Synthesis of opioidmimetics, 3-[H-Dmt-NH(CH(2))(m)]-6-[H-Dmt-NH(CH(2))(n)]-2(1H)-pyrazinones, and studies on structure-activity relationships.

PubMed

Shiotani, Kimitaka; Miyazaki, Anna; Li, Tingyou; Tsuda, Yuko; Yokoi, Toshio; Ambo, Akihiro; Sasaki, Yusuke; Bryant, Sharon D; Jinsmaa, Yunden; Lazarus, Lawrence H; Okada, Yoshio

2007-11-01

Opioidmimetics containing 3-[H-Dmt-NH-(CH(2))(m)]-6-[H-Dmt-NH-(CH(2))(n)]-2(1H)-pyrazinone symmetric (m = n, 1-4) (1 - 4) and asymmetric (m, n = 1 - 4) aliphatic chains (5 - 16) were synthesized using dipeptidyl chloromethylketone intermediates. They had high mu-affinity (K(i)mu = 0.021 - 2.94 nM), delta-affinity (K(i)delta = 1.06 - 152.6 nM), and mu selectivity (K(i)delta/K(i)mu = 14 - 3,126). The opioidmimetics (1 - 16) exhibited mu agonism in proportion to their mu-receptor affinity. delta-Agonism was essentially lacking in the compounds except (4) and (16), and (1) and (2) indicated weak delta antagonism (pA(2) = 6.47 and 6.56, respectively). The data verify that a specific length of aliphatic linker is required between the Dmt pharmacophore and the pyrazinone ring to produce unique mu-opioid receptor ligands.

River Protection Project (RPP) Readiness to Proceed 2 Internal Independent Review Team Final Report

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

SCHAUS, P.S.

This report describes the results of an independent review team brought in to assess CH2M Hill Hanford Group's readiness and ability to support the RPP's move into its next major phase - retrieval and delivery of tank waste to the Privatization Contractor

The C-H Stretching Features at 3.2--3.5 μm of Polycyclic Aromatic Hydrocarbons with Aliphatic Sidegroups

NASA Astrophysics Data System (ADS)

Yang, X. J.; Li, Aigen; Glaser, R.; Zhong, J. X.

2016-07-01

The so-called “unidentified” infrared emission (UIE) features at 3.3, 6.2, 7.7, 8.6, and 11.3 μm are ubiquitously seen in a wide variety of astrophysical regions. The UIE features are characteristic of the stretching and bending vibrations of aromatic hydrocarbon materials, e.g., polycyclic aromatic hydrocarbon (PAH) molecules. The 3.3 μm aromatic C-H stretching feature is often accompanied by a weaker feature at 3.4 μm. The latter is generally thought to result from the C-H stretch of aliphatic groups attached to the aromatic systems. The ratio of the observed intensity of the 3.3 μm aromatic C-H feature to that of the 3.4 μm aliphatic C-H feature allows one to estimate the aliphatic fraction of the UIE carriers, provided that the intrinsic oscillator strengths of the 3.3 μm aromatic C-H stretch ({A}3.3) and the 3.4 μm aliphatic C-H stretch ({A}3.4) are known. While previous studies on the aliphatic fraction of the UIE carriers were mostly based on the {A}3.4/{A}3.3 ratios derived from the mono-methyl derivatives of small PAH molecules, in this work we employ density functional theory to compute the infrared vibrational spectra of PAH molecules with a wide range of sidegroups including ethyl, propyl, butyl, and several unsaturated alkyl chains, as well as all the isomers of dimethyl-substituted pyrene. We find that, except for PAHs with unsaturated alkyl chains, the corresponding {A}3.4/{A}3.3 ratios are close to that of mono-methyl PAHs. This confirms the predominantly aromatic nature of the UIE carriers previously inferred from the {A}3.4/{A}3.3 ratio derived from mono-methyl PAHs.

Interaction of antitumor drug Sn(CH 3) 2Cl 2 with DNA and RNA

NASA Astrophysics Data System (ADS)

Nafisi, Shohreh; Sobhanmanesh, Amir; Esm-Hosseini, Majid; Alimoghaddam, Kamran; Tajmir-Riahi, Heidar Ali

2005-08-01

Sn(CH3)2Cl2 exerts its antitumor activity in a specific way. Unlike anticancer cis-Pt(NH3)2Cl2 drug which binds strongly to the nitrogen atoms of DNA bases, Sn(CH3)2Cl2 shows no major affinity towards base binding. Thus, the mechanism of action by which tinorganometallic compounds exert antitumor activity would be different from that of the cisplatin drug. The aim of this study was to examine the binding of Sn(CH3)2Cl2 with calf thymus DNA and yeast RNA in aqueous solutions at pH 7.1-6.6 with constant concentrations of DNA and RNA and various molar ratios of Sn(CH3)2Cl2/DNA (phosphate) and Sn(CH3)2Cl2/RNA of 1/40, 1/20, 1/10, 1/5. Fourier transform infrared (FTIR) and UV-visible difference spectroscopic methods were used to determine the Sn(CH3)2Cl2 binding mode, binding constant, sequence selectivity and structural variations of Sn(CH3)2Cl2/DNA and Sn(CH3)2Cl2/RNA complexes in aqueous solution. Sn(CH3)2Cl2 hydrolyzes in water to give Sn(CH3)2(OH)2 and [Sn(CH3)2(OH)(H2O)n]+ species. Spectroscopic evidence showed that interaction occurred mainly through (CH3)2Sn(IV) hydroxide and polynucleotide backbone phosphate group with overall binding constant of K(Sn(CH3)2Cl2-DNA)=1.47×105 M-1 and K(Sn(CH3)2Cl2-RNA)=7.33×105 M-1. Sn(CH3)2Cl2 induced no biopolymer conformational changes with DNA remaining in the B-family structure and RNA in A-conformation upon drug complexation.

Dangerous Waste Characteristics of Contact-Handled Transuranic Mixed Wastes from Hanford Tanks

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

Tingey, Joel M.; Bryan, Garry H.; Deschane, Jaquetta R.

2004-10-05

This report summarizes existing analytical data gleaned from samples taken from the Hanford tanks designated as potentially containing transuranic mixed process wastes. Process knowledge of the wastes transferred to these tanks has been reviewed to determine whether the dangerous waste characteristics now assigned to all Hanford underground storage tanks are applicable to these particular wastes. Supplemental technologies are being examined to accelerate the Hanford tank waste cleanup mission and accomplish waste treatment safely and efficiently. To date, 11 Hanford waste tanks have been designated as potentially containing contact-handled (CH) transuranic mixed (TRUM) wastes. The CH-TRUM wastes are found in single-shellmore » tanks B-201 through B-204, T-201 through T-204, T-104, T-110, and T-111. Methods and equipment to solidify and package the CH-TRUM wastes are part of the supplemental technologies being evaluated. The resulting packages and wastes must be acceptable for disposal at the Waste Isolation Pilot Plant (WIPP). The dangerous waste characteristics being considered include ignitability, corrosivity, reactivity, and toxicity arising from the presence of 2,4,5-trichlorophenol at levels above the dangerous waste threshold. The analytical data reviewed include concentrations of sulfur, sulfate, cyanide, 2,4,5-trichlorophenol, total organic carbon, and oxalate; the composition of the tank headspace, pH, and mercury. Differential scanning calorimetry results were used to determine the energetics of the wastes as a function of temperature. This report supercedes and replaces PNNL-14832.« less

Kinetics of OH- and Cl-initiated oxidation of CH2dbnd CHC(O)O(CH2)2CH3 and CH2dbnd CHCH2C(O)O(CH2)2CH3 and fate of the alkoxy radicals formed

NASA Astrophysics Data System (ADS)

Rivela, Cynthia; Blanco, María B.; Teruel, Mariano A.

2016-05-01

Rate coefficients of the reactions of OH and Cl radicals with vinyl and allyl butyrate were determined for the first time at 298 K and 1 atm using the relative method to be (in cm3 molecule-1 s-1): k1(OH + CH2dbnd CHC(O)O(CH2)2CH3) = (2.61 ± 0.31) × 10-11, k2(Cl + CH2dbnd CHC(O)O(CH2)2CH3) = (2.48 ± 0.89) × 10-10, k3(OH + CH2dbnd CHCH2C(O)O(CH2)2CH3) = (2.89 ± 0.31) × 10-11, and k4(Cl + CH2dbnd CHCH2C(O)O(CH2)2CH3) = (2.25 ± 0.96) × 10-10. Reactivity trends and atmospheric lifetimes of esters are presented. Additionally, a product study shown butyric acid and polifunctional products for the reactions of vinyl and allyl butyrate, respectively and general mechanism is proposed.

Hanford Tanks 241-C-203 and 241-C-204: Residual Waste Contaminant Release Model and Supporting Data

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

Deutsch, William J.; Krupka, Kenneth M.; Lindberg, Michael J.

This report describes the development of release models for key contaminants that are present in residual sludge remaining after closure of Hanford Tanks 241-C-203 (C-203) and 241-C-204 (C-204). The release models were developed from data generated by laboratory characterization and testing of samples from these two tanks. Key results from this work are (1) future releases from the tanks of the primary contaminants of concern (99Tc and 238U) can be represented by relatively simple solubility relationships between infiltrating water and solid phases containing the contaminants; and (2) high percentages of technetium-99 in the sludges (20 wt% in C-203 and 75more » wt% in C-204) are not readily water leachable, and, in fact, are very recalcitrant. This is similar to results found in related studies of sludges from Tank AY-102. These release models are being developed to support the tank closure risk assessments performed by CH2M HILL Hanford Group, Inc., for the U.S. Department of Energy.« less

Coupled-cluster sum-frequency generation nonlinear susceptibilities of methyl (CH3) and methylene (CH2) groups.

PubMed

Tetsassi Feugmo, Conrard Giresse; Liégeois, Vincent; Champagne, Benoît

2017-11-15

The first vibrational sum frequency generation (SFG) spectra based on molecular properties calculated at the coupled cluster singles and doubles (CCSD) level of approximation have been simulated for interfacial model alkyl chains, providing benchmark data for comparisons with approximate methods, including density functional theory (DFT). The approach proceeds in three steps. In the first two steps, the molecular spectral properties are determined: the vibrational normal modes and frequencies and then the derivatives of the dipole moment and of the polarizability with respect to the normal coordinates. These derivatives are evaluated with a numerical differentiation approach, of which the accuracy was monitored using Romberg's procedure. Then, in the last step, a three-layer model is employed to evaluate the macroscopic second-order nonlinear optical responses and thereby the simulated SFG spectra of the alkyl interface. Results emphasize the following facts: (i) the dipole and polarizability derivatives calculated at the DFT level with the B3LYP exchange-correlation functional can differ, with respect to CCSD, by as much as ±10 to 20% and ±20 to 50% for the CH 3 and CH 2 vibrations, respectively; (ii) these differences are enhanced when considering the SFG intensities as well as their variations as a function of the experimental configuration (ppp versus ssp) and as a function of the tilt and rotation angles, defining the orientation of the alkyl chain at the interface; (iii) these differences originate from both the vibrational normal coordinates and the Cartesian derivatives of the dipole moment and polarizability; (iv) freezing the successive fragments of the alkyl chain strongly modifies the SFG spectrum and enables highlighting the delocalization effects between the terminal CH 3 group and its neighboring CH 2 units; and finally (v) going from the free chain to the free methyl model, and further to C 3v constraints on leads to large variations of two ratios

CH(X2∏, a4∑-) ... OH2 and CH2(X˜3B1, ã1A1) ... OH2 interactions. A first principles investigation

NASA Astrophysics Data System (ADS)

Tzeli, Demeter; Mavridis, Aristides

We have investigated the interaction of the methylidene, CH(X2∏, a4∑-) and methylene, CH2(X˜3B1, ã1A1) with H2O, employing the (P)MPn (n = 2, 4) techniques in conjunction with the sequence of correlation consistent basis sets aug-cc-pVxZ, x = 2, 3, and 4. For the CH ... OH2 system, we have located four minima (m) and three transition states (ts) and for the CH2 ... OH2, five minima and four transition states. All our results have been corrected for zero-point energy (ZPE) and basis set superposition errors (BSSE), while for the most important m_ structures, we report complete basis set (CBS) interaction limits. We also report fully optimized geometries, harmonic frequencies, dipole moments, Mulliken charges, and potential energy curves. The highest CH(X2∏) ... OH2 (m1_2∏) and CH2(ã1A1) ... OH2 (m1_1A1) interactions are the result of electron transfer from the oxygen atom to the empty pπ orbitals of CH(X2∏) and CH2(ã1A1), respectively (ylide-like structures). At the (P)MP4/AQZ//MP2/ATZ level, including ZPE, BSSE, and CBS extrapolation, we obtain ΔE0(BSSE)+CBS = -9.36 kcal/mol at rC ... O = 1.752 Å, and -9.73 kcal/mol at rC ... O = 1.741 Å for the m1_2∏ and m1_1A1, respectively.

Synthesis and Thermal Stability of Novel Poly(M-Carborane-Siloxanes) with Various Pendant Groups

NASA Astrophysics Data System (ADS)

Yang, Xiaoxue; Zhao, Yanyan; Wang, Cuicui; Zhang, Xiaoa; Jiang, Shengling; Lyu, Yafei

2017-10-01

Poly(m-carborane-siloxanes) with various pendant groups (P15-P46) were synthesized via polycondensation of m-carborane-containing disilanols (1-4) and highly active bisureidosilanes (5 and 6). The obtained polymers exhibit controlled molecular weight by carefully adjusting the monomer ratio. Standard spectroscopic techniques including FTIR and NMR were utilized to characterize these polymers and satisfactory results were obtained. TGA analysis indicated that the thermal cyclization of polysiloxanes under nitrogen was greatly postponed by the incorporated m-carborane cage, since the siloxane bonds within the main chain were strengthened by the inductive effect of the latter. DSC and FTIR results confirmed that both siloxane unit and carborane cage were oxidized at elevated temperature under air, which contributed to the transformation of the polymers into the mixture of SiO2 and B2O3. Therefore, high char yield was obtained. Besides, the electronic effect of pendant groups greatly influenced the degradation behavior of m-carborane-containing polysiloxanes, having nothing to do with their position. The initial degradation temperature (T d5) increases with varying substituent in the order: CH2CH2CF3 < CH3 ≈ Ph < CH=CH2.

Competing E2 and SN2 Mechanisms for the F- + CH3CH2I Reaction.

PubMed

Yang, Li; Zhang, Jiaxu; Xie, Jing; Ma, Xinyou; Zhang, Linyao; Zhao, Chenyang; Hase, William L

2017-02-09

Anti-E2, syn-E2, inv-, and ret-S N 2 reaction channels for the gas-phase reaction of F - + CH 3 CH 2 I were characterized with a variety of electronic structure calculations. Geometrical analysis confirmed synchronous E2-type transition states for the elimination of the current reaction, instead of nonconcerted processes through E1cb-like and E1-like mechanisms. Importantly, the controversy concerning the reactant complex for anti-E2 and inv-S N 2 paths has been clarified in the present work. A positive barrier of +19.2 kcal/mol for ret-S N 2 shows the least feasibility to occur at room temperature. Negative activation energies (-16.9, -16.0, and -4.9 kcal/mol, respectively) for inv-S N 2, anti-E2, and syn-E2 indicate that inv-S N 2 and anti-E2 mechanisms significantly prevail over the eclipsed elimination. Varying the leaving group for a series of reactions F - + CH 3 CH 2 Y (Y = F, Cl, Br, and I) leads to monotonically decreasing barriers, which relates to the gradually looser TS structures following the order F > Cl > Br > I. The reactivity of each channel nearly holds unchanged except for the perturbation between anti-E2 and inv-S N 2. RRKM calculation reveals that the reaction of the fluorine ion with ethyl iodide occurs predominately via anti-E2 elimination, and the inv-S N 2 pathway is suppressed, although it is energetically favored. This phenomenon indicates that, in evaluating the competition between E2 and S N 2 processes, the kinetic or dynamical factors may play a significant role. By comparison with benchmark CCSD(T) energies, MP2, CAM-B3LYP, and M06 methods are recommended to perform dynamics simulations of the title reaction.

Dangerous Waste Characteristics of Contact-Handled Transuranic Mixed Wastes from the Hanford Tanks

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

Tingey, Joel M.; Bryan, Garry H.; Deschane, Jaquetta R.

2004-08-31

This report summarizes existing analytical data from samples taken from the Hanford tanks designated as potentially containing transuranic mixed process wastes. Process knowledge of the wastes transferred to these tanks has been reviewed to determine whether the dangerous waste characteristics now assigned to all Hanford underground storage tanks are applicable to these particular wastes. Supplemental technologies are being examined to accelerate the Hanford tank waste cleanup mission and accomplish waste treatment safely and efficiently. To date, 11 Hanford waste tanks have been designated as potentially containing contact-handled (CH) transuranic mixed (TRUM) wastes. The CH-TRUM wastes are found in single-shell tanksmore » B-201 through B-204, T-201 through T-204, T-104, T-110, and T-111. Methods and equipment to solidify and package the CH-TRUM wastes are part of the supplemental technologies being evaluated. The resulting packages and wastes must be acceptable for disposal at the Waste Isolation Pilot Plant (WIPP). The dangerous waste characteristics being considered include ignitability, corrosivity, reactivity, and toxicity arising from the presence of 2,4,5-trichlorophenol at levels above the dangerous waste threshold. The analytical data reviewed include concentrations of sulfur, sulfate, cyanide, 2,4,5-trichlorophenol, total organic carbon, and oxalate; the composition of the tank headspace, pH, and mercury. Differential scanning calorimetry results were used to determine the energetics of the wastes as a function of temperature.« less

2,2‧,2″-Thiotris(acetic acid) betaine, S(CH2COOH)2(CH2COO), and 2,2‧,2″-selenotris(acetic acid) betaine, Se(CH2COOH)2(CH2COO)

NASA Astrophysics Data System (ADS)

Doudin, Khalid; Törnroos, Karl W.

2017-04-01

The title compounds, X(CH2COOH)2(CH2COO), X = S, 1, and X = Se, 2, have been characterised by FTIR, NMR and MS and by their crystal structures at 123(2) K. The FTIR spectra show two major peaks, at 1396 and 1731 cm-1 in 1 and at 1390 and 1721 cm-1 in 2. The 77Se NMR signal of 2 at 325.5 ppm is 83.4 ppm downfield from the signal of Se(CH2COOH)2 indicating a substantial selenonium character of 2. The two compounds are isostructural and have a pyramidal configuration. The C-X-C bond angles range from 99.29 to 103.14° in 1 and from 97.56 to 99.87° in 2. The Xsbnd Csbnd Cdbnd O torsion angles for the three substituents are most different; one of the carboxylic acid groups attains the anti-conformation with rather short S⋯O(H) and Se⋯O(H) distances, 2.744 and 2.750 Å, the other acid group is synclinal and with longer S⋯Odbnd C and Se⋯Odbnd C distances, 3.063 and 3.090 Å, whereas the carboxylate group is in the Xsbnd Csbnd C plane with X⋯Osbnd C distances of 2.869 and 2.908 Å in 1 and 2. The presence of these strong X⋯O interactions is suggested to be the cause for the very low Bronsted basicity of this class of betaines preventing salts of the corresponding acids, the presently unknown [X(CH2COOH)3]+ - cations, to be isolated. The molecules are linked together with two fairly strong but different hydrogen bonds to the carboxylate oxygen atoms with O⋯O distances of 2.493 and 2.580 Å in 1 and 2.489 and 2.581 Å in 2 and with one X⋯Odbnd C contact, 3.244 Å in 1 and 3.209 Å in 2. The carbonyl oxygen atoms do not participate significantly in intermolecular hydrogen bonding and there are no contacts between the heteroatoms.

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.

New superhindered polydentate polyphosphine ligands P(CH2CH2P(t)Bu2)3, PhP(CH2CH2P(t)Bu2)2, P(CH2CH2CH2P(t)Bu2)3, and their ruthenium(II) chloride complexes.

PubMed

Gilbert-Wilson, Ryan; Field, Leslie D; Bhadbhade, Mohan M

2012-03-05

The synthesis and characterization of the extremely hindered phosphine ligands, P(CH(2)CH(2)P(t)Bu(2))(3) (P(2)P(3)(tBu), 1), PhP(CH(2)CH(2)P(t)Bu(2))(2) (PhP(2)P(2)(tBu), 2), and P(CH(2)CH(2)CH(2)P(t)Bu(2))(3) (P(3)P(3)(tBu), 3) are reported, along with the synthesis and characterization of ruthenium chloro complexes RuCl(2)(P(2)P(3)(tBu)) (4), RuCl(2)(PhP(2)P(2)(tBu)) (5), and RuCl(2)(P(3)P(3)(tBu)) (6). The bulky P(2)P(3)(tBu) (1) and P(3)P(3)(tBu) (3) ligands are the most sterically encumbered PP(3)-type ligands so far synthesized, and in all cases, only three phosphorus donors are able to bind to the metal center. Complexes RuCl(2)(PhP(2)P(2)(tBu)) (5) and RuCl(2)(P(3)P(3)(tBu)) (6) were characterized by crystallography. Low temperature solution and solid state (31)P{(1)H} NMR were used to demonstrate that the structure of RuCl(2)(P(2)P(3)(tBu)) (4) is probably analogous to that of RuCl(2)(PhP(2)P(2)(tBu)) (5) which had been structurally characterized.

Conformational and spectroscopic study of xanthogen ethyl formates, ROC(S)SC(O)OCH2CH3. Isolation of CH3CH2OC(O)SH

NASA Astrophysics Data System (ADS)

Juncal, Luciana C.; Cozzarín, Melina V.; Romano, Rosana M.

