad range in dielectric media, and at higher ε values, the global minimum shifts inward by about 1.0 Å. In bulk reactivity experiments, no reaction was observed between CH3CN and SiF4, SiCl4, or GeCl4, whereas CH3CN and TiCl4 were found to react immediately upon contact. Also, thin-film IR spectra indicate a strong interaction between CH3CN and TiCl4, yet only weak interactions between CH3CN and GeCl4 or SiF4 in the solid state.

Soil Methane uptake Model (MeMo): a process based model for global methane consumption by soils

NASA Astrophysics Data System (ADS)

Murguia-Flores, F.; Arndt, S.; Ganesan, A.; Hornibrook, E. R. C.; Murray-Tortarolo, G.

2016-12-01

Atmospheric methane (CH4) is a powerful greenhouse gas, responsible for 20% of global warming. The only terrestrial and biological sink is the uptake in the soils by methanotrophic bacteria, however there is large spatial and temporal heterogeneity in the magnitude of this sink. One way to provide a global understanding of this process is by using a mathematical model to simulate the mechanisms of the underlying physical and biological drivers. Here we present the soil Methane uptake Model (MeMo) a process-based model for the global methane consumption by soils. We have built on previous models by Ridgwell et al., (1999) and Curry et al., (2007), by making several advances. First, a general analytical solution of the one-dimensional diffusion-reaction equation was implemented that accounts for a maximum uptake depth and for a CH4 flux coming from below the surface (i.e. CH4 production in the soil). Secondly, we revisited and improved the effect of nitrogen inhibition, soil moisture and soil temperature on CH4 uptake in the light of newly available data and advances in our understanding of these drivers. Using observed forcing data, we estimated a global mean CH4 uptake of 31.2±1.2 Tg y-1 for the period 1990-2009 with an increasing trend of 0.1 Tg y-2. Our model represented the latitudinal pattern of uptake shown by field observations, with the highest uptake per unit area occurring over dry tropical forest and the lowest uptake in the polar desert. The highest seasonality occurred in the Northern Hemisphere, showing that the main driver of variability in a given year is from a combination of temperature and soil moisture. Our model showed that CH4 uptake is reduced from previous studies by approximately 10% at the regions with the highest nitrogen deposition: East Asia and Europe. Finally, our results suggest that more field measurements are needed to improve the modelling of the process, such as the basal oxidation rate for different ecosystems, the Q10 temperature response across different conditions and long term field CH4 uptake records.

Was Early Mars Warmed by CH4?

NASA Astrophysics Data System (ADS)

Justh, H. L.; Kasting, J. F.

2001-12-01

Images from the Mariner, Viking and Mars Global Surveyor missions have shown geologic features on the Martian surface that seem to indicate an earlier period of hydrologic activity. Many researchers have suggested that the early Martian climate was more Earth-like with a Ts of 273 K or higher. The presence of liquid water would require a greenhouse effect much larger than needed at present since S0 is 25% lower 3.8 billion years ago when the channels are thought to have formed. Research into the effects of CO2 clouds upon the climate of early Mars have yielded results that would not effectively warm the surface to the temperature needed to account for the presence of liquid water. Forget and Pierrehumbert (Science, 1997) showed that large crystals of CO2 ice in clouds that form in the upper troposphere would produce a strong warming effect. Obtaining mean surface temperatures above 273 K would require 100% cloud cover, a condition that is unrealistic for early Mars. It has also been shown that any reduction in cloud cover makes it difficult to achieve warm Martian surface temperatures except at high pressures. CO2 clouds could also cool the Martian surface if they were low and optically thick. CO2 ice may be hard to nucleate, leading to the formation of very large particles (Glandorf, private communication). CH4 has been suggested as an important greenhouse gas on the early Earth. This has led us to look at CH4 as a potential solution to the early Mars climate issue. To investigate the possible warming effect of CH4, we utilized a modified, one-dimensional, radiative-convective climate model that has been used in previous studies of the early Martian climate. New calculations of the effects of CH4 upon the early Martian climate will be presented. The use of CH4 to warm the surface of early Mars does not necessarily imply the presence of life on Mars. Abiotic sources of CH4, such as serpentinization of ultramafic rocks, could supply the concentrations needed to warm the surface.

Stability of peatland carbon to rising temperatures

DOE PAGES

Wilson, R. M.; Hopple, A. M.; Tfaily, M. M.; ...

2016-12-13

Peatlands contain one-third of soil carbon (C), mostly buried in deep, saturated anoxic zones (catotelm). The response of catotelm C to climate forcing is uncertain, because prior experiments have focused on surface warming. Here, we show that deep peat heating of a 2 m-thick peat column results in an exponential increase in CH 4 emissions. But, this response is due solely to surface processes and not degradation of catotelm peat. Incubations show that only the top 20–30 cm of peat from experimental plots have higher CH 4 production rates at elevated temperatures. Radiocarbon analyses demonstrate that CH 4 and COmore » 2 are produced primarily from decomposition of surface-derived modern photosynthate, not catotelm C. Furthermore, there are no differences in microbial abundances, dissolved organic matter concentrations or degradative enzyme activities among treatments. Our results suggest that although surface peat will respond to increasing temperature, the large reservoir of catotelm C is stable under current anoxic conditions.« less

Stability of peatland carbon to rising temperatures

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

Wilson, R. M.; Hopple, A. M.; Tfaily, M. M.