2015-03-01

ROC(S)SC(O)OCH2CH3, with R = CH3sbnd , (CH3)2CHsbnd and CH3(CH2)2sbnd , were obtained through the reaction between potassium xanthate salts, ROC(S)SK, and ethyl chloroformate, ClC(O)OCH2CH3. The liquid compounds were identified and characterized by 1H and 13C NMR and mass spectrometry. The conformations adopted by the molecules were studied by DFT methods. 6 conformers were theoretically predicted for R = CH3sbnd and (CH3)2CHsbnd , while the conformational flexibility of the n-propyl substituent increases the total number of feasible rotamers to 21. For the three molecules, the conformers can be associated in 3 groups, being the most stable the AS forms - the Cdbnd S double bond anti (A) with respect to the Csbnd S single bond and the Ssbnd C single bond syn (S) with respect to the Cdbnd O double bond - followed by AA and SS conformers. The vibrational spectra were interpreted in terms of the predicted conformational equilibrium, presenting the ν(Cdbnd O) spectral region signals corresponding to the three groups of conformers. A moderated pre-resonance Raman enhancement of the ν(Cdbnd S) vibrational mode of CH3(CH2)2OC(S)SC(O)OCH2CH3 was detected, when the excitation radiation approaches the energy of a n → π∗ electronic transition associated with the Cdbnd S chromophore. UV-visible spectra in different solvents were measured and interpreted in terms of TD-DFT calculations. The unknown molecule CH3CH2OC(O)SH was isolated by the UV-visible photolysis of CH3OC(S)SC(O)OCH2CH3 isolated in Ar matrix, and also obtained as a side-product of the reaction between potassium xanthate salts, ROC(S)SK, and ethyl chloroformate, ClC(O)OCH2CH3.

Efficiencies and Optimization of Weak Base Anion Ion-Exchange Resin for Groundwater Hexavalent Chromium Removal at Hanford

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

Nesham, Dean O.; Ivarson, Kristine A.; Hanson, James P.

2014-02-03

The U.S. Department of Energy’s (DOE’s) contractor, CH2M HILL Plateau Remediation Company, has successfully converted a series of groundwater treatment facilities to use a new treatment resin that is delivering more than $3 million in annual cost savings and efficiency in treating groundwater contamination at the DOE Hanford Site in southeastern Washington State. During the production era, the nuclear reactors at the Hanford Site required a continuous supply of high-quality cooling water during operations. Cooling water consumption ranged from about 151,417 to 378,541 L/min (40,000 to 100,000 gal/min) per reactor, depending on specific operating conditions. Water from the Columbia Rivermore » was filtered and treated chemically prior to use as cooling water, including the addition of sodium dichromate as a corrosion inhibitor. Hexavalent chromium was the primary component of the sodium dichromate and was introduced into the groundwater at the Hanford Site as a result of planned and unplanned discharges from the reactors starting in 1944. Groundwater contamination by hexavalent chromium and other contaminants related to nuclear reactor operations resulted in the need for groundwater remedial actions within the Hanford Site reactor areas. Beginning in 1995, groundwater treatment methods were evaluated, leading to the use of pump-and-treat facilities with ion exchange using Dowex™ 21K, a regenerable, strong-base anion exchange resin. This required regeneration of the resin, which was performed offsite. In 2008, DOE recognized that regulatory agreements would require significant expansion for the groundwater chromium treatment capacity. As a result, CH2M HILL performed testing at the Hanford Site in 2009 and 2010 to demonstrate resin performance in the specific groundwater chemistry at different waste sites. The testing demonstrated that a weak-base anion, single-use resin, specifically ResinTech SIR-700 ®, was effective at removing chromium, had a

Infrared photodissociation spectroscopy of H(+)(H2O)6·M(m) (M = Ne, Ar, Kr, Xe, H2, N2, and CH4): messenger-dependent balance between H3O(+) and H5O2(+) core isomers.

PubMed

Mizuse, Kenta; Fujii, Asuka

2011-04-21

Although messenger mediated spectroscopy is a widely-used technique to study gas phase ionic species, effects of messengers themselves are not necessarily clear. In this study, we report infrared photodissociation spectroscopy of H(+)(H(2)O)(6)·M(m) (M = Ne, Ar, Kr, Xe, H(2), N(2), and CH(4)) in the OH stretch region to investigate messenger(M)-dependent cluster structures of the H(+)(H(2)O)(6) moiety. The H(+)(H(2)O)(6), the protonated water hexamer, is the smallest system in which both the H(3)O(+) (Eigen) and H(5)O(2)(+) (Zundel) hydrated proton motifs coexist. All the spectra show narrower band widths reflecting reduced internal energy (lower vibrational temperature) in comparison with bare H(+)(H(2)O)(6). The Xe-, CH(4)-, and N(2)-mediated spectra show additional band features due to the relatively strong perturbation of the messenger. The observed band patterns in the Ar-, Kr-, Xe-, N(2)-, and CH(4)-mediated spectra are attributed mainly to the "Zundel" type isomer, which is more stable. On the other hand, the Ne- and H(2)-mediated spectra are accounted for by a mixture of the "Eigen" and "Zundel" types, like that of bare H(+)(H(2)O)(6). These results suggest that a messenger sometimes imposes unexpected isomer-selectivity even though it has been thought to be inert. Plausible origins of the isomer-selectivity are also discussed.

CO{sub 2} pellet decontamination technology at Westinghouse Hanford

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

Aldridge, T.L.; Aldrich, L.K. II; Bowman, E.V.

1995-03-01

Experimentation and testing with CO{sub 2} pellet decontamination technology is being conducted at Westinghosue Hanford Company (WHC), Richland, Washington. There are 1,100 known existing waste sites at Hanford. The sites specified by federal and state agencies are currently being studied to determine the appropriate cleanup methods best for each site. These sites are contaminated and work on them is in compliance with the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA). There are also 63 treatment, storage, and disposal units, for example: groups of waste tanks or drums. In 1992, there were 100 planned activities scheduled to bring these unitsmore » into the Resource Conservation and Recovery Act (RCRA) compliance or close them after waste removal. Ninety-six of these were completed. The remaining four were delayed or are being negotiated with regulatory agencies. As a result of past defense program activities at Hanford a tremendous volume of materials and equipment have accumulated and require remediation.« less

New acceptor-bridge-donor strategy for enhancing NLO response with long-range excess electron transfer from the NH2...M/M3O donor (M = Li, Na, K) to inside the electron hole cage C20F19 acceptor through the unusual σ chain bridge (CH2)4.

PubMed

Bai, Yang; Zhou, Zhong-Jun; Wang, Jia-Jun; Li, Ying; Wu, Di; Chen, Wei; Li, Zhi-Ru; Sun, Chia-Chung

2013-04-04

Using the strong electron hole cage C20F19 acceptor, the NH2...M/M3O (M = Li, Na, and K) complicated donors with excess electron, and the unusual σ chain (CH2)4 bridge, we construct a new kind of electride molecular salt e(-)@C20F19-(CH2)4-NH2...M(+)/M3O(+) (M = Li, Na, and K) with excess electron anion inside the hole cage (to be encapsulated excess electron-hole pair) serving as a new A-B-D strategy for enhancing nonlinear optical (NLO) response. An interesting push-pull mechanism of excess electron generation and its long-range transfer is exhibited. The excess electron is pushed out from the (super)alkali atom M/M3O by the lone pair of NH2 in the donor and further pulled inside the hole cage C20F19 acceptor through the efficient long σ chain (CH2)4 bridge. Owing to the long-range electron transfer, the new designed electride molecular salts with the excess electron-hole pair exhibit large NLO response. For the e(-)@C20F19-(CH2)4-NH2...Na(+), its large first hyperpolarizability (β0) reaches up to 9.5 × 10(6) au, which is about 2.4 × 10(4) times the 400 au for the relative e(-)@C20F20...Na(+) without the extended chain (CH2)4-NH2. It is shown that the new strategy is considerably efficient in enhancing the NLO response for the salts. In addition, the effects of different bridges and alkali atomic number on β0 are also exhibited. Further, three modulating factors are found for enhancing NLO response. They are the σ chain bridge, bridge-end group with lone pair, and (super)alkali atom. The new knowledge may be significant for designing new NLO materials and electronic devices with electrons inside the cages. They may also be the basis of establishing potential organic chemistry with electron-hole pair.

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

Reidel, Steve; Chamness, Mickie A.

This appendix provides a detailed description of geology under the Central Plateau of the Hanford Site, emphasizing the areas around tank farms. It is to be published by client CH2M HILL Hanford Group, Inc., as part of a larger, multi-contractor technical report.

3μm - 1.6μm Double Resonance Spectroscopy of CH_4

NASA Astrophysics Data System (ADS)

Schwartz, George; Belaas, Erik; Yang, Shaoyue; Lehmann, Kevin

2016-06-01

The Near-IR Spectrum of CH_4 is dense with many overlapping bands that perturb each other by vibrational and ro-vibrational interactions. Assignments of the individual lines are needed in order to simulate the spectrum as a function of pressure and temperature, as needed in the search for CH_4 in extrasolar planets. Both the group at the University College, London^1 and that at the University of Reins^2 have produced theoretical spectra that allows simulation up to the high temperatures expected on ``Hot Jupiters''. The accuracy of these theoretical spectra need to be further tested. Because CH_4 is a light spherical top, assignment of its perturbed spectra is a formable challenge as none of the lines allowed in the rigid rotor approximation have ground vibrational state combination differences. We are using IR-IR double resonance to observe modulation in the strength of near-IR absorption caused by a modulation of a 3 μm OPO beam that is tuned to a particular transition in the C-H stretching fundamental of CH_4. This produces V-type double resonance transitions (which share the lower state with the pump transition), which provides firm assignments for lines normally observed in absorption in the near-IR. We also observe sequential double resonance which reveals transitions that have a known rotational level of the ν_3 fundamental as the lower state and reaches final states in the 9000 cm-1 spectral region. These are states of A, E, F_1 vibrational symmetries which are forbidden in transitions from the ground vibrational state. These 3 level double resonance transitions are Doppler Free and have a linewidth of ˜10 MHz due to a combination of near-IR laser jitter and power broadening of the mid-IR transition. We also observed many 4-level double resonance transitions that we have tentatively assigned as arising from the ν_4 fundamental level. These are distinguished from the 3-level double resonance transitions by they being Doppler broadened and having a large

New assignments in the 2 μm transparency window of the 12CH4 Octad band system

NASA Astrophysics Data System (ADS)

Daumont, L.; Nikitin, A. V.; Thomas, X.; Régalia, L.; Von der Heyden, P.; Tyuterev, Vl. G.; Rey, M.; Boudon, V.; Wenger, Ch.; Loëte, M.; Brown, L. R.

2013-02-01

This paper reports new assignments of rovibrational transitions of 12CH4 bands in the range 4600-4887 cm-1 which is usually referred to as a part of the 2 μm methane transparency window. Several experimental data sources for methane line positions and intensities were combined for this analysis. Three long path Fourier transform spectra newly recorded in Reims with 1603 m absorption path length and pressures of 1, 7 and 34 hPa for samples of natural abundance CH4 provided new measurements of 12CH4 lines. Older spectra for 13CH4 (90% purity) from JPL with 73 m absorption path length were used to identify the corresponding lines. Most of the lines in this region belong to the Octad system of 12CH4. The new spectra allowed us to assign 1014 new line positions and to measure 1095 line intensities in the cold bands of the Octad. These new line positions and intensities were added to the global fit of Hamiltonian and dipole moment parameters of the Ground State, Dyad, Pentad and Octad systems. This leads to a noticeable improvement of the theoretical description in this methane transparency window and a better global prediction of the methane spectrum.

Trầm Cảm Ở Thành Viên Gia Đình Của Nam Tiêm Chích Ma Túy Nhiễm HIV Tại Hà Nội Năm 2016

PubMed Central

Thúy, Đào Thị Diệu; Hoàng, Trần Minh; Thúy, Đinh Thanh; Mai, Phạm Phương; Giang, Lê Minh

2018-01-01

Đa số người tiêm chích ma túy ở Việt Nam đang sống cùng gia đình và điều này tạo ra gánh nặng không nhỏ trong việc chăm sóc. Mục tiêu nghiên cứu là mô tả đặc điểm trầm cảm ở thành viên gia đình của nam tiêm chích ma túy nhiễm HIV và một số yếu tố liên quan. Số liệu nghiên cứu cắt ngang thu thập từ 138 người là thành viên gia đình của nam tiêm chích ma túy nhiễm HIV tại Hà Nội. Kết quả nghiên cứu cho thấy có xấp xỉ 20% mẫu nghiên cứu có dấu hiệu trầm cảm ở mức độ từ nhẹ đến rất nặng. Gánh nặng chăm sóc và mối quan hệ gia đình có liên quan với trầm cảm ở thành viên gia đình. Nghiên cứu cho thấy nhu cầu can thiệp để cải thiện mối quan hệ gia đình, giảm bớt gánh nặng chăm sóc nhằm nâng cao sức khỏe tinh thần ở thành viên gia đình người tiêm chích ma túy nhiễm HIV. PMID:29367942

Experimental and theoretical study on activation of the C-H bond in pyridine by [M(m)]- (M = Cu, Ag, Au, m = 1-3).

PubMed

Liu, Xiao-Jing; Hamilton, I P; Han, Ke-Li; Tang, Zi-Chao

2010-09-21

Activation of the C-H bond of pyridine by [M(m)](-) (M = Cu, Ag, Au, m = 1-3) is investigated by experiment and theory. Complexes of coinage metal clusters and the pyridyl group, [M(m)-C(5)H(4)N](-), are produced from reactions between metal clusters formed by laser ablation of coinage metal samples and pyridine molecules seeded in argon carrier gas. We examine the structure and formation mechanism of these pyridyl-coinage metal complexes. Our study shows that C(5)H(4)N bonds to the metal clusters through a M-C sigma bond and [M(m)-C(5)H(4)N](-) is produced via a stepwise mechanism. The first step is a direct insertion reaction between [M(m)](-) and C(5)H(5)N with activation of the C-H bond to yield the intermediate [HM(m)-C(5)H(4)N](-). The second step is H atom abstraction by a neutral metal atom to yield [M(m)-C(5)H(4)N](-).

The Rotational Spectrum of Anti-Ethylamine (CH3CH2NH2) from 10 to 270 GHz: A Laboratory Study and Astronomical Search in Sgr B2(N)

NASA Astrophysics Data System (ADS)

Apponi, A. J.; Sun, M.; Halfen, D. T.; Ziurys, L. M.; Müller, H. S. P.

2008-02-01

The pure rotational spectrum of the lowest energy (anti-) conformer of ethylamine (CH3CH2NH2) has been measured in the frequency range of 10-270 GHz. The spectrum was recorded using both millimeter-wave absorption spectroscopy and Fourier transform microwave (FTMW) techniques. Ten rotational transitions of this molecule were recorded in the frequency range of 10-40 GHz using FTMW methods, resulting in the assignment of 53 quadrupole-resolved hyperfine lines; in the millimeter-wave region (48-270 GHz), nearly 600 transitions were assigned to the ground (anti-) state. The amine group in CH3CH2NH2 undergoes inversion, resulting in a doubling that is frequently small and most apparent in the low-frequency K-doubling transitions. In addition, seemingly random rotational levels of this molecule were found to be significantly perturbed. The cause of these perturbations is presently uncertain, but torsion-rotation interactions with the higher lying gauche conformers seem to be a likely explanation. An astronomical search was conducted for ethylamine toward Sgr B2(N) using the Kitt Peak 12 m antenna and the Sub-Millimeter Telescope (SMT) of the Arizona Radio Observatory. Frequencies of 70 favorable rotational transitions were observed in this search, which covered the range 68-263 GHz. Ethylamine was not conclusively detected in Sgr B2(N), with an upper limit to the column density of (1-8) × 1013 cm-2 with f(CH3CH2NH2/H2) ~ (0.3-3) × 10-11, assuming a rotational temperature of 50-220 K. These observations indicate a gas-phase CH3CH2NH2/CH3NH2 ratio of <0.001-0.01, in contrast to the nearly equal ratio suggested by the acid hydrolysis of cometary solids from the Stardust mission.

Synthesis, structure and reactivity of rare-earth metallacarborane alkyls [η(1):η(5)-O(CH2)2C2B9H9]Ln(σ:η(1)-CH2C6H4-o-NMe2)(THF)2.

PubMed

Yang, Jingying; Xie, Zuowei

2015-04-14

Rare-earth metallacarborane alkyls can be stabilized by the incorporation of a functional sidearm into both π and σ ligands. Reaction of [Me3NH][7,8-O(CH2)2-7,8-C2B9H10] with one equiv. of Ln(CH2C6H4-o-NMe2)3 gave metallacarborane alkyls [η(1):η(5)-O(CH2)2C2B9H9]Ln(σ:η(1)-CH2C6H4-o-NMe2)(THF)2 (Ln = Y (), Gd (), Er ()) via alkane elimination. They represent the first examples of rare-earth metallacarborane alkyls. Treatment of with RN[double bond, length as m-dash]C[double bond, length as m-dash]NR (R = Cy, (i)Pr) or 2-benzoylpyridine afforded the corresponding mono-insertion products [η(1):η(5)-O(CH2)2C2B9H9]Y[η(2)-(RN)2C(CH2C6H4-o-NMe2)](DME) (R = Cy (), (i)Pr ()) or [η(1):η(5)-O(CH2)2C2B9H9]Y[C5H4NC(Ph)(CH2C6H4-o-NMe2)O](THF)2 (), respectively. Complex also reacted with ArNCO or ArNC (Ar = 2,6-diisopropylphenyl, 2,6-dimethylphenyl) to give di-insertion products [η(1):η(5)-O(CH2)2C2B9H9]Y[OC([double bond, length as m-dash]NC6H3Me2)N(C6H3Me2)C(CH2C6H4-o-NMe2)O](THF)2 () or [η(1):η(5)-O(CH2)2C2B9H9]Y[C([double bond, length as m-dash]NC6H3(i)Pr2)C([double bond, length as m-dash]NC6H3(i)Pr2)(CH2C6H4-o-NMe2)](DME) (). These results showed that the reactivity pattern of the Ln-C σ bond in rare-earth metallacarborane alkyls was dependent on the nature of the unsaturated organic molecules. New complexes were characterized by various spectroscopic techniques and elemental analysis. Some were further confirmed by single-crystal X-ray analysis.

Mechanical Demolition of Buildings with Concrete Asbestos Board Siding: Methodology, Precautions, and Results at the Hanford Central Plateau - 12417

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

Kehler, Kurt

Since the start of its contract in 2008, the CH2M Hill Plateau Remediation Company (CH2M HILL) has demolished 25 buildings with concrete asbestos board (CAB) siding using mechanical means. While the asbestos contained in CAB siding is not friable in its manufactured form, concerns persist that mechanical methods of demolition have the potential to render the asbestos friable and airborne, therefore posing a health risk to demolition workers and the public. CH2M HILL's experience demonstrates that when carefully managed, mechanical demolition of CAB siding can be undertaken safely, successfully, and in compliance with regulatory requirements for the disposal of Classmore » II Asbestos-Containing Material (ACM). While the number of buildings demolished at Hanford and the number of samples collected does not make a conclusive argument that CAB cannot be made friable with normal demolition techniques, it certainly provides a significant body of evidence for the success of the approach. Of course, there are many factors that affect how to demolish a structure and dispose of the waste. These factors will impact the success depending on each site. The most obvious factors which contribute to this success at Hanford are: 1. The availability of onsite waste disposal where the handling and cost of asbestos-containing waste is not much different than other potentially contaminated waste. Therefore, segregation of demolition debris from the potential asbestos contamination is not necessary from a debris handling or asbestos disposal aspect. 2. The space between structures is typically significant enough to allow for large exclusion zones. There are not many restrictions due to cohabitation issues or potential contamination of adjacent facilities. 3. The willingness of the regulators and client to understand the industrial safety issues associated with manual CAB removal. (authors)« less

One-Electron Oxidation of [M(P(t) Bu3 )2 ] (M=Pd, Pt): Isolation of Monomeric [Pd(P(t) Bu3 )2 ](+) and Redox-Promoted C-H Bond Cyclometalation.

PubMed

Troadec, Thibault; Tan, Sze-Yin; Wedge, Christopher J; Rourke, Jonathan P; Unwin, Patrick R; Chaplin, Adrian B

2016-03-07

Oxidation of zero-valent phosphine complexes [M(P(t) Bu3 )2 ] (M=Pd, Pt) has been investigated in 1,2-difluorobenzene solution using cyclic voltammetry and subsequently using the ferrocenium cation as a chemical redox agent. In the case of palladium, a mononuclear paramagnetic Pd(I) derivative was readily isolated from solution and fully characterized (EPR, X-ray crystallography). While in situ electrochemical measurements are consistent with initial one-electron oxidation, the heavier congener undergoes C-H bond cyclometalation and ultimately affords the 14 valence-electron Pt(II) complex [Pt(κ(2) PC -P(t) Bu2 CMe2 CH2 )(P(t) Bu3 )](+) with concomitant formation of [Pt(P(t) Bu3 )2 H](+) . © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

E2 and SN2 Reactions of X(-) + CH3CH2X (X = F, Cl); an ab Initio and DFT Benchmark Study.

PubMed

Bento, A Patrícia; Solà, Miquel; Bickelhaupt, F Matthias

2008-06-01

We have computed consistent benchmark potential energy surfaces (PESs) for the anti-E2, syn-E2, and SN2 pathways of X(-) + CH3CH2X with X = F and Cl. This benchmark has been used to evaluate the performance of 31 popular density functionals, covering local-density approximation, generalized gradient approximation (GGA), meta-GGA, and hybrid density-functional theory (DFT). The ab initio benchmark has been obtained by exploring the PESs using a hierarchical series of ab initio methods [up to CCSD(T)] in combination with a hierarchical series of Gaussian-type basis sets (up to aug-cc-pVQZ). Our best CCSD(T) estimates show that the overall barriers for the various pathways increase in the order anti-E2 (X = F) < SN2 (X = F) < SN2 (X = Cl) ∼ syn-E2 (X = F) < anti-E2 (X = Cl) < syn-E2 (X = Cl). Thus, anti-E2 dominates for F(-) + CH3CH2F, and SN2 dominates for Cl(-) + CH3CH2Cl, while syn-E2 is in all cases the least favorable pathway. Best overall agreement with our ab initio benchmark is obtained by representatives from each of the three categories of functionals, GGA, meta-GGA, and hybrid DFT, with mean absolute errors in, for example, central barriers of 4.3 (OPBE), 2.2 (M06-L), and 2.0 kcal/mol (M06), respectively. Importantly, the hybrid functional BHandH and the meta-GGA M06-L yield incorrect trends and qualitative features of the PESs (in particular, an erroneous preference for SN2 over the anti-E2 in the case of F(-) + CH3CH2F) even though they are among the best functionals as measured by their small mean absolute errors of 3.3 and 2.2 kcal/mol in reaction barriers. OLYP and B3LYP have somewhat higher mean absolute errors in central barriers (5.6 and 4.8 kcal/mol, respectively), but the error distribution is somewhat more uniform, and as a consequence, the correct trends are reproduced.

Crystal and molecular structure of the first dibino non-geminal macrocyclic dicyclophosphazene, & {;N 3P 3Cl 4[HN(CH 2) 3O(CH 2) 2O(CH 2) 3NH]&}; 2

NASA Astrophysics Data System (ADS)

Enjalbert, Renée; Galy, Jean; Sournies, François; Labarre, Jean-François

1990-04-01

Reaction of N 3P 3Cl 6 with the 4,7-dioxadecane-1,10-diamine (coded as 3O2O3) using an Et 2O/Na 2CO 3 water interface process leads to the DIBINO non-geminal 30-membered macrocyclic dicyclophosphazene &{;N 3P 3Cl 4[HN(CH 2) 3O(CH 2) 2O(CH 2) 3NH]&}; 2. This 30-crown-ether-like architecture crystallizes in the triclinic system, P1, a=9.019(6), b=9.224(5), c=11.542(8) Å, α=94.87(4), β=95.97(4), γ=99.68(3)°, V=936(1) Å 3, Dx=1.599 Mg m -3, R=0.049 for 2862 unique reflections and 199 variable parameters. The structure exhibits a spatial arrangement of two N 3P 3Cl 4 with two [HN(CH 2) 3O(CH 2) 3O(CH 2) 3NH] as bridges on different P atoms of N 3P 3 rings. Moreover, the two N 3P 3 rings are trans to the average plane of the 30-membered macrocycle ("chair" conformation).

Rare-earth transition-metal gallium chalcogenides RE3MGaCh7 (M=Fe, Co, Ni; Ch=S, Se)

NASA Astrophysics Data System (ADS)

Rudyk, Brent W.; Stoyko, Stanislav S.; Oliynyk, Anton O.; Mar, Arthur

2014-02-01

Six series of quaternary rare-earth transition-metal chalcogenides RE3MGaCh7 (M=Fe, Co, Ni; Ch=S, Se), comprising 33 compounds in total, have been prepared by reactions of the elements at 1050 °C (for the sulphides) or 900 °C (for the selenides). They adopt noncentrosymmetric hexagonal structures (ordered Ce3Al1.67S7-type, space group P63, Z=2) with cell parameters in the ranges of a=9.5-10.2 Å and c=6.0-6.1 Å for the sulphides and a=10.0-10.5 Å and c=6.3-6.4 Å for the selenides as refined from powder X-ray diffraction data. Single-crystal structures were determined for five members of the sulphide series RE3FeGaS7 (RE=La, Pr, Tb) and RE3CoGaS7 (RE=La, Tb). The highly anisotropic crystal structures consist of one-dimensional chains of M-centred face-sharing octahedra and stacks of Ga-centred tetrahedra all pointing in the same direction. Magnetic measurements on the sulphides reveal paramagnetic behaviour in some cases and long-range antiferromagnetic behaviour with low Néel temperatures (15 K or lower) in others. Ga L-edge XANES spectra support the presence of highly cationic Ga tetrahedral centres with a tendency towards more covalent Ga-Ch character on proceeding from the sulphides to the selenides. Band structure calculations on La3FeGaS7 indicate that the electronic structure is dominated by Fe 3d-based states near the Fermi level.

Crystallization and X-ray diffraction analysis of the CH domain of the cotton kinesin GhKCH2

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

Qin, Xinghua; The Fourth Military Medical University, No. 169 Changlexi Road, Xincheng District, Xi’an 710032, People’s Republic of; Chen, Ziwei

The cloning, expression, purification and crystallization of the CH domain of the plant-specific kinesin GhKCH2 is reported. GhKCH2 belongs to a group of plant-specific kinesins (KCHs) containing an actin-binding calponin homology (CH) domain in the N-terminus. Previous studies revealed that the GhKCH2 CH domain (GhKCH2-CH) had a higher affinity for F-actin (K{sub d} = 0.42 ± 0.02 µM) than most other CH-domain-containing proteins. To understand the underlying mechanism, prokaryotically expressed GhKCH2-CH (amino acids 30–166) was purified and crystallized. Crystals were grown by the sitting-drop vapour-diffusion method using 0.1 M Tris–HCl pH 7.0, 20%(w/v) PEG 8000 as a precipitant. The crystalsmore » diffracted to a resolution of 2.5 Å and belonged to space group P2{sub 1}, with unit-cell parameters a = 41.57, b = 81.92, c = 83.00 Å, α = 90.00, β = 97.31, γ = 90.00°. Four molecules were found in the asymmetric unit with a Matthews coefficient of 2.22 Å{sup 3} Da{sup −1}, corresponding to a solvent content of 44.8%.« less

Preliminary assignments of 2 ν 3 - ν 4 hot band of 12 CH 4 in the 2 μm transparency window from long-path FTS spectra

NASA Astrophysics Data System (ADS)

Nikitin, A. V.; Daumont, L.; Thomas, X.; Régalia, L.; Rey, M.; Tyuterev, Vl. G.; Brown, L. R.

2011-07-01

New measurements and assignments for the rovibrational transitions of the hot band 2 v3- v4 of 12CH 4 are reported from 4600 to 4880 cm -1 and refer to lower part of the 2 μm methane transparency window. Three long-path spectra were recorded with a Fourier transform spectrometer (FTS) in Reims using an L = 1603 m absorption path length at 1, 7, 34 h Pa for the natural samples of CH 4; a spectrum of enriched 13CH 4 was also used. Assignments were made for 196 lines of 2 v3(F 2,E)- v4. These transitions had an integrated intensity of 5 × 10 -24 cm/molecule at 296 K and improved the overall description of absorption in the 2.1 μm region. The empirical upper state levels of these assignments belong to Tetradecad (4800-6200 cm -1). The new analysis provided much better accuracies of badly blended positions of 2 v3(F 2)-ground state manifolds at 1.66 μm.

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.

Exploring the Reactivity Trends in the E2 and SN2 Reactions of X(-) + CH3CH2Cl (X = F, Cl, Br, HO, HS, HSe, NH2 PH2, AsH2, CH3, SiH3, and GeH3).

PubMed

Wu, Xiao-Peng; Sun, Xiao-Ming; Wei, Xi-Guang; Ren, Yi; Wong, Ning-Bew; Li, Wai-Kee

2009-06-09

The reactivity order of 12 anions toward ethyl chloride has been investigated by using the G2(+) method, and the competitive E2 and SN2 reactions are discussed and compared. The reactions studied are X(-) + CH3CH2Cl → HX + CH2═CH2 + Cl(-) and X(-) + CH3CH2Cl → CH3CH2X + Cl(-), with X = F, Cl, Br, HO, HS, HSe, NH2 PH2, AsH2, CH3, SiH3, and GeH3. Our results indicate that there is no general and straightforward relationship between the overall barriers and the proton affinity (PA) of X(-); instead, discernible linear correlations only exist for the X's within the same group of the periodic table. Similar correlations are also found with the electronegativity of central atoms in X, deformation energy of the E2 transition state (TS), and the overall enthalpy of reaction. It is revealed that the electronegativity will significantly affect the barrier height, and a more electronegative X will stabilize the E2 and SN2 transition states. Multiple linear regression analysis shows that there is a reasonable linear correlation between E2 (or SN2) overall barriers and the linear combination of PA of X(-) and electronegativity of the central atom.

Luminescence, magnetic and vibrational properties of novel heterometallic niccolites [(CH3)2NH2][CrIIIMII(HCOO)6] (MII=Zn, Ni, Cu) and [(CH3)2NH2][AlIIIZnII(HCOO)6]:Cr3+

NASA Astrophysics Data System (ADS)

Mączka, Mirosław; Pietraszko, Adam; Pikul, Adam; Hermanowicz, Krzysztof

2016-01-01

We report synthesis of three novel heterometallic MOFs, [(CH3)2NH2][CrIIIMII(HCOO)6] with M=Zn (DMCrZn), Ni (DMCrNi) and Cu (DMCrCu), crystallizing in the niccolite type structure. We also successfully synthesized [(CH3)2NH2][AlCu(HCOO)6] (DMAlCu) and [(CH3)2NH2][AlZn(HCOO)6] doped with 5.8 mol% of Cr3+ (DMAlZn: Cr). X-ray diffraction shows that DMCrZn, DMCrNi and DMAlZn: Cr3+ crystallize in the trigonal structure (space group P 3 bar1c) while DMCrCu and DMAlCu crystallize in the monoclinic structure (space group C2/c). Magnetic investigation of the chromium-based niccolites reveals no magnetic order in DMCrZn and ferromagnetic order in DMCrNi and DMCrCu below 23 and 11 K, respectively. Optical studies show that DMCrZn and DMAlZn: Cr samples exhibit efficient emission typical for chromium ions located at sites of strong crystal field with the Dq/B values 2.62 and 2.67, respectively. We also discuss role of geometrical parameters in stability of the perovskite and niccolite structures.

Luminescent Copper(I) Halide Butterfly Dimers Coordinated to [Au(CH3imCH2py)2]BF4 and [Au(CH3imCH2quin)2]BF4

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

Catalano, V.; Moore, A; Shearer, J

2009-01-01

The coordination chemistry of copper(I) halides to the homoleptic, N-heterocyclic carbene Au(I) complexes [Au(CH{sub 3}imCH{sub 2}quin){sub 2}]BF{sub 4} and [Au(CH{sub 3}imCH{sub 2}py){sub 2}]BF{sub 4} was explored. The reaction of CuX (X = Cl, Br, I) with either [Au(CH{sub 3}imCH{sub 2}quin){sub 2}]BF{sub 4} or [Au(CH{sub 3}imCH{sub 2}py){sub 2}]BF{sub 4} produces trimetallic complexes containing Cu{sub 2}X{sub 2}-butterfly copper clusters coordinated to the two imine moieties. The triangular arrangement of the metals places the gold(I) center in close proximity ({approx}2.5-2.6 {angstrom}) to the centroid of the Cu-Cu vector. The Cu-Cu separations vary as a function of bridging halide with the shortest Cu-Cu separationsmore » of {approx}2.5 {angstrom} found in the iodo-complexes and the longest separations of 2.9 {angstrom} found in the bridging chloride complexes. In all six complexes the Au-Cu separations range from {approx}2.8 to 3.0 {angstrom}. In the absence of halides, the dimetallic complex [AuCu(CH{sub 3}imCH{sub 2}py){sub 2}(NCCH{sub 3}){sub 2}](BF{sub 4}){sub 2}, containing a long Au-Cu distance of {approx}4.72 {angstrom} is formed. Additionally, as the byproduct of the reaction of CuBr with [Au(CH{sub 3}imCH{sub 2}quin){sub 2}]BF{sub 4} the deep-red, dimetallic compound, AuCuBr{sub 2}(CH{sub 3}imCH{sub 2}quin){sub 2}, was isolated in very low yield. All of these complexes were studied by NMR spectroscopy, mass spectrometry, and the copper containing species were additionally characterized by X-ray crystallography. In solution the copper centers dissociate from the gold complexes, but as shown by XANES and EXAFS spectroscopy, at low temperature the Cu-Cu linkage is broken, and the individual copper(I) halides reposition themselves to opposite sides of the gold complex while remaining coordinated to one imine moiety. In the solid state all of the complexes are photoluminescent, though the nature of the excited state was not determined.« less

Spatial distribution of CH3 and CH2 radicals in a methane rf discharge

NASA Astrophysics Data System (ADS)

Sugai, H.; Kojima, H.; Ishida, A.; Toyoda, H.

1990-06-01

Spatial distributions of neutral radicals CH3 and CH2 in a capacitively coupled rf glow discharge of methane were measured by threshold ionization mass spectrometry. A strong asymmetry of the density profile was found for the CH2 radical in the high-pressure (˜100 mTorr) discharge. In addition, comprehensive measurements of electron energy distribution, ionic composition, and radical sticking coefficient were made to use as inputs to theoretical modeling of radicals in the methane plasma. The model predictions agree substantially with the measured radical distributions.

Microwave Spectroscopic Investigations of the C-H\\cdotsπ Containing Complexes CH_2F_2\\cdotsPROPYNE and CH_2ClF\\cdotsPROPYNE

NASA Astrophysics Data System (ADS)

Peebles, Rebecca A.; Peebles, Sean A.; Christenholz, Cori L.; Ernst, Anthony A.; Dhahir, Yasser J.

2013-06-01

The spectra of the CH_2F_2\\cdotspropyne and CH_2ClF\\cdotspropyne complexes have been studied by chirped-pulse and resonant cavity Fourier-transform microwave spectroscopy and by ab initio calculations at the MP2/6-311++G(2d,2p) level. Both complexes contain C-H\\cdotsπ contacts, with the halogen atoms angled towards the methyl group end of the propyne. While CH_2F_2\\cdotspropyne has C_s symmetry, CH_2ClF\\cdotspropyne has C_1 symmetry, with the fluorine and chlorine atoms straddling the propyne. Investigation of four single ^{13}C and the DC≡CCH_3 isotopologues in CH_2F_2\\cdotspropyne has allowed a detailed structural determination, while only the ^{35}Cl and ^{37}Cl isotopologues have so far been assigned for CH_2ClF\\cdotspropyne. Experimental data will be compared with ab initio results and with the analogous acetylene complexes, both of which have C_s symmetry structures, with double C-H\\cdotsπ interactions.

Periodic mesoporous organosilicas containing interconnected [Si(CH2)]3 rings.

PubMed

Landskron, Kai; Hatton, Benjamin D; Perovic, Doug D; Ozin, Geoffrey A

2003-10-10

A periodic mesoporous organosilica composed of interconnected three-ring [Si(CH2)]3 units built of three SiO2(CH2)2 tetrahedral subunits is reported. It represents the archetype of a previously unknown class of nanocomposite materials in which two bridging organic groups are bound to each silicon atom. It can be obtained with powder and oriented film morphologies. The nanocomposite is self-assembled from the cyclic three-ring silsesquioxane [(EtO)2Si(CH2)]3 precursor and a surfactant mesophase to give a well-ordered mesoporous framework. Low dielectric constants and good mechanical stability of the films were measured, making this material interesting for microelectronic applications. Methylene group reactivity of the three-ring precursor provides entry to a family of nanocomposites, exemplified by the synthesis and self-assembly of [(EtO)2Si(CHR)][(EtO)2Si(CH2)]2 (where R indicates iodine, bromine, or an ethyl group).

Methanesulfonates of high-valent metals: syntheses and structural features of MoO2(CH3SO3)2, UO2(CH3SO3)2, ReO3(CH3SO3), VO(CH3SO3)2, and V2O3(CH3SO3)4 and their thermal decomposition under N2 and O2 atmosphere.

PubMed

Betke, Ulf; Neuschulz, Kai; Wickleder, Mathias S

2011-11-04

Oxide methanesulfonates of Mo, U, Re, and V have been prepared by reaction of MoO(3), UO(2)(CH(3)COO)(2)·2H(2)O, Re(2)O(7)(H(2)O)(2), and V(2)O(5) with CH(3)SO(3)H or mixtures thereof with its anhydride. These compounds are the first examples of solvent-free oxide methanesulfonates of these elements. MoO(2)(CH(3)SO(3))(2) (Pbca, a=1487.05(4), b=752.55(2), c=1549.61(5) pm, V=1.73414(9) nm(3), Z=8) contains [MoO(2)] moieties connected by [CH(3)SO(3)] ions to form layers parallel to (100). UO(2)(CH(3)SO(3))(2) (P2(1)/c, a=1320.4(1), b=1014.41(6), c=1533.7(1) pm, β=112.80(1)°, V=1.8937(3) nm(3), Z=8) consists of linear UO(2)(2+) ions coordinated by five [CH(3)SO(3)] ions, forming a layer structure. VO(CH(3)SO(3))(2) (P2(1)/c, a=1136.5(1), b=869.87(7), c=915.5(1) pm, β=113.66(1)°, V=0.8290(2) nm(3), Z=4) contains [VO] units connected by methanesulfonate anions to form corrugated layers parallel to (100). In ReO(3)(CH(3)SO(3)) (P1, a=574.0(1), b=1279.6(3), c=1641.9(3) pm, α=102.08(2), β=96.11(2), γ=99.04(2)°, V=1.1523(4) nm(3), Z=8) a chain structure exhibiting infinite O-[ReO(2)]-O-[ReO(2)]-O chains is formed. Each [ReO(2)]-O-[ReO(2)] unit is coordinated by two bidentate [CH(3)SO(3)] ions. V(2)O(3)(CH(3)SO(3))(4) (I2/a, a=1645.2(3), b=583.1(1), c=1670.2(3) pm, β=102.58(3), V=1.5637(5) pm(3), Z=4) adopts a chain structure, too, but contains discrete [VO]-O-[VO] moieties, each coordinated by two bidentate [CH(3)SO(3)] ligands. Additional methanesulfonate ions connect the [V(2)O(3)] groups along [001]. Thermal decomposition of the compounds was monitored under N(2) and O(2) atmosphere by thermogravimetric/differential thermal analysis and XRD measurements. Under N(2) the decomposition proceeds with reduction of the metal leading to the oxides MoO(2), U(3)O(7), V(4)O(7), and VO(2); for MoO(2)(CH(3)SO(3))(2), a small amount of MoS(2) is formed. If the thermal decomposition is carried out in a atmosphere of O(2) the oxides MoO(3) and V(2)O(5) are formed. Copyright �

Late metal carbene complexes generated by multiple C-H activations: examining the continuum of M=C bond reactivity.

PubMed

Whited, Matthew T; Grubbs, Robert H

2009-10-20

Unactivated C(sp(3))-H bonds are ubiquitous in organic chemicals and hydrocarbon feedstocks. However, these resources remain largely untapped, and the development of efficient homogeneous methods for hydrocarbon functionalization by C-H activation is an attractive and unresolved challenge for synthetic chemists. Transition-metal catalysis offers an attractive possible means for achieving selective, catalytic C-H functionalization given the thermodynamically favorable nature of many desirable partial oxidation schemes and the propensity of transition-metal complexes to cleave C-H bonds. Selective C-H activation, typically by a single cleavage event to produce M-C(sp(3)) products, is possible through myriad reported transition-metal species. In contrast, several recent reports have shown that late transition metals may react with certain substrates to perform multiple C-H activations, generating M=C(sp(2)) complexes for further elaboration. In light of the rich reactivity of metal-bound carbenes, such a route could open a new manifold of reactivity for catalytic C-H functionalization, and we have targeted this strategy in our studies. In this Account, we highlight several early examples of late transition-metal complexes that have been shown to generate metal-bound carbenes by multiple C-H activations and briefly examine factors leading to the selective generation of metal carbenes through this route. Using these reports as a backdrop, we focus on the double C-H activation of ethers and amines at iridium complexes supported by Ozerov's amidophosphine PNP ligand (PNP = [N(2-P(i)Pr(2)-4-Me-C(6)H(3))(2)](-)), allowing isolation of unusual square-planar iridium(I) carbenes. These species exhibit reactivity that is distinct from the archetypal Fischer and Schrock designations. We present experimental and theoretical studies showing that, like the classical square-planar iridium(I) organometallics, these complexes are best described as nucleophilic at iridium. We discuss

On the formation of the ·CH 2CH 2CH=NH 2+ distonic radical cation upon ionization of cyclopropylamine and allylamine

NASA Astrophysics Data System (ADS)

Nguyen, Minh Tho; Creve, Steven; Ha, Tae-Kyu

1998-08-01

Ab initio molecular orbital and density functional theory calculations have been applied to determine the relative stability of the cyclopropylamine 1 and allylamine (CH 2=CHCH 2NH 2+·2) radical cations and their isomers. It is confirmed that, upon ionization, 1 undergoes barrier-free ring-opening giving the distonic species ·CH 2CH 2CH=NH 2+3. 2 also rearranges by a 1,2-H-shift to the more stable 3 (by 70 kJ/mol) which is, however, less stable than the 1-aminopropene ion (CH 3-CH=CH-NH 2+·4) by 60 kJ/mol. The transition structure TS 2/3 lies 40 kJ/mol higher in energy than TS 3/4. Although QCISD and B3LYP calculations of isotropic hyperfine coupling constants agree reasonably with observed values, supporting the presence of the distonic 3 in ESR matrix experiments, the exclusive observation of 3, but not 4, is intriguing. This emphasizes the role of the matrix in stabilizing 3.

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.

Capture and dissociation in the complex-forming CH + H2 → CH2 + H, CH + H2 reactions.