Peatlands contain one-third of soil carbon (C), mostly buried in deep, saturated anoxic zones (catotelm). The response of catotelm C to climate forcing is uncertain, because prior experiments have focused on surface warming. Here, we show that deep peat heating of a 2 m-thick peat column results in an exponential increase in CH 4 emissions. But, this response is due solely to surface processes and not degradation of catotelm peat. Incubations show that only the top 20–30 cm of peat from experimental plots have higher CH 4 production rates at elevated temperatures. Radiocarbon analyses demonstrate that CH 4 and COmore » 2 are produced primarily from decomposition of surface-derived modern photosynthate, not catotelm C. Furthermore, there are no differences in microbial abundances, dissolved organic matter concentrations or degradative enzyme activities among treatments. Our results suggest that although surface peat will respond to increasing temperature, the large reservoir of catotelm C is stable under current anoxic conditions.« less

Growth, and magnetic study of Sm0.4Er0.6FeO3 single crystal grown by optical floating zone technique

NASA Astrophysics Data System (ADS)

Wu, Anhua; Zhao, Xiangyang; Man, Peiwen; Su, Liangbi; Kalashnikova, A. M.; Pisarev, R. V.

2018-03-01

Sm0.4Er0.6FeO3 single crystals were successfully grown by optical floating zone method; high quality samples with various orientations were manufactured. Based on these samples, Magnetic property of Sm0.4Er0.6FeO3 single crystals were investigated systemically by means of the temperature dependence of magnetization. It indicated that compositional variations not only alter the spin reorientation temperature, but also the compensation temperature of the orthoferrites. Unlike single rare earth orthoferrites, the reversal transition temperature point of Sm0.4Er0.6FeO3 increases as magnetic field increases, which is positive for designing novel spin switching or magnetic sensor device.

Effects of Different Vegetation Zones on CH4 and N2O Emissions in Coastal Wetlands: A Model Case Study

PubMed Central

Liu, Yuhong; Wang, Lixin; Bao, Shumei; Liu, Huamin; Yu, Junbao; Wang, Yu; Shao, Hongbo; Ouyang, Yan; An, Shuqing

2014-01-01

The coastal wetland ecosystems are important in the global carbon and nitrogen cycle and global climate change. For higher fragility of coastal wetlands induced by human activities, the roles of coastal wetland ecosystems in CH4 and N2O emissions are becoming more important. This study used a DNDC model to simulate current and future CH4 and N2O emissions of coastal wetlands in four sites along the latitude in China. The simulation results showed that different vegetation zones, including bare beach, Spartina beach, and Phragmites beach, produced different emissions of CH4 and N2O in the same latitude region. Correlation analysis indicated that vegetation types, water level, temperature, and soil organic carbon content are the main factors affecting emissions of CH4 and N2O in coastal wetlands. PMID:24892044

Large-scale controls of methanogenesis inferred from methane and gravity spaceborne data.

PubMed

Bloom, A Anthony; Palmer, Paul I; Fraser, Annemarie; Reay, David S; Frankenberg, Christian

2010-01-15

Wetlands are the largest individual source of methane (CH4), but the magnitude and distribution of this source are poorly understood on continental scales. We isolated the wetland and rice paddy contributions to spaceborne CH4 measurements over 2003-2005 using satellite observations of gravity anomalies, a proxy for water-table depth Gamma, and surface temperature analyses TS. We find that tropical and higher-latitude CH4 variations are largely described by Gamma and TS variations, respectively. Our work suggests that tropical wetlands contribute 52 to 58% of global emissions, with the remainder coming from the extra-tropics, 2% of which is from Arctic latitudes. We estimate a 7% rise in wetland CH4 emissions over 2003-2007, due to warming of mid-latitude and Arctic wetland regions, which we find is consistent with recent changes in atmospheric CH4.

Large-Scale Controls of Methanogenesis Inferred from Methane and Gravity Spaceborne Data

NASA Astrophysics Data System (ADS)

Bloom, A. Anthony; Palmer, Paul I.; Fraser, Annemarie; Reay, David S.; Frankenberg, Christian

2010-01-01

Wetlands are the largest individual source of methane (CH4), but the magnitude and distribution of this source are poorly understood on continental scales. We isolated the wetland and rice paddy contributions to spaceborne CH4 measurements over 2003-2005 using satellite observations of gravity anomalies, a proxy for water-table depth Γ, and surface temperature analyses TS. We find that tropical and higher-latitude CH4 variations are largely described by Γ and TS variations, respectively. Our work suggests that tropical wetlands contribute 52 to 58% of global emissions, with the remainder coming from the extra-tropics, 2% of which is from Arctic latitudes. We estimate a 7% rise in wetland CH4 emissions over 2003-2007, due to warming of mid-latitude and Arctic wetland regions, which we find is consistent with recent changes in atmospheric CH4.

Finite-temperature dynamics of the Mott insulating Hubbard chain

NASA Astrophysics Data System (ADS)

Nocera, Alberto; Essler, Fabian H. L.; Feiguin, Adrian E.

2018-01-01

We study the dynamical response of the half-filled one-dimensional Hubbard model for a range of interaction strengths U and temperatures T by a combination of numerical and analytical techniques. Using time-dependent density matrix renormalization group computations we find that the single-particle spectral function undergoes a crossover to a spin-incoherent Luttinger liquid regime at temperatures T ˜J =4 t2/U for sufficiently large U >4 t . At smaller values of U and elevated temperatures the spectral function is found to exhibit two thermally broadened bands of excitations, reminiscent of what is found in the Hubbard-I approximation. The dynamical density-density response function is shown to exhibit a finite-temperature resonance at low frequencies inside the Mott gap, with a physical origin similar to the Villain mode in gapped quantum spin chains. We complement our numerical computations by developing an analytic strong-coupling approach to the low-temperature dynamics in the spin-incoherent regime.