PubMed

González, Miguel; Saracibar, Amaia; Garcia, Ernesto

2011-02-28

The rate coefficients for the capture process CH + H(2)→ CH(3) and the reactions CH + H(2)→ CH(2) + H (abstraction), CH + H(2) (exchange) have been calculated in the 200-800 K temperature range, using the quasiclassical trajectory (QCT) method and the most recent global potential energy surface. The reactions, which are of interest in combustion and in astrochemistry, proceed via the formation of long-lived CH(3) collision complexes, and the three H atoms become equivalent. QCT rate coefficients for capture are in quite good agreement with experiments. However, an important zero point energy (ZPE) leakage problem occurs in the QCT calculations for the abstraction, exchange and inelastic exit channels. To account for this issue, a pragmatic but accurate approach has been applied, leading to a good agreement with experimental abstraction rate coefficients. Exchange rate coefficients have also been calculated using this approach. Finally, calculations employing QCT capture/phase space theory (PST) models have been carried out, leading to similar values for the abstraction rate coefficients as the QCT and previous quantum mechanical capture/PST methods. This suggests that QCT capture/PST models are a good alternative to the QCT method for this and similar systems.

Axial zero-field splitting in mononuclear Co(ii) 2-N substituted N-confused porphyrin: Co(2-NC3H5-21-Y-CH2C6H4CH3-NCTPP)Cl (Y = o, m, p) and Co(2-NC3H5-21-CH2C6H5-NCTPP)Cl.

PubMed

Lai, Ya-Yuan; Chang, Yu-Chang; Chen, Jyh-Horung; Wang, Shin-Shin; Tung, Jo-Yu

2016-03-21

The inner C-benzyl- and C-o-xylyl (or m-xylyl, p-xylyl)-substituted cobalt(ii) complexes of a 2-N-substituted N-confused porphyrin were synthesized from the reaction of 2-NC3H5NCTPPH (1) and CoCl2·6H2O in toluene (or o-xylene, m-xylene, p-xylene). The crystal structures of diamagnetic chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-hydrogen-21-carbaporphyrinato-N,N',N'')zinc(ii) [Zn(2-NC3H5-21-H-NCTPP)Cl; 3 ] and paramagnetic chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-benzyl-21-carbaporphyrinato-N,N',N'')cobalt(ii) [Co(2-NC3H5-21-CH2C6H5NCTPP)Cl; 7], and chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-Y-xylyl-21-carbaporphyrinato-N,N',N'')cobalt(ii) [Co(2-NC3H5-21-Y-CH2C6H4CH3NCTPP)Cl] [Y = o (8), m (9), p (10)] were determined. The coordination sphere around the Zn(2+) (or Co(2+)) ion in 3 (or 7-10) is a distorted tetrahedron (DT). The free energy of activation at the coalescence temperature Tc for the exchange of phenyl ortho protons o-H (26) with o-H (22) in 3 in a CDCl3 solvent is found to be ΔG = 61.4 kJ mol(-1) through (1)H NMR temperature-dependent measurements. The axial zero-field splitting parameter |D| was found to vary from 35.6 cm(-1) in 7 (or 30.7 cm(-1) in 8) to 42.0 cm(-1) in 9 and 46.9 cm(-1) in 10 through paramagnetic susceptibility measurements. The magnitude of |D| can be related to the coordination sphere at the cobalt sites.

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.

ChIP-PaM: an algorithm to identify protein-DNA interaction using ChIP-Seq data.

PubMed

Wu, Song; Wang, Jianmin; Zhao, Wei; Pounds, Stanley; Cheng, Cheng

2010-06-03

ChIP-Seq is a powerful tool for identifying the interaction between genomic regulators and their bound DNAs, especially for locating transcription factor binding sites. However, high cost and high rate of false discovery of transcription factor binding sites identified from ChIP-Seq data significantly limit its application. Here we report a new algorithm, ChIP-PaM, for identifying transcription factor target regions in ChIP-Seq datasets. This algorithm makes full use of a protein-DNA binding pattern by capitalizing on three lines of evidence: 1) the tag count modelling at the peak position, 2) pattern matching of a specific tag count distribution, and 3) motif searching along the genome. A novel data-based two-step eFDR procedure is proposed to integrate the three lines of evidence to determine significantly enriched regions. Our algorithm requires no technical controls and efficiently discriminates falsely enriched regions from regions enriched by true transcription factor (TF) binding on the basis of ChIP-Seq data only. An analysis of real genomic data is presented to demonstrate our method. In a comparison with other existing methods, we found that our algorithm provides more accurate binding site discovery while maintaining comparable statistical power.

Atmospheric chemistry of cyc-CF2CF2CF2CH=CH-: Kinetics, products, and mechanism of gas-phase reaction with OH radicals, and atmospheric implications

NASA Astrophysics Data System (ADS)

Guo, Qin; Zhang, Ni; Uchimaru, Tadafumi; Chen, Liang; Quan, Hengdao; Mizukado, Junji

2018-04-01

The rate constants for the gas-phase reactions of cyc-CF2CF2CF2CH=CH- with OH radicals were determined by a relative rate method between 253 and 328 K. The rate constant k1 at 298 K was measured to be (1.08 ± 0.04) × 10-13 cm3 molecule-1 s-1, and the Arrhenius expression was k1 = (3.72 ± 0.14) × 10-13 exp [(-370 ± 12)/T]. The atmospheric lifetime of cyc-CF2CF2CF2CH=CH- was calculated to be 107 d. The products and mechanism for the reaction of cyc-CF2CF2CF2CH=CH- with OH radicals were also investigated. CO, CO2, and COF2 were identified as the main carbon-containing products following the OH-initiated reaction. Moreover, the radiative efficiency (RE) was determined to be 0.143 W m-2 ppb-1, and the global warming potentials (GWPs) for 20, 100, and 500 yr were 54, 15, and 4, respectively. The photochemical ozone creation potential of the title compound was estimated to be 1.3.

Anharmonic Effect in CH3CH2C(=O)OCH2CH3 Decomposition

NASA Astrophysics Data System (ADS)

Ding, Yang; Song, Liguo; Yao, Li; Xia, Wenwen

2017-12-01

In this paper, using the B3LYP functional and CCSD(T) method with 6-311++G** basis set, the harmonic and anharmonic rate constants in the unimolecular dissociation of ethyl propanoate have been calculated using Rice-Ramsperger-Kassel-Marcus theory. The anharmonic rate constants of the title reaction have also been examined, the comparison shows that, the anharmonic effect especially in the case of high total energies and temperature for channels 3 to 6 is significant, so that the anharmonic effect cannot be neglected for unimolecular dissociation reaction of CH3CH2C(=O)OCH2CH3 both in microcanonical and canonical systems.

Thermochemistry and kinetics for 2-butanone-1-yl radical (CH2·C(═O)CH2CH3) reactions with O2.

PubMed

Sebbar, N; Bozzelli, J W; Bockhorn, H

2014-01-09

Thermochemistry of reactants, intermediates, transition state structures, and products along with kinetics on the association of CH2·C(═O)CH2CH3 (2-butanone-1-yl) with O2 and dissociation of the peroxy adduct isomers are studied. Thermochemical properties are determined using ab initio (G3MP2B3 and G3) composite methods along with density functional theory (B3LYP/6-311g(d,p)). Entropy and heat capacity contributions versus temperature are determined from structures, vibration frequencies, and internal rotor potentials. The CH2·C(═O)CH2CH3 radical + O2 association results in a chemically activated peroxy radical with 27 kcal mol(-1) excess of energy. The chemically activated adduct can react to stabilized peroxy or hydroperoxide alkyl radical adducts, further react to lactones plus hydroxyl radical, or form olefinic ketones and a hydroperoxy radical. Kinetic parameters are determined from the G3 composite methods derived thermochemical parameters, and quantum Rice-Ramsperger-Kassel (QRRK) analysis to calculate k(E) with master equation analysis to evaluate falloff in the chemically activated and dissociation reactions. One new, not previously reported, peroxy chemistry reaction is presented. It has a low barrier path and involves a concerted reaction resulting in olefin formation, H2O elimination, and an alkoxy radical.

THE POSITIVE IMPACTS OF AMERICAN REINVESTMENT AND RECOVERY ACT (ARRA) FUNDING TO THE WASTE MANAGEMENT PROGRAM ON HANFORD'S PLATEAU REMEDIATION PROJECT

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

BLACKFORD LT

In April 2009, the Department of Energy (DOE) Richland Operations Office (RL) was allocated $1.6 billion (B) in ARRA funding to be applied to cleanup projects at the Hanford Site. DOE-RL selected projects to receive ARRA funding based on 3-criteria: creating/saving jobs, reducing the footprint of the Hanford Site, and reducing life-cycle costs for cleanup. They further selected projects that were currently covered under regulatory documents and existing prime contracts, which allowed work to proceed quickly. CH2M HILL Plateau Remediation Company (CHPRC) is a prime contractor to the DOE focused on the environmental cleanup of the DOE Hanford Site Centralmore » Plateau. CHPRC was slated to receive $1.36B in ARRA funding. As of January, 2010, CHPRC has awarded over $200 million (M) in subcontracts (64% to small businesses), created more that 1,100 jobs, and touched more than 2,300 lives - all in support of long-term objectives for remediation of the Central Plateau, on or ahead of schedule. ARRA funding is being used to accelerate and augment cleanup activities already underway under the baseline Plateau Remediation Contract (PRC). This paper details challenges and accomplishments using ARRA funding to meet DOE-RL objectives of creating/saving jobs, expediting cleanup, and reducing lifecycle costs for cleanup during the first months of implementation.« less

Energetics of the O-H bond and of intramolecular hydrogen bonding in HOC6H4C(O)Y (Y = H, CH3, CH2CH=CH2, C[triple bond]CH, CH2F, NH2, NHCH3, NO2, OH, OCH3, OCN, CN, F, Cl, SH, and SCH3) compounds.

PubMed

Bernardes, Carlos E S; Minas da Piedade, Manuel E

2008-10-09

The energetics of the phenolic O-H bond in a series of 2- and 4-HOC 6H 4C(O)Y (Y = H, CH3, CH 2CH=CH2, C[triple bond]CH, CH2F, NH2, NHCH 3, NO2, OH, OCH3, OCN, CN, F, Cl, SH, and SCH3) compounds and of the intramolecular O...H hydrogen bond in 2-HOC 6H 4C(O)Y, was investigated by using a combination of experimental and theoretical methods. The standard molar enthalpies of formation of 2-hydroxybenzaldehyde (2HBA), 4-hydroxybenzaldehyde (4HBA), 2'-hydroxyacetophenone (2HAP), 2-hydroxybenzamide (2HBM), and 4-hydroxybenzamide (4HBM), at 298.15 K, were determined by micro- or macrocombustion calorimetry. The corresponding enthalpies of vaporization or sublimation were also measured by Calvet drop-calorimetry and Knudsen effusion measurements. The combination of the obtained experimental data led to Delta f H m (o)(2HBA, g) = -238.3 +/- 2.5 kJ.mol (-1), DeltafHm(o)(4HBA, g) = -220.3 +/- 2.0 kJ.mol(-1), Delta f H m (o)(2HAP, g) = -291.8 +/- 2.1 kJ.mol(-1), DeltafHm(o)(2HBM, g) = -304.8 +/- 1.5 kJ.mol (-1), and DeltafHm(o) (4HBM, g) = -278.4 +/- 2.4 kJ.mol (-1). These values, were used to assess the predictions of the B3LYP/6-31G(d,p), B3LYP/6-311+G(d,p), B3LYP/aug-cc-pVDZ, B3P86/6-31G(d,p), B3P86/6-311+G(d,p), B3P86/aug-cc-pVDZ, and CBS-QB3 methods, for the enthalpies of a series of isodesmic gas phase reactions. In general, the CBS-QB3 method was able to reproduce the experimental enthalpies of reaction within their uncertainties. The B3LYP/6-311+G(d,p) method, with a slightly poorer accuracy than the CBS-QB3 approach, achieved the best performance of the tested DFT models. It was further used to analyze the trends of the intramolecular O...H hydrogen bond in 2-HOC 6H 4C(O)Y evaluated by the ortho-para method and to compare the energetics of the phenolic O-H bond in 2- and 4-HOC 6H 4C(O)Y compounds. It was concluded that the O-H bond "strength" is systematically larger for 2-hydroxybenzoyl than for the corresponding 4-hydroxybenzoyl isomers mainly due to the presence of

CH3Cl, CH2Cl2, CHCl3, and CCl4: Infrared spectra, radiative efficiencies, and global warming potentials

NASA Astrophysics Data System (ADS)

Wallington, Timothy J.; Pivesso, Bruno Pasquini; Lira, Alane Moura; Anderson, James E.; Nielsen, Claus Jørgen; Andersen, Niels Højmark; Hodnebrog, Øivind

2016-05-01

Infrared spectra for the title compounds were measured experimentally in 700 Torr of air at 295 K and systematically modeled in B3LYP, M06-2X and MP2 calculations employing various basis sets. Calibrated infrared spectra over the wavenumber range 600-3500 cm-1 are reported and combined with literature data to provide spectra for use in experimental studies and radiative transfer calculations. Integrated absorption cross sections are (units of cm-1 molecule-1): CH3Cl, 660-780 cm-1, (3.89±0.19)×10-18; CH2Cl2, 650-800 cm-1, (2.16±0.11)×10-17; CHCl3, 720-810 cm-1, (4.08±0.20)×10-17; and CCl4, 730-825 cm-1, (6.30±0.31)×10-17. CH3Cl, CH2Cl2, CHCl3, and CCl4 have radiative efficiencies of 0.004, 0.028, 0.070, and 0.174 W m-2 ppb-1 and global warming potentials (100 year horizon) of 5, 8, 15, and 1775, respectively. Quantum chemistry calculations generally predict larger band intensities than the experimental values. The best agreement with experiments is obtained in MP2(Full) calculations employing basis sets of at least triple-zeta quality augmented by diffuse functions. The B3LYP functional is found ill-suited for calculating vibrational frequencies and infrared intensities of halocarbons.

Hanford Tanks 241-C-203 and 241 C 204: Residual Waste Contaminant Release Model and Supporting Data

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

Deutsch, William J.; Krupka, Kenneth M.; Lindberg, Michael J.

This report was revised in May 2007 to correct 90Sr values in Chapter 3. The changes were made on page 3.9, paragraph two and Table 3.10; page 3.16, last paragraph on the page; and Tables 3.21 and 3.31. The rest of the text remains unchanged from the original report issued in October 2004. This report describes the development of release models for key contaminants that are present in residual sludge remaining after closure of Hanford Tanks 241-C-203 (C-203) and 241-C-204 (C-204). The release models were developed from data generated by laboratory characterization and testing of samples from these two tanks.more » Key results from this work are (1) future releases from the tanks of the primary contaminants of concern (99Tc and 238U) can be represented by relatively simple solubility relationships between infiltrating water and solid phases containing the contaminants; and (2) high percentages of technetium-99 in the sludges (20 wt% in C-203 and 75 wt% in C-204) are not readily water leachable, and, in fact, are very recalcitrant. This is similar to results found in related studies of sludges from Tank AY-102. These release models are being developed to support the tank closure risk assessments performed by CH2M HILL Hanford Group, Inc., for the U.S. Department of Energy.« less

The catalytic effects of H2CO3, CH3COOH, HCOOH and H2O on the addition reaction of CH2OO + H2O → CH2(OH)OOH

NASA Astrophysics Data System (ADS)

Zhang, Tianlei; Lan, Xinguang; Wang, Rui; Roy, Soumendra; Qiao, Zhangyu; Lu, Yousong; Wang, Zhuqing

2018-07-01

The addition reaction of CH2OO + H2O → CH2(OH)OOH without and with X (X = H2CO3, CH3COOH and HCOOH) and H2O was studied at CCSD(T)/6-311+ G(3df,2dp)//B3LYP/6-311+G(2d,2p) level of theory. Our results show that X can catalyse CH2OO + H2O → CH2(OH)OOH reaction both by increasing the number of rings, and by adding the size of the ring in which ring enlargement by COOH moiety of X inserting into CH2OO...H2O is favourable one. Water-assisted CH2OO + H2O → CH2(OH)OOH can occur by H2O moiety of (H2O)2 or the whole (H2O)2 forming cyclic structure with CH2OO, where the latter form is more favourable. Because the concentration of H2CO3 is unknown, the influence of CH3COOH, HCOOH and H2O were calculated within 0-30 km altitude of the Earth's atmosphere. The results calculated within 0-5 km altitude show that H2O and HCOOH have obvious effect on enhancing the rate with the enhancement factors are, respectively, 62.47%-77.26% and 0.04%-1.76%. Within 5-30 km altitude, HCOOH has obvious effect on enhancing the title rate with the enhancement factor of 2.69%-98.28%. However, compared with the reaction of CH2OO + HCOOH, the rate of CH2OO...H2O + HCOOH is much slower.

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

The River Corridor Closure Contract How Washington Closure Hanford is Closing A Unique Department of Energy Project - 12425

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

Feist, E.T.

2012-07-01

Cleanup of the Hanford River Corridor has been one of Hanford Site's top priorities since the early 1990's. This urgency is due to the proximity of hundreds of waste sites to the Columbia River and the groundwater that continues to threaten the Columbia River. In April 2005, the U.S. Department of Energy, Richland Operations Office (DOE-RL) awarded the Hanford River Corridor Closure Contract (RCCC), a cost-plus incentive-fee closure contract with a 2015 end date and first of its kind at Hanford Site, to Washington Closure Hanford (WCH), a limited-liability company owned by URS, Bechtel National, and CH2M HILL. WCH ismore » a single-purpose company whose goal is to safely, compliantly, and efficiently accelerate cleanup in the Hanford River Corridor and reduce or eliminate future obligations to DOE-RL for maintaining long-term stewardship over the site. Accelerated performance of the work-scope while keeping a perspective on contract completion presents challenges that require proactive strategies to support the remaining work-scope through the end of the RCCC. This paper outlines the processes to address the challenges of completing work-scope while planning for contract termination. WCH is responsible for cleanup of the River Corridor 569.8 km{sup 2} (220 mi{sup 2}) of the 1,517.7 km{sup 2} (586 mi{sup 2}) Hanford Site's footprint reduction. At the end of calendar year 2011, WCH's closure implementation is well underway. Fieldwork is complete in three of the largest areas within the RCCC scope (Segments 1, 2, and 3), approximately 44.5% of the River Corridor (Figure 3). Working together, DOE-RL and WCH are in the process of completing the 'paper work' that will document the completion of the work-scope and allow DOE-RL to relieve WCH of contractual responsibilities and transition the completed areas to the Long-Term Stewardship Program, pending final action RODs. Within the next 4 years, WCH will continue to complete cleanup of the River Corridor following the

Synthesis, characterization, structural and biological aspects of copper(II) dithiocarbamate complexes - Part II, [Cu{S2CN(Me)(R1)}2], [Cu{S2CN(Me)(R2)}2] and [Cu{S2CN(R3)(R4)}2] {R1 = CH2CH(OMe)2, R2 = 2-methyl-1,3-dioxolane, R3 = CH2(CH2)2NCHPhOCH2Ph and R4 = CH2CH2OH}

NASA Astrophysics Data System (ADS)

Ferreira, Isabella P.; de Lima, Geraldo M.; Paniago, Eucler B.; Takahashi, Jacqueline A.; Krambrock, Klaus; Pinheiro, Carlos B.; Wardell, James L.; Visentin, Lorenzo C.

2013-09-01

Three new copper(II) dithiocarbamates (DTC), [Cu{S2CN(Me)(R1)}2] (1), [Cu{S2CN(Me)(R2)}2] (2) and [Cu{S2CN(R3)(R4)}2] (3) with R1 = CH2CH(OMe)2, R2 = 2-methyl-1,3-dioxolane, R3 = CH2(CH2)2NCHPhOCH2Ph and R4 = CH2CH2OH, have been synthesized and characterized by different spectroscopic techniques. Complexes (1) and (2) display typical EPR spectra for separated Cu(II) centers, and the spectrum of (3) is characteristic of two magnetically coupled Cu(II) ions with S = 1. The X-ray crystallographic determination has shown that complexes (1) and (2) crystallise in the triclinic and monoclinic systems. In addition both complexes are monomers in which the geometry at each Cu(II) is square planar. The in vitro antimicrobial activity of the sodium salts of ligands, and of the Cu(II)-DTC complexes have been screened against Aspergillus flavus, Aspergillus niger, Aspergillus parasiticus, Penicillium citrinum and Curvularia senegalensis, as well as Gram positive and Gram negative bacteria. Finally, the toxic effects of complexes (1)-(3) were performed using Chlorella vulgaris.

High-Resolution OH and CH2O Visualization in a Premixed Cavity-Anchored Ethylene-Air Flame in a M = 0.6 Flowfield

NASA Technical Reports Server (NTRS)

Geipel, Clayton M.; Rockwell, Robert D.; Chelliah, Harsha K.; Cutler, Andrew D.; Spelker, Christopher A.; Hashem, Zeid; Danehy, Paul M.

2017-01-01

OH and CH2O were imaged in a premixed, cavity-anchored, ethylene-air turbulent flame using a high resolution planar laser-induced fluorescence (PLIF) system. The electrically-heated, continuous flow facility (UVa Supersonic Combustion Facility, Configuration E) consisted of a Mach 2 nozzle, an isolator with fuel injectors, a test section with a cavity flame holder and optical access, and an extender. Standard test conditions comprised total temperature 1200 K, total pressure 300 kPa, local equivalence ratio near 0.4, and local Mach number near 0.6. OH PLIF data was also collected for a case with reduced total temperature and another with reduced equivalence ratio. OH and CH2O were excited in separate experiments with light sheets at 283.55 nm and 352.48 nm, respectively. A light sheet of approximate thickness 25 ?m illuminated the stream-wise midplane. This plane was imaged for 120 mm downstream of the backward-facing step. The intensified camera system imaged OH with magnification 1.97, a square 6.67 mm field of view, and in-plane resolution of 39 ?m. The smallest observed OH structures observed were approximately 100 ?m wide. The CH2O PLIF image signal was much weaker; the smallest observed structures were approximately 200 ?m wide. Composite fluorescence images were computed for the observed area.

Ab Initio Chemical Kinetics for the CH3 + O((3)P) Reaction and Related Isomerization-Decomposition of CH3O and CH2OH Radicals.

PubMed

Xu, Z F; Raghunath, P; Lin, M C

2015-07-16

The kinetics and mechanism of the CH3 + O reaction and related isomerization-decomposition of CH3O and CH2OH radicals have been studied by ab initio molecular orbital theory based on the CCSD(T)/aug-cc-pVTZ//CCSD/aug-cc-pVTZ, CCSD/aug-cc-pVDZ, and G2M//B3LYP/6-311+G(3df,2p) levels of theory. The predicted potential energy surface of the CH3 + O reaction shows that the CHO + H2 products can be directly generated from CH3O by the TS3 → LM1 → TS7 → LM2 → TS4 path, in which both LM1 and LM2 are very loose and TS7 is roaming-like. The result for the CH2O + H reaction shows that there are three low-energy barrier processes including CH2O + H → CHO + H2 via H-abstraction and CH2O + H → CH2OH and CH2O + H → CH3O by addition reactions. The predicted enthalpies of formation of the CH2OH and CH3O radicals at 0 K are in good agreement with available experimental data. Furthermore, the rate constants for the forward and some key reverse reactions have been predicted at 200-3000 K under various pressures. Based on the new reaction pathway for CH3 + O, the rate constants for the CH2O + H and CHO + H2 reactions were predicted with the microcanonical variational transition-state/Rice-Ramsperger-Kassel-Marcus (VTST/RRKM) theory. The predicted total and individual product branching ratios (i.e., CO versus CH2O) are in good agreement with experimental data. The rate constant for the hydrogen abstraction reaction of CH2O + H has been calculated by the canonical variational transition-state theory with quantum tunneling and small-curvature corrections to be k(CH2O + H → CHO + H2) = 2.28 × 10(-19) T(2.65) exp(-766.5/T) cm(3) molecule(-1) s(-1) for the 200-3000 K temperature range. The rate constants for the addition giving CH3O and CH2OH and the decomposition of the two radicals have been calculated by the microcanonical RRKM theory with the time-dependent master equation solution of the multiple quantum well system in the 200-3000 K temperature range at 1 Torr to

1,2-Dibenzyl and -Diaryltetradimethylamido-dimolybdenum and -Ditungsten Compounds: M2R2(NMe2)4 (M=M). Structural Effects of Me2N-to-M Alpha-Bonding.

DTIC Science & Technology

1982-07-07

CHETCUTI, M H CHISHOLM. K FOLTING N00OON 79-C 00144 UNCL’ASS IF IED INDU/DC/TR-82/2-MC NL mh~hEhEEo. OFFICE OF NAVAL RESEARCH Contract No. N00014-79...ldo i, n,.aowy a"d Identf ’ mko.) ’ / a, From the reactions between RMgCI (R = CH C H and CH-p-tolyl) or LiR.(R C6H, ~~,-- ;n 6o5 C"-tolyl) (2euv . 6...ligands u-donate to metal atomic Availability Codes V Avail and/or D special 4 orbitals which would otherwise be available for mischevious M--- H -C

Rotational spectrum of CH3CN⋯ClF and evidence for the +I effect of a CH3 group on the ‘chlorine’ bond N⋯ClF

NASA Astrophysics Data System (ADS)

Page, M. D.; Waclawik, E. R.; Holloway, J. H.; Legon, A. C.

1999-10-01

The ground-state rotational spectra of the isotopomers CH 3C 14N⋯ 35ClF, CH 3C 14N⋯ 37ClF, CD 3C 14N⋯ 35ClF and CH 3C 15N⋯ 35ClF of a symmetric-rotor complex formed by methyl cyanide and chlorine monofluoride have been observed and analysed to give the spectroscopic constants B0, DJ, DJK, χaa( 14N), χaa(Cl) and Mbb. Interpretations of these quantities on the basis of simple models enabled the geometry and strength of binding of the complex to be determined. It is found that the atoms C-CN⋯ClF lie on the C 3 axis of this complex of C 3v symmetry and that the distance r(N⋯Cl)=2.561(2) Å. The quadratic force constants associated with the intermolecular stretching mode and with the bending motion of the CH 3CN subunit pivoted at its mass centre were determined from the centrifugal distortion constants DJ and 2 DJ+ DJK. Their values were k σ=13.9(3) N m -1 and k α=3.0(1)×10 -20 J rad -2, respectively. A comparison of r(N⋯Cl) values and of k σ values establishes that the +I effect of the CH 3 group when it replaces H in HCN leads to a similar shortening of r(N⋯Cl) and to a similar increase in k σ in the two series RCN⋯ClF and RCN⋯HCl (R=H or CH 3).

Co-processing CH4 and oxygenates on Mo/H-ZSM-5: 2. CH4-CO2 and CH4-HCOOH mixtures.

PubMed

Bedard, Jeremy; Hong, Do-Young; Bhan, Aditya

2013-08-07

Co-processing of formic acid or carbon dioxide with CH4 (FA/CH4 = 0.01-0.03 and CO2/CH4 = 0.01-0.03) on Mo/H-ZSM-5 catalysts at 950 K with the prospect of kinetically coupling dehydrogenation and deoxygenation cycles results instead in a two-zone, staged bed reactor configuration consisting of upstream oxygenate/CH4 reforming and downstream CH4 dehydroaromatization. The addition of an oxygenate co-feed (oxygenate/CH4 = 0.01-0.03) causes oxidation of the active molybdenum carbide catalyst while producing CO and H2 until completely converted. Forward rates of C6H6 synthesis are unaffected by the introduction of an oxygenate co-feed after rigorously accounting for the thermodynamic reversibility caused by the H2 produced in oxygenate reforming reactions and the fraction of the active catalyst deemed unavailable for CH4 DHA. All effects of co-processing oxygenates with CH4 can be construed in terms of an approach to equilibrium.

Effects of Boreal Lake Wetlands on Atmospheric 13CH3D and 12CH2D2

NASA Astrophysics Data System (ADS)

Haghnegahdar, M. A.; Kohl, I. E.; Schauble, E. A.; Walter Anthony, K. M.; Young, E. D.

2017-12-01

Recently, we developed a theoretical model to investigate the potential use of 13CH3D and 12CH2D2 as tools for tracking atmospheric methane budget. We used electronic structure methods to estimate kinetic isotope fractionations associated with the major sink reactions of CH4 in air (reactions with •OH and Cl•), and literature data with reconnaissance measurements of the relative abundances of 13CH3D and 12CH2D2 to estimate the compositions of the largest atmospheric sources. Here we present new methane rare isotopologue data from boreal wetlands, comprising one of the most important sources, in order to evaluate the robustness of the model. Boreal wetlands (>55° N) account for more than half of the wetland area in the Northern hemisphere. We analyzed methane samples from high latitude lakes representing different geographical regions, geological and ecological contexts, methane fluxes, and isotopic signatures. Using clumped isotopes of CH4 we are able to determine the likely production mechanism for natural CH4 samples. So far, all of our analyzed samples except one plot in the microbial pure-culture methanogenesis field (Young et al. 2017) with ranges of -0.2‰ to +1.2‰ for Δ13CH3D, and -29.6‰ to -18.2‰ for Δ12CH2D2. These compositions are far from equilibrium. The one exception, from Lake Doughnut, Alaska, exhibits Δ13CH3D and Δ12CH2D2 values of +5.2‰ and +18.7‰, respectively, which fall near ambient thermodynamic equilibrium values. This may be an effect of methanotrophy. Mean Δ13CH3D and Δ12CH2D2 for all lake samples are +1.7‰ and -15.4‰ respectively, compared to our original estimate of +6.1‰ and +21.2‰ for the wetland methane source based on an assumption of equilibrium. If we assume that these samples are representative of the overall wetland source, Δ13CH3D decreases by 0.8‰ and Δ12CH2D2 decreases by 0.6‰ in our model of bulk atmospheric methane. Δ13CH3D and Δ12CH2D2 values of air (including •OH and Cl• sink

Phase stabilities of pyrite-related MTCh compounds (M=Ni, Pd, Pt; T=Si, Ge, Sn, Pb; Ch=S, Se, Te): A systematic DFT study

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

Bachhuber, Frederik; School of Chemical Sciences, University of Auckland, Private Bag 92019, Auckland; Krach, Alexander

2015-03-15

Pyrite-type and related systems appear for a wide range of binary and ternary combinations of transition metals and main group elements that form Zintl type dumbbell anion units. Those representatives with 20 valence electrons exhibit an extraordinary structural flexibility and interesting properties as low-gap semiconductors or thermoelectric and electrode materials. This work is devoted to the systematic exploration of novel compounds within the class of MTCh compounds (M=Ni, Pd, Pt; T=Si, Ge, Sn, Pb; Ch=S, Se, Te) by means of density functional calculations. Their preferred structures are predicted from an extended scheme of colored pyrites and marcasites. To determine theirmore » stabilities, competing binary MT{sub 2} and MCh{sub 2} boundary phases are taken into account as well as ternary M{sub 3}T{sub 2}Ch{sub 2} and M{sub 2}T{sub 3}Ch{sub 3} systems. Recently established stability diagrams are presented to account for MTCh ordering phenomena with a focus on a not-yet-reported ordering variant of the NiAs{sub 2} type. Due to the good agreement with experimental data available for several PtTCh systems, the predictions for the residual systems are considered sufficiently accurate. - Graphical abstract: Compositional and structural stability of MTCh compounds is investigated from first principle calculations. A conceptional approach is presented to study and predict novel stable and metastable compounds and structures of low gap semiconductors with TCh dumbbell units that are isoelectronic and structurally related to pyrite (FeS{sub 2}). - Highlights: • Study of compositional stability of MTCh vs. M{sub 3}T{sub 2}Ch{sub 2} and M{sub 2}T{sub 3}Ch{sub 3} compounds. • Study of structural stability of known and novel MTCh compounds. • Prediction of novel stable and metastable structures and compounds isoelectronic to pyrite, FeS{sub 2}.« less

Infrared observations and laboratory simulations of interstellar CH_4_ and SO_2_.

NASA Astrophysics Data System (ADS)

Boogert, A. C. A.; Schutte, W. A.; Helmich, F. P.; Tielens, A. G. G. M.; Wooden, D. H.

1997-02-01

Interstellar CH_4_ may consume a fair amount of the carbon budget in dense molecular clouds, but probably less than CO, CH_3_OH, and CO_2_. However, it can only be observed at wavelength regions in the infrared that are heavily affected by the earth atmosphere. With new space and airborne missions (e.g. ISO, SOFIA) in mind we have studied the near infrared absorption spectra of solid and gaseous CH_4_. We obtained laboratory spectra of the ν_4_ deformation mode (1302cm^-1^, 7.68μm) of solid CH_4_ in astrophysically relevant mixtures. We found that the peak position and width of this absorption band vary strongly as a function of molecular environment, compared to temperature and particle shape effects. Hence, observations of this feature will provide a powerful probe of the molecular composition of interstellar ices. Also the gas phase CH_4_ ro-vibrational spectrum of the same band has been calculated. Using observed physical conditions around the protostar W 33A, we show that unresolved gaseous CH_4_ lines are detectable (at the 2-5% level) at a resolution R>1000, when the column density N>=10^16^ cm^-2^. An astrophysically relevant molecule with a very strong transition in the same wavelength regime, is SO_2_. We studied the ν _3_ asymmetric stretching mode (1319 cm^-1^, 7.58 μm) of solid SO_2_ in several mixtures, revealing that the peak position, width and detailed profile of this band are very sensitive to the molecular environment. Besides probing the composition of ice mantles, observations of solid SO_2_ will provide important information on the sulfur budget locked up in grain mantles, which is currently poorly known. We compare the laboratory and calculated spectra of CH_4_ and SO_2_ with previously published ground based spectra and new airborne observations of young stellar objects in the 7-8μm region. W 33A, NGC 7538 : IRS1 and IRS9 show a feature near 7.68μm that is consistent with absorption by solid CH_4_ or the Q-branch of gaseous CH_4_. The

Infrared absorption of 1-chloro-2-methyl-2-propyl [⋅C(CH3)2CH2Cl] and 2-chloro-2-methylpropyl [⋅CH2C(CH3)2Cl] radicals produced in the addition reactions of Cl with isobutene (i-C4H8) in solid para-hydrogen.

PubMed

Chou, Ching-Yin; Lee, Yuan-Pern

2016-10-07

The addition reactions of chlorine atom with isobutene (i-C 4 H 8 ) in solid para-hydrogen (p-H 2 ) were investigated with infrared (IR) absorption spectra. When a p-H 2 matrix containing Cl 2 and isobutene was irradiated with ultraviolet light at 365 nm, intense lines in a set at 534.5, 1001.0, 1212.9, 1366.0, 2961.6, and 2934.7 cm -1 , and several weaker others due to the 1-chloro-2-methyl-2-propyl radical, ⋅ C(CH 3 ) 2 CH 2 Cl, and those in a second set including intense ones at 642.7, 799.2, 1098.2, 1371.8, and 3027.3 cm -1 due to the 2-chloro-2-methylpropyl radical, ⋅ CH 2 C(CH 3 ) 2 Cl, appeared; the ratio of ⋅ C(CH 3 ) 2 CH 2 Cl to ⋅ CH 2 C(CH 3 ) 2 Cl was approximately (3 ± 1):1. The observed wavenumbers and relative intensities agree with the vibrational wavenumbers and IR intensities predicted with the B3PW91/aug-cc-pVTZ method. That the Cl atom adds to both carbons of the C=C bond of isobutene with the terminal site slightly favored is consistent with the energies of products predicted theoretically, but is in contrast to the reaction of Cl + propene in solid p-H 2 in which the addition of Cl to mainly the central C atom was previously reported. The role of the p-H 2 matrix in affecting the reaction paths is discussed. Absorption lines of the complex i-C 4 H 8 ⋅Cl 2 and the dichloro-product anti-1,2-dichloro-2-methylpropane, a-CH 2 ClCCl(CH 3 ) 2 , are also characterized.

Microstructural evolution of diamond films from CH{sub 4}/H{sub 2}/N{sub 2} plasma and their enhanced electrical properties

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

Sankaran, K. J.; Tai, N. H., E-mail: nhtai@mx.nthu.edu.tw; Lin, I. N., E-mail: inanlin@mail.tku.edu.tw

2015-02-21

The influence of N{sub 2} concentration in CH{sub 4}/H{sub 2}/N{sub 2} plasma on microstructural evolution and electrical properties of diamond films is systematically investigated. While the diamond films grown in CH{sub 4}/H{sub 2} plasma contain large diamond grains, for the diamond films grown using CH{sub 4}/H{sub 2}/(4%)N{sub 2} plasma, the microstructure drastically changed, resulting in ultra-nanosized diamond grains with Fd3m structure and a{sub 0} = 0.356 nm, along with the formation of n-diamond (n-D), a metastable form of diamond with space group Fm3m and a{sub 0} = 0.356 nm, and i-carbon (i-C) clusters, the bcc structured carbon with a{sub 0} = 0.432 nm. In addition, these films contain widemore » grain boundaries containing amorphous carbon (a-C). The electron field emission (EFE) studies show the best EFE behavior for 4% N{sub 2} films among the CH{sub 4}/H{sub 2}/N{sub 2} grown diamond films. They possess the lowest turn-on field value of 14.3 V/μm and the highest EFE current density value of 0.37 mA/cm{sup 2} at an applied field of 25.4 V/μm. The optical emission spectroscopy studies confirm that CN species are the major criterion to judge the changes in the microstructure of the films. It seems that the grain boundaries can provide electron conduction networks to transport efficiently the electrons to emission sites for field emission, as long as they have sufficient thickness. Whether the matrix nano-sized grains are 3C-diamond, n-D or i-C is immaterial.« less

Total cross sections of electron scattering by molecules NF3, PF3, N(CH3)3, P(CH3)3, NH(CH3)2, PH(CH3)2, NH2CH3 and PH2CH3 at 30-5000 eV

NASA Astrophysics Data System (ADS)

Shi, D. H.; Sun, J. F.; Zhu, Z. L.; Liu, Y. F.

2010-04-01

Total cross sections of electron scattering by eight molecules NF3, PF3, N(CH3)3, P(CH3)3, NH(CH3)2, PH(CH3)2, NH2CH3 and PH2CH3, which have some structural similarities, are calculated at the Hartree-Fork level by the modified additivity rule approach [D.H. Shi, J.F. Sun, Z.L. Zhu, H. Ma, Y.F. Liu, Eur. Phys. J. D 45, 253 (2007); D.H. Shi, J.F. Sun, Y.F. Liu, Z.L. Zhu, X.D. Yang, Chin. Opt. Lett. 4, 192 (2006)]. The modified additivity rule approach takes into considerations that the contributions of the geometric shielding effect vary as the energy of incident electrons, the dimension of target molecule, the number of electrons in the molecule and the number of atoms constituting the molecule. The present investigations cover the impact energy range from 30 to 5000 eV. The quantitative total cross sections are compared with those obtained by experiments and other theories. Excellent agreement is observed even at energies of several tens of eV. It shows that the modified additivity rule approach is applicable to carry out the total cross section calculations of electron scattering by these molecules at intermediate and high energies, in particular over the energy range above 80 eV or so. It proves that the microscopic molecular properties, such as the geometrical size of the target and the number of atoms constituting the molecule, are of crucial importance in the TCS calculations. The new results for PH(CH3)2 and PH2CH3 are also presented at energies from 30 to 5000 eV, although no experimental and theoretical data are available for comparison. In the present calculations, the atoms are still represented by the spherical complex optical potential, which is composed of static, exchange, polarization and absorption terms.

Effect of substituent groups (R= sbnd CH3, sbnd Br and sbnd CF3) on the structure, stability and redox property of [Cr(R-pic)2(H2O)2]NO3·H2O complexes

NASA Astrophysics Data System (ADS)

Chai, Jie; Liu, Yanfei; Liu, Bin; Yang, Binsheng

2017-12-01

Complexes [Cr(3-CH3-pic)2(H2O)2]NO3·H2O (1), [Cr(5-Br-pic)2(H2O)2]NO3·H2O (2) and [Cr(5-CF3-pic)2(H2O)2]NO3·H2O (3) were synthesized (pic = pyridine-2-carboxylic acid) and characterized by X-ray crystal diffraction. Crystal structure indicates that two bidentate ligands occupy equatorial position and two H2O occupy axial positions in trans-configuration. (i) Decomposition of complexes 1, 2 and 3 in different medium (phosphate buffered saline (PBS), apo-ovotransferrin (apootf) and EDTA) indicates that decomposition rate constants of these complexes follow the sequence of 1 < 2 < 3. (ii) The redox potential of Cr(III)/Cr(II) by cyclic voltammetry follows the sequence of 1 (-1.20 V) > 3 (-1.29 V) > 2 (-1.31 V). (iii) In addition, ·OH-generation of the new synthesized complexes was determined by Fenton-like reaction in comparison with Cr(pic)3, and it may be related to the reduction potential of the complexes. (iv) Moreover, Hammett substituent constants σp (inductive) and σm (resonance) (R = 3-CH3, 5-Br, 5-CF3) were introduced to evaluate the impact of substituent groups on the bond length and decomposition kinetics. The substituent group on the ligand has great effect on the properties of the complexes.

Copper-Catalyzed, Directing Group-Assisted Fluorination of Arene and Heteroarene C-H Bonds

PubMed Central

Truong, Thanh; Klimovica, Kristine; Daugulis, Olafs

2013-01-01

We have developed a method for direct, copper-catalyzed, auxiliary-assisted fluorination of β-sp2 C-H bonds of benzoic acid derivatives and γ-sp2 C-H bonds of α,α-disubstituted benzylamine derivatives. The reaction employs CuI catalyst, AgF fluoride source, and DMF, pyridine, or DMPU solvent at moderately elevated temperatures. Selective mono- or difluorination can be achieved by simply changing reaction conditions. The method shows excellent functional group tolerance and provides a straightforward way for the preparation of ortho-fluorinated benzoic acids. PMID:23758609

Construction of (CuX)2n cluster-containing (X = Br, I; n = 1, 2) coordination polymers assembled by dithioethers ArS(CH2)(m)SAr (Ar = Ph, p-Tol; m = 3, 5): effect of the spacer length, aryl group, and metal-to-ligand ratio on the dimensionality, cluster nuclearity, and the luminescence properties of the metal-organic frameworks.

PubMed

Knorr, Michael; Guyon, Fabrice; Khatyr, Abderrahim; Strohmann, Carsten; Allain, Magali; Aly, Shawkat M; Lapprand, Antony; Fortin, Daniel; Harvey, Pierre D

2012-09-17

Reaction of CuI with bis(phenylthio)propane in a 1:1 ratio yields the two-dimensional coordination polymer [{Cu(μ(2)-I)(2)Cu}{μ-PhS(CH(2))(3)SPh}(2)](n) (1). The 2D-sheet structure of 1 is built up by dimeric Cu(2)I(2) units, which are connected via four bridging 1,3-bis(phenylthio)propane ligands. In contrast, treatment of 2 equiv of CuI with 1,3-bis(phenylthio)propane in MeCN solution affords in a self-assembly reaction the strongly luminescent metal-organic 2D-coordination polymer [Cu(4)I(4){μ-PhS(CH(2))(3)Ph}(2)](n) (2), in which cubane-like Cu(4)(μ(3)-I)(4) cluster units are linked by the dithioether ligands. The crystallographically characterized one-dimensional (1D) compound [{Cu(μ(2)-Br)(2)Cu}{μ-PhS(CH(2))(3)SPh}(2)](n) (3) is obtained using CuBr. The outcome of the reaction of PhS(CH(2))(5)SPh with CuI also depends of the metal-to-ligand ratio employed. Mixing CuI and the dithioether in a 2:1 ratio results in formation of [Cu(4)I(4){μ-PhS(CH(2))(5)Ph}(2)](n) (4) in which cubane-like Cu(4)(μ(3)-I)(4) clusters are linked by the bridging dithioether ligand giving rise to a 1D necklace structure. A ribbon-like 1D-polymer with composition [{Cu(μ(2)-I)(2)Cu}{μ-PhS(CH(2))(5)SPh}(2)](n) (5), incorporating rhomboid Cu(2)I(2) units, is produced upon treatment of CuI with 1,5-bis(phenylthio)pentane in a 1:1 ratio. Reaction of CuBr with PhS(CH(2))(5)SPh produces the isomorphous 1D-compound [{Cu(μ(2)-Br)(2)Cu}{μ-PhS(CH(2))(5)SPh}(2)](n) (6). Strongly luminescent [Cu(4)I(4){μ-p-TolS(CH(2))(5)STol-p}(2)](n) (7) is obtained after mixing 1,5-bis(p-tolylthio)pentane with CuI in a 1:2 ratio, and the 2D-polymer [{Cu(μ(2)-I)(2)Cu}(2){μ-p-TolS(CH(2))(5)STol-p}(2)](n) (8) results from reaction in a 1:1 metal-to-ligand ratio. Under the same reaction conditions, 1D-polymeric [{Cu(μ(2)-Br)(2)Cu}{μ-p-TolS(CH(2))(5)STol-p}(2)](n) (9) is formed using CuBr. This study reveals that the structure of the self-assembly process between CuX and ArS(CH(2))(m)SAr ligands is

Rate Constants for the Reactions of OH with CH(sub 3)Cl, CH(sub 2) C1(sub 2), CHC1(sub 3)and CH(sub 3)Br

NASA Technical Reports Server (NTRS)

Hsu, H-J.; DeMore, W.

1994-01-01

Rate constants for the reactions of OH with CH3C1, 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).

Au99(SPh)42 nanomolecules: aromatic thiolate ligand induced conversion of Au144(SCH2CH2Ph)60.

PubMed

Nimmala, Praneeth Reddy; Dass, Amala

2014-12-10

A new aromatic thiolate protected gold nanomolecule Au99(SPh)42 has been synthesized by reacting the highly stable Au144(SCH2CH2Ph)60 with thiophenol, HSPh. The ubiquitous Au144(SR)60 is known for its high stability even at elevated temperature and in the presence of excess thiol. This report demonstrates for the first time the reactivity of the Au144(SCH2CH2Ph)60 with thiophenol to form a different 99-Au atom species. The resulting Au99(SPh)42 compound, however, is unreactive and highly stable in the presence of excess aromatic thiol. The molecular formula of the title compound is determined by high resolution electrospray mass spectrometry (ESI-MS) and confirmed by the preparation of the 99-atom nanomolecule using two ligands, namely, Au99(SPh)42 and Au99(SPh-OMe)42. This mass spectrometry study is an unprecedented advance in nanoparticle reaction monitoring, in studying the 144-atom to 99-atom size evolution at such high m/z (∼12k) and resolution. The optical and electrochemical properties of Au99(SPh)42 are reported. Other substituents on the phenyl group, HS-Ph-X, where X = -F, -CH3, -OCH3, also show the Au144 to Au99 core size conversion, suggesting minimal electronic effects for these substituents. Control experiments were conducted by reacting Au144(SCH2CH2Ph)60 with HS-(CH2)n-Ph (where n = 1 and 2), bulky ligands like adamantanethiol and cyclohexanethiol. It was observed that conversion of Au144 to Au99 occurs only when the phenyl group is directly attached to the thiol, suggesting that the formation of a 99-atom species is largely influenced by aromaticity of the ligand and less so on the bulkiness of the ligand.

Modeling the CH Stretch Vibrational Spectroscopy of M(+)[Cyclohexane] (M = Li, Na, and K) Ions.

PubMed

Sibert, Edwin L; Tabor, Daniel P; Lisy, James M

2015-10-15

The CH stretch vibrations of M(+)[cyclohexane][Ar] (M = Li, Na, and K) cluster ions were theoretically modeled. Results were compared to the corresponding infrared photodissociation spectra of Patwari and Lisy [ J. Chem. Phys A 2007 , 111 , 7585 ]. The experimental spectra feature a substantial spread in CH stretch vibration frequencies due to the alkali metal cation binding to select hydrogens of cyclohexane. This spread was observed to increase with decreasing metal ion size. Exploring the potential energy landscape revealed the presence of three conformers whose energy minima lie within ∼1 kcal of each other. It was determined that in all conformers the metal ion interacts with three hydrogen atoms; these hydrogen atoms can be either equatorial or axial. The corresponding spectra for these conformers were obtained with a theoretical model Hamiltonian [ J. Chem. Phys. 2013 , 138 , 064308 ] that consists of local mode CH stretches bilinearly coupled to each other and Fermi coupled to lower frequency modes. Frequencies and coupling parameters were obtained from electronic structure calculations that were subsequently scaled on the basis of previous studies. Theoretical spectra of a single low energy conformer were found to match well with the experimental spectra. The relative frequency shifts with changing metal ion size were accurately modeled with parameters generated by using ωB97X-D/6-311++(2d,p) calculations.

ChIA-PET2: a versatile and flexible pipeline for ChIA-PET data analysis

PubMed Central

Li, Guipeng; Chen, Yang; Snyder, Michael P.; Zhang, Michael Q.

2017-01-01

ChIA-PET2 is a versatile and flexible pipeline for analyzing different types of ChIA-PET data from raw sequencing reads to chromatin loops. ChIA-PET2 integrates all steps required for ChIA-PET data analysis, including linker trimming, read alignment, duplicate removal, peak calling and chromatin loop calling. It supports different kinds of ChIA-PET data generated from different ChIA-PET protocols and also provides quality controls for different steps of ChIA-PET analysis. In addition, ChIA-PET2 can use phased genotype data to call allele-specific chromatin interactions. We applied ChIA-PET2 to different ChIA-PET datasets, demonstrating its significantly improved performance as well as its ability to easily process ChIA-PET raw data. ChIA-PET2 is available at https://github.com/GuipengLi/ChIA-PET2. PMID:27625391

Micellar induced regioselectivity in the two-step consecutive reaction of SO3(2-) with Br-(CH2CH2)n-Br (n=2-5).

PubMed

Currie, Fredrik; Jarvoll, Patrik; Holmberg, Krister; Romsted, Laurence S; Gunaseelan, Krishnan

2007-08-15

High field (800 MHz) (1)H NMR was used to monitor the two-step consecutive reaction of excess SO(3)(2-) with symmetrical bifunctional alpha,omega-dibromoalkanes with butane (DBB), hexane (DBH), octane (DBO), and decane (DBD) chains in CTAB micelles at 25 degrees C. The first-order rate constant for the first substitution step for DBB and DBH is about 5 times faster than for the second, but the kinetics for DBO and DBD were not cleanly first-order. After 40 min, the solution contained about 80% of the intermediate bromoalkanesulfonate from DBB and DBH and the remainder is alkanedisulfonate and unreacted starting material. The same reactions were carried out in homogeneous MeOH/D(2)O solutions at 50 degrees C. The rate constants for all four alpha,omega-dibromoalkanes were first-order throughout the time course of the reaction and the same within +/-10%. However, because micellar solutions are organized on the nanoscale and bring together lipophilic and hydrophilic reactants into a small reaction volume at the micellar interface, they speed this substitution reaction considerably compared to reaction in MeOH/D(2)O. The CTAB micelles also induce a significant regioselectivity in product formation by speeding the first step of the consecutive reaction more than the second. The results are consistent with the bromoalkanesulfonate intermediates having a radial orientation within the micelles with the -CH(2)SO(3)(-) group in the interfacial region and the -CH(2)Br group directed into the micellar core such that the concentration of -CH(2)Br groups in the reactive zone, i.e., the micellar interface, is significantly reduced. These results provide the first example of self-assembled surfactant system altering the relative rates of the reaction steps of a consecutive reaction and, in doing so, enhancing monosubstitution of a symmetrically disubstituted species.

Dynamics of the F(-) + CH3I → HF + CH2I(-) Proton Transfer Reaction.

PubMed

Zhang, Jiaxu; Xie, Jing; Hase, William L

2015-12-17

Direct chemical dynamics simulations, at collision energies Erel of 0.32 and 1.53 eV, were performed to obtain an atomistic understanding of the F(-) + CH3I reaction dynamics. There is only the F(-) + CH3I → CH3F + I(-) bimolecular nucleophilic substitution SN2 product channel at 0.32 eV. Increasing Erel to 1.53 eV opens the endothermic F(-) + CH3I → HF + CH2I(-) proton transfer reaction, which is less competitive than the SN2 reaction. The simulations reveal proton transfer occurs by two direct atomic-level mechanisms, rebound and stripping, and indirect mechanisms, involving formation of the F(-)···HCH2I complex and the roundabout. For the indirect trajectories all of the CH2I(-) is formed with zero-point energy (ZPE), while for the direct trajectories 50% form CH2I(-) without ZPE. Without a ZPE constraint for CH2I(-), the reaction cross sections for the rebound, stripping, and indirect mechanisms are 0.2 ± 0.1, 1.2 ± 0.4, and 0.7 ± 0.2 Å(2), respectively. Discarding trajectories that do not form CH2I(-) with ZPE reduces the rebound and stripping cross sections to 0.1 ± 0.1 and 0.7 ± 0.5 Å(2). The HF product is formed rotationally and vibrationally unexcited. The average value of J is 2.6 and with histogram binning n = 0. CH2I(-) is formed rotationally excited. The partitioning between CH2I(-) vibration and HF + CH2I(-) relative translation energy depends on the treatment of CH2I(-) ZPE. Without a CH2I(-) ZPE constraint the energy partitioning is primarily to relative translation with little CH2I(-) vibration. With a ZPE constraint, energy partitioning to CH2I(-) rotation, CH2I(-) vibration, and relative translation are statistically the same. The overall F(-) + CH3I rate constant at Erel of both 0.32 and 1.53 eV is in good agreement with experiment and negligibly affected by the treatment of CH2I(-) ZPE, since the SN2 reaction is the major contributor to the total reaction rate constant. The potential energy surface and reaction dynamics for F

Hanford tank initiative vehicle/based waste retrieval demonstration report phase II, track 2

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

Berglin, E.J.

1997-07-31

Using the versatile TracPUMpTm, Environmental Specialties Group, LLC (ES) performed a successful Phase 11 demonstration of a Vehicle- Based Waste Retrieval System (VWRS) for removal of waste material and residual liquid found in the Hanford Underground Storage Tanks (ousts). The purpose of this demonstration was to address issues pertaining to the use of a VWRS in OUSTS. The demonstration also revealed the waste removal capabilities of the TracPumpTm and the most effective techniques and equipment to safely and effectively remove waste simulants. ES successfully addressed the following primary issues: I . Dislodge and convey the waste forms present in themore » Hanford OUSTS; 2. Access the UST through tank openings as small as twenty-four inches in diameter; 3. Traverse a variety of terrains including slopes, sludges, rocks and hard, slippery surfaces without becoming mired; 4. Dislodge and convey waste within the confinement of the Decontamination Containment Capture Vessel (DCCV) and with minimal personnel exposure; 5. Decontaminate equipment to acceptable limits during retrieval from the UST; 6. Perform any required maintenance within the confinement of the DCCV; and 7. Maintain contaminate levels ``as low as reasonably achievable`` (ALARA) within the DCCV due to its crevice and comer-free design. The following materials were used to simulate the physical characteristics of wastes found in Hanford`s OUSTS: (1) Hardpan: a clay-type material that has high shear strength; (2) Saltcake: a fertilizer-based material that has high compressive strength; and (3) Wet Sludge.- a sticky, peanut- butter- like material with low shear strength. Four test beds were constructed of plywood and filled with a different simulant to a depth of eight to ten inches. Three of the test beds were of homogenous simulant material, while the fourth bed consisted of a mixture of all three simulant types.« less

Synchrotron Photoionization Study of Furan and 2-Methylfuran Reactions with Methylidyne Radical (CH) at 298 K.

PubMed

Carrasco, Erica; Smith, Kenneth J; Meloni, Giovanni

2018-01-11

The reactions of furan and 2-methylfuran with methylidyne CH (X 2 Π) radical were investigated at 298 K using synchrotron radiation produced at the Advanced Light Source of the Lawrence Berkeley National Laboratory. Reaction products were observed by multiplexed photoionization mass spectrometry and characterized based on their photoionization spectra and kinetic time traces. Primary products observed in furan + CH are 2,4-cyclopentadien-1-one (m/z = 80), 2-penten-4-ynal (m/z = 80), and vinylacetylene (m/z = 52). From 2-methylfuran + CH, 2-4-cyclopentadien-1-carbaldehyde (m/z = 94), 2,3,4-hexatrienal (m/z = 94), 1,3 cyclopentadiene (m/z = 66), 3-penten-1-yne (Z) (m/z = 66), and vinylacetylene (m/z = 52) are the primary products observed. Using potential energy surface scans, thermodynamically favorable reaction pathways are proposed. CH addition to the π-bonds in furan and 2-methylfuran rings was found to be the entrance channel that led to formation of all identified primary products. Both reactions follow patterns of H loss and CHO loss, as well as formation of cyclic and acyclic isomers.

IR Spectra of n-Bu4M (M = Si, Ge, Sn, Pb), n-BuAuPPh3-d15, and "n-Bu" on a Gold Surface.

PubMed

Kaleta, Jiří; Bednárová, Lucie; Čížková, Martina; Wen, Jin; Kaletová, Eva; Michl, Josef

2017-06-22

Observed and DFT-calculated IR spectra of n-Bu 4 M (M = Si, Ge, Sn, Pb), (CH 3 CH 2 CH 2 13 CD 2 ) 4 Sn, and n-BuAuPPh 3 -d 15 are reported and assigned. The asymmetric CH stretching vibration of the CH 2 group adjacent to the metal atom appears as a distinct shoulder at ∼2934 cm -1 , whereas for other CH 2 groups it is located at ∼2922 cm -1 . The characteristic peak at ∼2899 cm -1 is attributed to an overtone of a symmetric CH 2 bend at ∼1445 cm -1 . In n-BuAuPPh 3 -d 15 , the CH stretching vibrations of the butyl group are shifted to lower frequencies by ∼10 cm -1 , and two possible rationalizations are offered.

High Resolution Direct Frequency Comb Spectroscopy of Vinyl Bromide (C_2H_3Br) and Nitromethane (CH_3NO_2) in the CH Stretch Region

NASA Astrophysics Data System (ADS)

Changala, Bryan; Spaun, Ben; Patterson, David; Ye, Jun

2016-06-01

We present high resolution rovibrational spectra of buffer gas cooled vinyl bromide (C_2H_3Br) and nitromethane (CH_3NO_2) in the 3 μm CH stretch region, acquired via cavity-enhanced direct frequency comb absorption spectroscopy. The ˜10 K translational and rotational temperatures of the molecular gas, as well as the narrow linewidth of the frequency comb, yield well resolved rotational structure, isotope shifts, and nuclear hyperfine splittings. Given the wide bandwidth of the light source and the long path length of the enhancement cavity, we measure entire vibrational bands in a single shot with high signal-to-noise ratios. We discuss spectra of the entire fundamental CH stretch manifolds of both C_2H_3Br and CH_3NO_2, which provide contrasting examples of rovibrational structure of rigid and non-rigid systems. C_2H_3Br is a relatively normal asymmetric top, exhibiting local perturbations to its rotational structure. Conversely, CH_3NO_2 contains an essentially unhindered methyl rotor. Of particular interest are its quasi-degenerate asymmetric CH stretch modes. Here, one must consider multiple couplings between torsional, rotational, and vibrational angular momentum, leading to qualitatively new level patterns and structure.

Methane Provenance Determined by CH2D2 and 13CH3D Abundances

NASA Astrophysics Data System (ADS)

Kohl, I. E.; Giunta, T.; Warr, O.; Ash, J. L.; Ruffine, L.; Sherwood Lollar, B.; Young, E. D.

2017-12-01

Determining the provenance of naturally occurring methane gases is of major interest to energy companies and atmospheric climate modelers, among others. Bulk isotopic compositions and other geochemical tracers sometimes fail to provide definitive determinations of sources of methane due to complications from mixing and complicated chemical pathways of origin. Recent measurements of doubly-substituted isotopologues of methane, CH2D2 (UCLA) and 13CH3D (UCLA, CalTech, and MIT) have allowed for major improvements in sourcing natural methane gases. Early work has focused on formation temperatures obtained when the relative abundances of both doubly-substituted mass-18 species are consistent with internal equilibrium. When methane gases do not plot on the thermodynamic equilibrium curve in D12CH2D2 vs D13CH3D space, temperatures determined from D13CH3D values alone are usually spurious, even when appearing reasonable. We find that the equilibrium case is actually rare and almost exclusive to thermogenic gases produced at temperatures exceeding 100°C. All other relevant methane production processes appear to generate gases that are not in isotopologue-temperature equilibrium. When gases show departures from equilibrium as determined by the relationship between CH2D2 and 13CH3D abundances, data fall within empirically defined fields representing formation pathways. These fields are thus far consistent between different geological settings and and between lab experiments and natural samples. We have now defined fields for thermogenic gas production, microbial methanogenesis, low temperature abiotic (Sabatier) synthesis and higher temperature FTT synthesis. The majority of our natural methane data can be explained by mixing between end members originating within these production fields. Mixing can appear complex, resulting in both hyper-clumped and anti-clumped isotopologue abundances. In systems where mixtures dominate and end-members are difficult to sample, mixing models

Soil CO2, CH4 and N2O effluxes and concentrations in soil profiles down to 15.5m depth in eucalypt plantations under contrasted rainfall regimes

NASA Astrophysics Data System (ADS)

Germon, A.; Nouvellon, Y.; Christophe, J.; Chapuis-Lardy, L.; Robin, A.; Rosolem, C. A.; Gonçalves, J. L. D. M.; Guerrini, I. A.; Laclau, J. P.

2017-12-01

Silvicultural practices in planted forests affect the fluxes of greenhouse gases at the soil surface and the major factors driving greenhouse gas production in forest soils (substrate supply, temperature, water content,…) vary with soil depth. Our study aimed to assess the consequences of drought on the temporal variability of CO2, CH4 and N2O fluxes throughout very deep soil profiles in Eucalyptus grandis plantations 3 months before the harvest then in coppice, the first 18 months after clear-cutting. Two treatments were compared: one with 37% of throughfall excluded by plastic sheets (TE), and one without rainfall exclusion (WE). Measurements of soil CO2 efflux were made every two weeks for 30 months using a closed-path Li8100 system in both treatment. Every two weeks for 21 months, CO2, CH4 and N2O surface effluxes were measured using the closed-chamber method and concentrations in the soil were measured at 7 depths down to 15.5 m in both TE and WE. At most measurement dates, soil CO2 efflux were significantly higher in TE than in WE. Across the two treatments and the measurement dates, CO2 concentrations increased from 4446 ± 2188 ppm at 10 cm deep to 15622 ± 3523 ppm at 15.5 m, CH4 concentrations increased from 0.41 ± 0.17 ppm at 10 cm deep to 0.77 ± 0.24 ppm at 15.5 m and N2O concentrations remained roughly constant and were on average 478 ± 55 ppb between soil surface and 15.5 m deep. CO2 and N2O concentrations were on average 20.7 and 7.6% lower in TE than in WE, respectively, across the sampling depths. However, CH4 concentrations in TE were on average 44.4% higher than in WE, throughout the soil profile. Those results suggest that extended drought periods might reduce the production of CO2 and N2O but increase the accumulation of CH4 in eucalypt plantations established in deep tropical soils. Very deep tropical soils cover huge areas worldwide and improving our understanding of the spatiotemporal dynamics of gas concentrations in deep soil layers

Development of occupational exposure limits for the Hanford tank farms.

PubMed

Still, Kenneth R; Gardner, Donald E; Snyder, Robert; Anderson, Thomas J; Honeyman, James O; Timchalk, Charles

2010-04-01

Production of plutonium for the United States' nuclear weapons program from the 1940s to the 1980s generated 53 million gallons of radioactive chemical waste, which is stored in 177 underground tanks at the Hanford site in southeastern Washington State. Recent attempts to begin the retrieval and treatment of these wastes require moving the waste to more modern tanks and result in potential exposure of the workers to unfamiliar odors emanating from headspace in the tanks. Given the unknown risks involved, workers were placed on supplied air respiratory protection. CH2MHILL, the managers of the Hanford site tank farms, asked an Independent Toxicology Panel (ITP) to assist them in issues relating to an industrial hygiene and risk assessment problem. The ITP was called upon to help determine the risk of exposure to vapors from the tanks, and in general develop a strategy for solution of the problem. This paper presents the methods used to determine the chemicals of potential concern (COPCs) and the resultant development of screening values and Acceptable Occupational Exposure Limits (AOELs) for these COPCs. A total of 1826 chemicals were inventoried and evaluated. Over 1500 chemicals were identified in the waste tanks headspaces and more than 600 of these were assigned screening values; 72 of these compounds were recommended for AOEL development. Included in this list of 72 were 57 COPCs identified by the ITP and of these 47 were subsequently assigned AOELs. An exhaustive exposure assessment strategy was developed by the CH2MHILL industrial hygiene department to evaluate these COPCs.

Utilisation of an eta(3)-allyl hydride complex, formed by UV irradiation, as a controlled source of 16-electron (eta(5)-C(5)Me(5))Rh(CH(2)[double bond, length as m-dash]CHMe).

PubMed

Sexton, Catherine J; López-Serrano, Joaquín; Lledós, Agustí; Duckett, Simon B

2008-10-21

Low temperature UV irradiation of solutions of (eta(5)-C(5)Me(5))Rh(CH(2)[double bond, length as m-dash]CHMe)(2) yields (eta(5)-C(5)Me(5))Rh(eta(3)-CH(2)CHCH(2))(H), which provides controlled access to the 16-electron fragment (eta(5)-C(5)Me(5))Rh(CH(2)[double bond, length as m-dash]CHMe).

HANFORD SCIENCE & TECHNOLOGY NEEDS STATEMENTS 2002

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

WIBLE, R.A.

This document: (a) provides a comprehensive listing of the Hanford sites science and technology needs for fiscal year (FY) 2002; and (b) identifies partnering and commercialization opportunities within industry, other federal and state agencies, and the academic community. These needs were prepared by the Hanford projects (within the Project Hanford Management Contract, the Environmental Restoration Contract and the River Protection Project) and subsequently reviewed and endorsed by the Hanford Site Technology Coordination Group (STCG). The STCG reviews included participation of DOE-RL and DOE-ORP Management, site stakeholders, state and federal regulators, and Tribal Nations. These needs are reviewed and updated onmore » an annual basis and given a broad distribution.« less

Hanford science and technology needs statements document

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

Piper, L.L.

This document is a compilation of the Hanford science and technology needs statements for FY 1998. The needs were developed by the Hanford Site Technology Coordination Group (STCG) with full participation and endorsement of site user organizations, stakeholders, and regulators. The purpose of this document is to: (a) provide a comprehensive listing of Hanford science and technology needs, and (b) identify partnering and commercialization opportunities with industry, other federal and state agencies, and the academic community. The Hanford STCG reviews and updates the needs annually. Once completed, the needs are communicated to DOE for use in the development and prioritizationmore » of their science and technology programs, including the Focus Areas, Cross-Cutting Programs, and the Environmental Management Science Program. The needs are also transmitted to DOE through the Accelerating Cleanup: 2006 Plan. The public may access the need statements on the Internet on: the Hanford Home Page (www.hanford.gov), the Pacific Rim Enterprise Center`s web site (www2.pacific-rim.org/pacific rim), or the STCG web site at DOE headquarters (em-52.em.doegov/ifd/stcg/stcg.htm). This page includes links to science and technology needs for many DOE sites. Private industry is encouraged to review the need statements and contact the Hanford STCG if they can provide technologies that meet these needs. On-site points of contact are included at the ends of each need statement. The Pacific Rim Enterprise Center (206-224-9934) can also provide assistance to businesses interested in marketing technologies to the DOE.« less

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

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.

Metal ion displacements in noncentrosymmetric chalcogenides La3Ga1.67S7, La3Ag0.6GaCh7 (Ch=S, Se), and La3MGaSe7 (M=Zn, Cd)

NASA Astrophysics Data System (ADS)

Iyer, Abishek K.; Yin, Wenlong; Rudyk, Brent W.; Lin, Xinsong; Nilges, Tom; Mar, Arthur

2016-11-01

The quaternary Ga-containing chalcogenides La3Ag0.6GaS7, La3Ag0.6GaSe7, La3ZnGaSe7, and La3CdGaSe7, as well as the related ternary chalcogenide La3Ga1.67S7, were prepared by reactions of the elements at 950 °C. They adopt noncentrosymmetric hexagonal structures (space group P63, Z=2) with cell parameters (a=10.2 Å, c=6.1 Å for the sulfides; a=10.6 Å, c=6.4 Å for the selenides) that are largely controlled by the geometrical requirements of one-dimensional stacks of Ga-centered tetrahedra separated by the La atoms. Among these compounds, which share the common formulation La3M1-xGaCh7 (M=Ga, Ag, Zn, Cd; Ch=S, Se), the M atoms occupy sites within a stacking of trigonal antiprisms formed by Ch atoms. The location of the M site varies between extremes with trigonal antiprismatic (CN6) and trigonal planar (CN3) geometry. Partial occupation of these sites and intermediate ones accounts for the considerable versatility of these structures and the occurrence of large metal displacement parameters. The site occupations can be understood in a simple way as being driven by the need to satisfy appropriate bond valence sums for both the M and Ch atoms. Band structure calculations rationalize the substoichiometry observed in the Ag-containing compounds (La3Ag0.6GaS7, La3Ag0.6GaSe7) as a response to overbonding. X-ray photoelectron spectroscopy supports the presence of monovalent Ag atoms in these compounds, which are not charge-balanced.

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.

Resolved 12CH2D2 and 13CH3D in CH4 as Sensitive Indicators of Disequilibrium and Equilibrium during Microbial Methane Cycling

NASA Astrophysics Data System (ADS)

Ash, J. L.; Egger, M.; Slomp, C. P.; Kohl, I. E.; Treude, T.; Rumble, D.; Young, E. D.

2016-12-01

The ability to measure the relative concentrations of at least two doubly-substituted rare isotopologues of gases with biogeochemical relevance provides new constraints on sources and sinks of these gases. In particular, as shown recently for O2, the use of two independent, rare isotopologues allows for detection of thermodynamic intra-species equilibrium and disequilibrium. Here, we report the first measurements of fully resolved 13CH3D and 12CH2D2 from natural samples of microbial methane gas. A suite of sedimentary methane samples from the Bornholm Basin in the Baltic Sea was collected during IODP Exp. 347. Sample depths range from 2-20 meters below seafloor (mbsf). Methane concentrations decrease with depth, and mcrA (a marker for methanogenesis and methanotropy) is present throughout. See Figure. Both Δ13CH3D and Δ12CH2D2 increase with depth as methane concentrations decrease with the shallowest samples exhibiting disequilibrium by up to 2‰ in Δ13CH3D and 13‰ in Δ12CH2D2 while the deepest samples approach isotopic thermodynamic equilibrium (marked by grey bars in Figure). The Fe-mediated anaerobic oxidation of methane (Fe-AOM) has been inferred in these sediments by geochemical modeling . Slow methane cycling by methanogensis and methanotrophy is likely responsible for the approach to isotopic bond order equilibrium in CH4 with depth, consistent with Fe-AOM. While axenic culturing experiments generate methane with large deficits in 12CH2D2 (reported at this meeting), these data from the Baltic Sea demonstrate that isotopic equilibrium can be achieved during microbial recycling of methane. In the absence of Δ12CH2D2, the Δ13CH3D values alone could be misinterpreted as representing gradients in temperature due perhaps to exothermic organic matter degradation. The combination of both mass-18 rare isotopologues of methane provides the means to distinguish equilibrium from disequilibrium and probe microbial methane cycling even where Δ13CH3D suggests

Polarizable Force Fields for CO2 and CH4 Adsorption in M-MOF-74

PubMed Central

2017-01-01

The family of M-MOF-74, with M = Co, Cr, Cu, Fe, Mg, Mn, Ni, Ti, V, and Zn, provides opportunities for numerous energy related gas separation applications. The pore structure of M-MOF-74 exhibits a high internal surface area and an exceptionally large adsorption capacity. The chemical environment of the adsorbate molecule in M-MOF-74 can be tuned by exchanging the metal ion incorporated in the structure. To optimize materials for a given separation process, insights into how the choice of the metal ion affects the interaction strength with adsorbate molecules and how to model these interactions are essential. Here, we quantitatively highlight the importance of polarization by comparing the proposed polarizable force field to orbital interaction energies from DFT calculations. Adsorption isotherms and heats of adsorption are computed for CO2, CH4, and their mixtures in M-MOF-74 with all 10 metal ions. The results are compared to experimental data, and to previous simulation results using nonpolarizable force fields derived from quantum mechanics. To the best of our knowledge, the developed polarizable force field is the only one so far trying to cover such a large set of possible metal ions. For the majority of metal ions, our simulations are in good agreement with experiments, demonstrating the effectiveness of our polarizable potential and the transferability of the adopted approach. PMID:28286598

Infrared spectroscopy of solid normal hydrogen doped with CH3F and O2 at 4.2 K: CH3F:O2 complex and CH3F migration

NASA Astrophysics Data System (ADS)

Abouaf-Marguin, L.; Vasserot, A.-M.

2011-04-01

Double doping of solid normal hydrogen with CH3F and O2 at about 4.2 K gives evidence of (ortho-H2)n:CH3F clusters and of O2:CH3F complex formation. FTIR analysis of the time evolution of the spectra in the region of the v3 C-F stretching mode indicates that these clusters behave very differently from (ortho-H2)n:H2O clusters. The main point is the observed migration of CH3F molecules in solid para-H2 at 4.2 K which differs from that of H2O under identical experimental conditions. This is confirmed by an increase over time of the integrated intensity of the CH3F:O2 complex with a rate constant K = 2.7(2) . 10-4 s-1.

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

Background CH4 and N2O fluxes in low-input short rotation coppice

NASA Astrophysics Data System (ADS)

Görres, Carolyn-Monika; Zenone, Terenzio; Ceulemans, Reinhart

2016-04-01

Extensively managed short rotation coppice systems are characterized by low fluxes of CH4 and N2O. However due to the large global warming potential of these trace gases (GWP100: CH4: 34, N2O: 298), such background fluxes can still significantly contribute to offsetting the CO2 uptake of short rotation coppice systems. Recent technological advances in fast-response CH4 and N2O analysers have improved our capability to capture these background fluxes, but their quantification still remains a challenge. As an example, we present here CH4 and N2O fluxes from a short-rotation bioenergy plantation in Belgium. Poplars have been planted in a double-row system on a loamy sand in 2010 and coppiced in the beginning of 2012 and 2014 (two-year rotation system). In 2013 (June - November) and 2014 (April - August), the plantation's CH4 and N2O fluxes were measured in parallel with an eddy covariance tower (EC) and an automated chamber system (AC). The EC had a detection limit of 13.68 and 0.76 μmol m-2 h-1 for CH4 and N2O, respectively. The median detection limit of the AC was 0.38 and 0.08 μmol m-2 h-1 for CH4 and N2O, respectively. The EC picked up a few high CH4 emission events with daily averages >100 μmol m-2 h-1, but a large proportion of the measured fluxes were within the EC's detection limit. The same was true for the EC-derived N2O fluxes where the daily average flux was often close to the detection limit. Sporadically, some negative (uptake) fluxes of N2O were observed. On the basis of the EC data, no clear link was found between CH4 and N2O fluxes and environmental variables. The problem with fluxes within the EC detection limit is that a significant amount of the values can show the opposite sign, thus "mirroring" the true flux. Subsequently, environmental controls of background trace gas fluxes might be disguised in the analysis. As a next step, it will be tested if potential environmental drivers of background CH4 and N2O fluxes at the plantation can be

Development of Occupational Exposure Limits for the Hanford Tank Farms

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

Still, Kenneth; Gardner, Donald; Snyder, Robert

Production of plutonium for the United States’ nuclear weapons program from the 1940’s to the 1980’s generated 53 million gallons of radioactive chemical waste, which is storedin 177 underground tanks at the Hanford Site in southeastern W 18 ashington State. Recent 19 attempts to begin the retrieval and treatment of these wastes require moving the waste to 20 more modern tanks results in potential exposure of the workers to unfamiliar odors 21 emanating from headspace in the tanks. Given the unknown risks involved, workers 22 were placed on supplied air respiratory protection. CH2M HILL, the managers of the 23 Hanfordmore » Site Tank Farms, asked an Independent Toxicology Panel (ITP) to assist them in issues relating to an Industrial Hygiene and risk assessment problem. The ITP was called upon to help determine the risk of exposure to vapors from the tanks, and in general develop a strategy for solution of the problem. This paper presents the methods used to determine the chemicals of potential concern (COPC) and the resultant development of screening values and Acceptable Occupational Exposure Limits (AOELs) for these COPCs. A total of 1,826 chemicals were inventoried and evaluated. Over 1,500 chemicals were identified in the waste tanks headspaces and more than 600 of these were assigned screening values; 72 of these compounds were recommended for AOEL development. Included in this list of 72 were 57 COPCs identified by the ITP and of these 47 were subsequently assigned AOELs. An exhaustive exposure assessment strategy was developed by the CH2M HILL industrial hygiene department to evaluate these COPCs.« less

Annual dynamics of N2O, CH4 and CO2 fluxes from the agricultural irrigation watersheds in southeast China

NASA Astrophysics Data System (ADS)

Wu, S.; Zou, J.; Liu, S.; Chen, J.; Kong, D.; Geng, Y.

2017-12-01

Agricultural irrigation watershed covers a large area in southeast of China and is a potentially important source of carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O). However, the flux magnitudes contribution to the overall catchment greenhouse gas (GHGs) fluxes and their drivers of seasonal variability are limited in agricultural irrigation watersheds. An in-situ observation was performed to measure annual CO2, CH4 and N2O fluxes from an agricultural irrigation watershed in southeast of China from September 2014 to September 2016. GHGs fluxes were measured using floating chambers and a gas exchange model was also used to predict CH4 and N2O fluxes. All GHGs showed varied seasonally with highest fluxes in early summer (July) and lowest in winter. Estimated seasonal CH4-C fluxes (11.5-97.6 mg m-2 hr-1) and N2O-N fluxes (2.8-80.8μg m-2 hr-1) were in relative agreement with measured CH4-C fluxes (0.05-74.9mg m-2 hr-1) and N2O-N fluxes (3.9-68.7μg m-2 hr-1) fluxes using floating chambers. Both CH4 and N2O fluxes were positively related to water temperature. The CH4 fluxes were negatively related to water dissolved oxygen (DO) concentration but positively related to sediment dissolved organic carbon (DOC). The N2O fluxes were positively related to water NH4+ and NO3-. The calculated EF5-r value in this study (mean = 0.0016; range = 0.0013-0.0018) was below the current IPCC (2006) default value of 0.0025. This implied that IPCC methodology may over estimates of N2O emissions associated with nitrogen leaching and runoff from agriculture.

A flux-gradient system for simultaneous measurement of the CH4, CO2, and H2O fluxes at a lake-air interface.

PubMed

Xiao, Wei; Liu, Shoudong; Li, Hanchao; Xiao, Qitao; Wang, Wei; Hu, Zhenghua; Hu, Cheng; Gao, Yunqiu; Shen, Jing; Zhao, Xiaoyan; Zhang, Mi; Lee, Xuhui

2014-12-16

Inland lakes play important roles in water and greenhouse gas cycling in the environment. This study aims to test the performance of a flux-gradient system for simultaneous measurement of the fluxes of water vapor, CO2, and CH4 at a lake-air interface. The concentration gradients over the water surface were measured with an analyzer based on the wavelength-scanned cavity ring-down spectroscopy technology, and the eddy diffusivity was measured with a sonic anemometer. Results of a zero-gradient test indicate a flux measurement precision of 4.8 W m(-2) for water vapor, 0.010 mg m(-2) s(-1) for CO2, and 0.029 μg m(-2) s(-1) for CH4. During the 620 day measurement period, 97%, 69%, and 67% of H2O, CO2, and CH4 hourly fluxes were higher in magnitude than the measurement precision, which confirms that the flux-gradient system had adequate precision for the measurement of the lake-air exchanges. This study illustrates four strengths of the flux-gradient method: (1) the ability to simultaneously measure the flux of H2O, CO2, and CH4; (2) negligibly small density corrections; (3) the ability to resolve small CH4 gradient and flux; and (4) continuous and noninvasive operation. The annual mean CH4 flux (1.8 g CH4 m(-2) year(-1)) at this hypereutrophic lake was close to the median value for inland lakes in the world (1.6 g CH4 m(-2) year(-1)). The system has adequate precision for CH4 flux for broad applications but requires further improvement to resolve small CO2 flux in many lakes.

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

Metal ion displacements in noncentrosymmetric chalcogenides La{sub 3}Ga{sub 1.67}S{sub 7}, La{sub 3}Ag{sub 0.6}GaCh{sub 7} (Ch=S, Se), and La{sub 3}MGaSe{sub 7} (M=Zn, Cd)

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

Iyer, Abishek K.; Yin, Wenlong; Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang 621900

The quaternary Ga-containing chalcogenides La{sub 3}Ag{sub 0.6}GaS{sub 7}, La{sub 3}Ag{sub 0.6}GaSe{sub 7}, La{sub 3}ZnGaSe{sub 7}, and La{sub 3}CdGaSe{sub 7}, as well as the related ternary chalcogenide La{sub 3}Ga{sub 1.67}S{sub 7}, were prepared by reactions of the elements at 950 °C. They adopt noncentrosymmetric hexagonal structures (space group P6{sub 3}, Z=2) with cell parameters (a=10.2 Å, c=6.1 Å for the sulfides; a=10.6 Å, c=6.4 Å for the selenides) that are largely controlled by the geometrical requirements of one-dimensional stacks of Ga-centered tetrahedra separated by the La atoms. Among these compounds, which share the common formulation La{sub 3}M{sub 1–x}GaCh{sub 7} (M=Ga, Ag,more » Zn, Cd; Ch=S, Se), the M atoms occupy sites within a stacking of trigonal antiprisms formed by Ch atoms. The location of the M site varies between extremes with trigonal antiprismatic (CN6) and trigonal planar (CN3) geometry. Partial occupation of these sites and intermediate ones accounts for the considerable versatility of these structures and the occurrence of large metal displacement parameters. The site occupations can be understood in a simple way as being driven by the need to satisfy appropriate bond valence sums for both the M and Ch atoms. Band structure calculations rationalize the substoichiometry observed in the Ag-containing compounds (La{sub 3}Ag{sub 0.6}GaS{sub 7}, La{sub 3}Ag{sub 0.6}GaSe{sub 7}) as a response to overbonding. X-ray photoelectron spectroscopy supports the presence of monovalent Ag atoms in these compounds, which are not charge-balanced. - Graphical abstract: Partial occupation of metal atoms in multiple sites accounts for versatility in Ga-containing chalcogenides La{sub 3}M{sub 1–x}GaCh{sub 7} with noncentrosymmetric hexagonal structures. - Highlights: • La{sub 3}M{sub 1–x}GaCh{sub 7} (M =Ga, Ag, Zn, Cd; Ch =S, Se) adopt related hexagonal structures. • Large displacements of M atoms originate from partial occupation of

Rate coefficients for the gas-phase reaction of the hydroxyl radical with CH2=CHF and CH2=CF2.

PubMed

Baasandorj, Munkhbayar; Knight, Gary; Papadimitriou, Vassileios C; Talukdar, Ranajit K; Ravishankara, A R; Burkholder, James B

2010-04-08

Rate coefficients, k, for the gas-phase reaction of the OH radical with CH(2)=CHF (k(1)) and CH(2)=CF(2) (k(2)) were measured under pseudo-first-order conditions in OH using pulsed laser photolysis to produce OH and laser-induced fluorescence (PLP-LIF) to detect it. Rate coefficients were measured over a range of temperature (220-373 K) and bath gas pressure (20-600 Torr; He, N(2)). The rate coefficients were found to be independent of pressure. The measured rate coefficient for reaction 1 at room temperature was k(1)(296 K) = (5.18 +/- 0.50) x 10(-12) cm(3) molecule(-1) s(-1), independent of pressure, and the temperature dependence is given by the Arrhenius expression k(1)(T) = (1.75 +/- 0.20) x 10(-12) exp[(316 +/- 25)/T] cm(3) molecule(-1) s(-1); the rate coefficients for reaction 2 were k(2)(296 K) = (2.79 +/- 0.25) x 10(-12) cm(3) molecule(-1) s(-1) and k(2)(T) = (1.75 +/- 0.20) x 10(-12) exp[(140 +/- 20)/T] cm(3) molecule(-1) s(-1). The quoted uncertainties are 2sigma (95% confidence level) and include estimated systematic errors. The fall-off parameters for reaction 2 of k(infinity) = 3 x 10(-12) cm(3) molecule(-1) s(-1) and k(0)(296 K) = 1.8 x 10(-28) cm(6) molecule(-2) s(-1) with F(c) = 0.6 reproduce the room temperature data obtained in this study combined with the low pressure rate coefficient data from Howard (J. Chem. Phys. 1976, 65, 4771). OH radical formation was observed for reactions 1 and 2 in the presence of O(2), and the mechanism was investigated using (18)OH and OD rate coefficient measurements with CH(2)=CHF and CH(2)=CF(2) over a range of temperature (260-373 K) and pressure (20-100 Torr, He). Quantum chemical calculations using density functional theory (DFT) were used to determine the geometries and energies of the reactants and adducts formed in reactions 1 and 2 and the peroxy radicals formed following the addition of O(2). The atmospheric lifetimes of CH(2)=CHF and CH(2)=CF(2) due to loss by reaction with OH are approximately 2 and 4

1.2V, 24mW/ch, 10bit, 80MSample/s Pipelined A/D Converters

NASA Astrophysics Data System (ADS)

Ueno, Takeshi; Ito, Tomohiko; Kurose, Daisuke; Yamaji, Takafumi; Itakura, Tetsuro

This paper describes 10-bit, 80-MSample/s pipelined A/D converters for wireless-communication terminals. To reduce power consumption, we employed the I/Q amplifier sharing technique [1] in which an amplifier is used for both I and Q channels. In addition, common-source, pseudo-differential (PD) amplifiers are used in all the conversion stages for further power reduction. Common-mode disturbances are removed by the proposed common-mode feedforward (CMFF) technique without using fully differential (FD) amplifiers. The converter was implemented in a 90-nm CMOS technology, and it consumes only 24mW/ch from a 1.2V power supply. The measured SNR and SNDR are 58.6dB and 52.2dB, respectively.

Large CO2 and CH4 release from a flooded formerly drained fen

NASA Astrophysics Data System (ADS)

Sachs, T.; Franz, D.; Koebsch, F.; Larmanou, E.; Augustin, J.

2016-12-01

Drained peatlands are usually strong carbon dioxide (CO2) sources. In Germany, up to 4.5 % of the national CO2 emissions are estimated to be released from agriculturally used peatlands and for some peatland-rich northern states, such as Mecklenburg-Western Pomerania, this share increases to about 20%. Reducing this CO2 source and restoring the peatlands' natural carbon sink is one objective of large-scale nature protection and restoration measures, in which 37.000 ha of drained and degraded peatlands in Mecklenburg-Western Pomerania are slated for rewetting. It is well known, however, that in the initial phase of rewetting, a reduction of the CO2 source strength is usually accompanied by an increase in CH4 emissions. Thus, whether and when the intended effects of rewetting with regard to greenhouse gases are achieved, depends on the balance of CO2 and CH4 fluxes and on the duration of the initial CH4 emission phase. In 2013, a new Fluxnet site went online at a flooded formerly drained river valley fen site near Zarnekow, NE Germany (DE-Zrk), to investigate the combined CO2 and CH4 dynamics at such a heavily degraded and rewetted peatland. The site is dominated by open water with submerged and floating vegetation and surrounding Typha latifolia.Nine year after rewetting, we found large CH4 emissions of 53 g CH4 m-2 a-1 from the open water area, which are 4-fold higher than from the surrounding vegetation zone (13 g CH4 m-2 a-1). Surprisingly, both the open water and the vegetated area were net CO2 sources of 158 and 750 g CO2 m-2 a-1, respectively. Unusual meteorological conditions with a warm and dry summer and a mild winter might have facilitated high respiration rates, particularly from temporally non-inundated organic mud in the vegetation zone.

Characterization of the Minimum Energy Paths for the Reactions of CH(X(sup 2 Pi) and (1)CH2 with C2H2

NASA Technical Reports Server (NTRS)

Walch, Stephen P.; Langhoff, S. R. (Technical Monitor)

1994-01-01

The reactions of CH(sup 2 Pi) and singlet methylene (1)CH2 with acetylene lead to intermediates which may be important in soot formation. CH(sup 2 Pi) + acetylene leads to CHCHCH (C3H3), CHCCH (C3H2), and propargyl (CH2CCH). (1)CH2 + acetylene leads to cyclopropene and propargyl. All of these reaction products are formed with no barrier. Miller and Melius have previously discussed the dimerization of propargyl to give benzene. C3H3 and C3H2 can dimerize with no barrier to give benzene and para-benzyne, respectively. C3H3 and C3H2 can also add to smaller polynuclear aromatic hydrocarbons (PAH), and may be important species in forming larger PAH or fullerenes.

New Hires, Building Demolition

ScienceCinema

None

2017-12-09

Using Recovery Act funding, Department of Energy contractor CH2M HILL Plateau Remediation Company has hired hundreds of new employees to do cleanup work at the Hanford Site, including demolition of dozens of excess facilities.This video was produced by CH2M HILL on Jan. 8, 2010.

Tree species influence soil-atmosphere fluxes of the greenhouse gases CO2, CH4 and N2O

NASA Astrophysics Data System (ADS)

Steffens, Christina; Vesterdal, Lars; Pfeiffer, Eva-Maria

2016-04-01

In the temperate zone, forests are the greatest terrestrial sink for atmospheric CO2, and tree species affect soil C stocks and soil CO2 emissions. When considering the total greenhouse gas (GHG) balance of the forest soil, the relevant GHGs CH4 and N2O should also be considered as they have a higher global warming potential than CO2. The presented data are first results from a field study in a common garden site in Denmark where tree species with ectomycorrhizal colonization (beech - Fagus sylvatica, oak - Quercus robur) and with arbuscular mycorrhizal colonization (maple - Acer pseudoplatanus, ash - Fraxinus excelsior) have been planted in monocultures in adjacent blocks of about 0.25 ha in the year 1973 on former arable land. The soil-atmosphere fluxes of all three gases were measured every second week since August 2015. The hypothesis is that the total GHG efflux from forest soil would differ between species, and that these differences could be related to the type of mycorrhizal association and leaf litter quality. Preliminary results (August to December 2015) indicate that tree species influence the fluxes (converted to CO2-eq) of the three GHGs. Total soil CO2 efflux was in the low end of the range reported for temperate broadleaved forests but similar to the measurements at the same site approximately ten years ago. It was highest under oak (9.6±2.4 g CO2 m-2 d-1) and lowest under maple (5.2±1.6 g CO2 m-2 d-1). In contrast, soil under oak was a small but significant sink for CH4(-0.005±0.003 g CO2-eq m-2 d-1), while there were almost no detectable CH4 fluxes in maple. Emissions of N2O were highest under beech (0.6±0.6 g CO2-eq m-2 d-1) and oak (0.2±0.09 g CO2-eq m-2 d-1) and lowest under ash (0.03±0.04 g CO2-eq m-2 d-1). In the total GHG balance, soil CH4 uptake was negligible (≤0.1% of total emissions). Emissions of N2O (converted to CO2-eq) contributed <1% (ash) to 8% (beech) to total GHG emissions. Summing up all GHG emissions, the tree species

Assembly of [Cu2(COO)4] and [M3(μ3-O)(COO)6] (M = Sc, Fe, Ga, and In) building blocks into porous frameworks towards ultra-high C2H2/CO2 and C2H2/CH4 separation performance.

PubMed

Zhang, Jian-Wei; Hu, Man-Cheng; Li, Shu-Ni; Jiang, Yu-Cheng; Qu, Peng; Zhai, Quan-Guo

2018-02-20

A porous MOF platform (SNNU-65s) formed by creatively combining paddle-wheel-like [Cu 2 (COO) 4 ] and trigonal prismatic [M 3 (μ 3 -O)(COO) 6 ] building blocks was designed herein. The mixed and high-density open metal sites and the OH-functionalized pore surface promote SNNU-65s to exhibit ultra-high C 2 H 2 uptake and separation performance. Impressively, SNNU-65-Cu-Ga stands out for the highest C 2 H 2 /CO 2 (18.7) and C 2 H 2 /CH 4 (120.6) selectivity among all the reported MOFs at room temperature.

The role of Phragmites in the CH4 and CO2 fluxes in a minerotrophic peatland in southwest Germany

NASA Astrophysics Data System (ADS)

van den Berg, Merit; Ingwersen, Joachim; Lamers, Marc; Streck, Thilo

2016-11-01

Peatlands are interesting as a carbon storage option, but are also natural emitters of the greenhouse gas methane (CH4). Phragmites peatlands are particularly interesting due to the global abundance of this wetland plant (Phragmites australis) and the highly efficient internal gas transport mechanism, which is called humidity-induced convection (HIC). The research aims were to (1) clarify how this plant-mediated gas transport influences the CH4 fluxes, (2) which other environmental variables influence the CO2 and CH4 fluxes, and (3) whether Phragmites peatlands are a net source or sink of greenhouse gases. CO2 and CH4 fluxes were measured with the eddy covariance technique within a Phragmites-dominated fen in southwest Germany. One year of flux data (March 2013-February 2014) shows very clear diurnal and seasonal patterns for both CO2 and CH4. The diurnal pattern of CH4 fluxes was only visible when living, green reed was present. In August the diurnal cycle of CH4 was the most distinct, with 11 times higher midday fluxes (15.7 mg CH4 m-2 h-1) than night fluxes (1.41 mg CH4 m-2 h-1). This diurnal cycle has the highest correlation with global radiation, which suggests a high influence of the plants on the CH4 flux. But if the cause were the HIC, it would be expected that relative humidity would correlate stronger with CH4 flux. Therefore, we conclude that in addition to HIC, at least one additional mechanism must be involved in the creation of the convective flow within the Phragmites plants. Overall, the fen was a sink for carbon and greenhouse gases in the measured year, with a total carbon uptake of 221 g C m-2 yr-1 (26 % of the total assimilated carbon). The net uptake of greenhouse gases was 52 g CO2 eq. m-2 yr-1, which is obtained from an uptake of CO2 of 894 g CO2 eq. m-2 yr-1 and a release of CH4 of 842 g CO2 eq. m-2 yr-1.

Submillimeter observations of OH and CH in M42

NASA Technical Reports Server (NTRS)

Viscuso, P. J.; Stacy, G. J.; Fuller, C. E.; Kurtz, N. T.; Harwit, M.

1985-01-01

The (sup 2) pi sub 1/2 (J = 3/2 to 1/2) transitions of OH at 163.12 and 163.40 micro m have been detected and upper limits have been obtained for the (sup 2) pi sub 3/2 (J = 3/2 to 1/2) transitions of CH at 149.09 and 149.39 micro m, in observations of the Kleinmann-Low Nebula of Orion. All four flux levels lie between 1 and 1.2 x 10 to the 17th power/sq.cm. The OH lines are bright when compared to the lower, (sup 2) pi sub 3/2 (J = 5/2 to 3/2) fluxes reported and imply that the 119 micro m emission observed is partially self-absorbed. The combined results provide strong constraints. Taken together with existing data on molecular hydrogen and CO and recent data on other OH transition, they suggest OH emission from post-shock regions at temperatures T approx 1000 k, densities approx. 7 x 10 to the 6th powr/cu cm N sub OH approx 80/cu cm optically thick for the (sup 2) pi sub 3/2 (J = 5/2 to 3/2), 119 micro m but only partially self-absorbing in the (J = 7/2 to 3/2), 84 micro m transitions over a Doppler velocity bandwidth of 30 km/sec. The OH column density is N sub OH approx 4 x 10 to the 16th powr/sq cm. in the emitting regions which occupy a fraction of approx 0.1 of a 1' x 1' field of view centered on the Becklin-Neugebauer source. The CO (J = 31 to 30), 84 micro m transition appears to lie sufficiently close to one of the 84 micro m OH line components to be partially absorbed as well, through a Bowen-type mechanism.

Direct production of OH radicals upon CH overtone activation of (CH{sub 3}){sub 2}COO Criegee intermediates

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

Liu, Fang; Beames, Joseph M.; Lester, Marsha I., E-mail: milester@sas.upenn.edu

2014-12-21

Ozonolysis of alkenes, a principle non-photolytic source of atmospheric OH radicals, proceeds through unimolecular decay of energized carbonyl oxide intermediates, known as Criegee intermediates. In this work, cold dimethyl-substituted Criegee intermediates are vibrationally activated in the CH stretch overtone region to drive the 1,4 hydrogen transfer reaction that leads to OH radical products. IR excitation of (CH{sub 3}){sub 2}COO reveals the vibrational states with sufficient oscillator strength, coupling to the reaction coordinate, and energy to surmount the effective barrier (≤ 16.0 kcal mol{sup −1}) to reaction. Insight on the dissociation dynamics is gleaned from homogeneous broadening of the spectral features,more » indicative of rapid intramolecular vibrational energy redistribution and/or reaction, as well as the quantum state distribution of the OH X{sup 2}Π (v = 0) products. The experimental results are compared with complementary electronic structure calculations, which provide the IR absorption spectrum and geometric changes along the intrinsic reaction coordinate. Additional theoretical analysis reveals the vibrational modes and couplings that permit (CH{sub 3}){sub 2}COO to access to the transition state region for reaction. The experimental and theoretical results are compared with an analogous recent study of the IR activation of syn-CH{sub 3}CHOO and its unimolecular decay to OH products [F. Liu, J. M. Beames, A. S. Petit, A. B. McCoy, and M. I. Lester, Science 345, 1596 (2014)].« less

Annual Greenhouse Gas (CO2, CH4, and N2O) Fluxes Via Ebullition from a Temperate Emergent Wetland

NASA Astrophysics Data System (ADS)

Mcnicol, G.; Sturtevant, C. S.; Knox, S. H.; Baldocchi, D. D.; Silver, W. L.

2014-12-01

Quantifying wetland greenhouse gas exchange is necessary to evaluate their potential for mitigating climate change via carbon sequestration. However measuring greenhouse gas fluxes of carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O) in wetlands is difficult due to high spatial and temporal variability, and multiple transport pathways of emission. Transport of biogenic soil gas via highly sporadic ebullition (bubbling) events is often ignored or quantified poorly in wetland greenhouse gas budgets, but can rapidly release large volumes of gas to the atmosphere. To quantify a robust annual ebullition flux we measured rates continuously for a year (2013-2014) using custom-built chambers deployed in a restored emergent wetland located in the Sacramento-San Joaquin Delta, CA. We combined ebullition flux rates with observations of gas concentrations to estimate annual ebullition emissions of CO2, CH4, and N2O and compare flux rates to whole-ecosystem exchange of CO2 and CH4 measured simultaneously by eddy covariance.Mean ebullition flux rates were 18.3 ± 5.6 L m-2 yr-1. Ebullition CH4 concentrations were very high and ranged from 23-76 % with a mean of 47 ± 2.9 %; CO2 concentrations were lower and ranged from 0.7-6.6 % with a mean of 2.8 ± 0.3 %; N2O concentrations were below atmospheric concentrations and ranged from 130-389 ppb(v) with a mean of 257 ± 13 ppb(v). We calculated well-constrained annual ebullition fluxes of: 6.2 ± 1.9 g CH4 m-2 yr-1, 1.0 ± 0.3 g CO2 m-2 yr-1 and 9.3 ± 2.8 mg N2O m-2 yr-1. Methane emissions via ebullition were very large, representing 15-25 % of total wetland CH4 emissions measured at this site, whereas ebullition released only relatively small quantities of CO2 and N2O. Our results demonstrate that large releases of CH4 via ebullition from open water surfaces can be a significant component of restored wetland greenhouse gas budgets.

Multiple bonds between transition metals and main-group elements. 73. Synthetic routes to rhenium(V) alkyl and rhenium(VII) alkylidyne complexes. X-ray crystal structures of (. eta. sup 5 -C sub 5 Me sub 5 )Re( double bond O)(CH sub 3 )(CH sub 2 C(CH sub 3 ) sub 3 ) and (. eta. sup 5 -C sub 5 Me sub 5 )(Br) sub 3 Re triple bond CC(CH sub 3 ) sub 3

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

Herrmann, W.A.; Felixberger, J.K.; Anwander, R.

1990-05-01

Dialkyloxo({eta}{sup 5}pentamethylcyclopentadienyl)rhenium(V) complexes ({eta}{sup 5}-C{sub 5}Me{sub 5})Re({double bond}O)(CH{sub 3})R{prime}(R{prime} = C{sub 2}H{sub 5}, CH{sub 2}Si(CH{sub 3}){sub 3}, CH{sub 2}C(CH{sub 3}){sub 3}), 1c-e, have become accessible through alkylation of ({eta}{sup 5}-C{sub 5}Me{sub 5})Re({double bond}O)(Cl)(CH{sub 3}) (7) with R{prime}MgCl. 1c-e are the first rhenium complexes containing different alkyl ligands. The neopentyl derivative 1e (R{prime} = CH{sub 2}C(CH{sub 3}){sub 3}) crystallizes in the orthorhombic space group Pbca with a = 960.7 (2), b = 2.844.5 (4), c = 1,260.7 (2) pm, and Z = 8. The X-ray crystal structure was refined to R{sub W} = 3.9%. The chiral molecule shows a distorted tetrahedralmore » geometry around the rhenium center. The tribromide 3b has been structurally characterized. Brown crystals of 3b belong to space group P2{sub 1}/c with unit cell dimensions a = 1,311.5 (2), b = 723.0 (1), c = 1,901.6 (2) pm, {beta} = 92.68 (1){degree}, and Z = 4. The structure exhibits a four-legged piano stool geometry with no trans influence of the neopentylidyne ligand to the bromine atom.« less

Unraveling the Fate and Transport of SrEDTA-2 and Sr+2 in Hanford Sediments

NASA Astrophysics Data System (ADS)

Pace, M. N.; Mayes, M. A.; Jardine, P. M.; Mehlhorn, T. L.; Liu, Q. G.; Yin, X. L.

2004-12-01

Accelerated migration of strontium-90 has been observed in the vadose zone beneath the Hanford tank farm. The goal of this paper is to provide an improved understanding of the hydrogeochemical processes that contribute to strontium transport in the far-field Hanford vadose zone. Laboratory scale batch, saturated packed column experiments, and an unsaturated transport experiment in an undisturbed core were conducted to quantify geochemical and hydrological processes controlling Sr+2 and SrEDTA-2 sorption to Hanford flood deposits. After experimentation, the undisturbed core was disassembled and samples were collected from different bedding units as a function of depth. Sequential extractions were then performed on the samples. It has been suggested that organic chelates such as EDTA may be responsible for the accelerated transport of strontium due to the formation of stable anionic complexes. Duplicate batch and column experiments performed with Sr+2 and SrEDTA-2 suggested that the SrEDTA-2 complex was not stable in the presence of soil and rapid dissociation allowed strontium to be transported as a divalent cation. Batch experiments indicated a decrease in sorption with increasing rock:water ratios, whereas saturated packed column experiments indicated equal retardation in columns of different lengths. This difference between the batch and column experiments is primarily due to the difference between equilibrium conditions where dissolution of cations may compete for sorption sites versus flowing conditions where any dissolved cations are flushed through the system minimizing competition for sorption sites. Unsaturated transport in the undisturbed core resulted in significant Sr+2 retardation despite the presence of physical nonequilibrium. Core disassembly and sequential extractions revealed the mass wetness distribution and reactive mineral phases associated with strontium in the core. Overall, results indicated that strontium will most likely be transported

Model Package Report: Hanford Soil Inventory Model SIM v.2 Build 1

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

Nichols, Will E.; Zaher, U.; Mehta, S.

The Hanford Soil Inventory Model (SIM) is a tool for the estimation of inventory of contaminants that were released to soil from liquid discharges during the U.S. Department of Energy’s Hanford Site operations. This model package report documents the construction and development of a second version of SIM (SIM-v2) to support the needs of Hanford Site Composite Analysis. The SIM-v2 is implemented using GoldSim Pro®1 software with a new model architecture that preserves the uncertainty in inventory estimates while reducing the computational burden (compared to the previous version) and allowing more traceability and transparency in calculation methodology. The calculation architecturemore » is designed in such a manner that future updates to the waste stream composition along with addition or deletion of waste sites can be performed with relative ease. In addition, the new computational platform allows for continued hardware upgrade.« less

HANFORD FACILITY ANNUAL DANGEROUS WASTE REPORT CY2003 [SEC 1 & 2

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

FREEMAN, D.A.

2004-02-17

The Hanford Facility Annual Dangerous Waste Report (ADWR) is prepared to meet the requirements of Washington Administrative Code Sections 173-303-220, Generator Reporting, and 173-303-390, Facility Reporting. In addition, the ADWR is required to meet Hanford Facility RCRA Permit Condition I.E.22, Annual Reporting. The ADWR provides summary information on dangerous waste generation and management activities for the Calendar Year for the Hanford Facility EPA ID number assigned to the Department of Energy for RCRA regulated waste, as well as Washington State only designated waste and radioactive mixed waste. The Solid Waste Information and Tracking System (SWITS) database is utilized to collectmore » and compile the large array of data needed for preparation of this report. Information includes details of waste generated on the Hanford Facility, waste generated offsite and sent to Hanford for management, and other waste management activities conducted at Hanford, including treatment, storage, and disposal. Report details consist of waste descriptions and weights, waste codes and designations, and waste handling codes. In addition, for waste shipped to Hanford for treatment and or disposal, information on manifest numbers, the waste transporter, the waste receiving facility, and the original waste generators are included. In addition to paper copies, the report is also transmitted electronically to a web site maintained by the Washington State Department of Ecology.« less

Combining two complementary micrometeorological methods to measure CH4 and N2O fluxes over pasture

NASA Astrophysics Data System (ADS)

Laubach, J.; Barthel, M.; Fraser, A.; Hunt, J. E.; Griffith, D. W. T.

2015-09-01

New Zealand's largest industrial sector is pastoral agriculture, giving rise to a large fraction of the country's emissions of methane (CH4) and nitrous oxide (N2O). We designed a system to continuously measure CH4 and N2O fluxes at the field scale on two adjacent pastures that differed with respect to management. At the core of this system was a closed-cell Fourier-transform infrared spectrometer (FTIR), measuring the mole fractions of CH4, N2O and carbon dioxide (CO2) at two heights at each site. In parallel, CO2 fluxes were measured using eddy-covariance instrumentation. We applied two different micrometeorological ratio methods to infer the CH4 and N2O fluxes from their respective mole fractions and the CO2 fluxes. The first is a variant of the flux-gradient method, where it is assumed that the turbulent diffusivities of CH4 and N2O equal that of CO2. This method was reliable when the CO2 mole-fraction difference between heights was at least 4 times greater than the FTIR's resolution of differences. For the second method, the temporal increases of mole fractions in the stable nocturnal boundary layer, which are correlated for concurrently-emitted gases, are used to infer the unknown fluxes of CH4 and N2O from the known flux of CO2. This method was sensitive to "contamination" from trace gas sources other than the pasture of interest and therefore required careful filtering. With both methods combined, estimates of mean daily CH4 and N2O fluxes were obtained for 60 % of days at one site and 77 % at the other. Both methods indicated both sites as net sources of CH4 and N2O. Mean emission rates for one year at the unfertilised, winter-grazed site were 8.2 (± 0.91) nmol CH4 m-2 s-1 and 0.40 (± 0.018) nmol N2O m-2 s-1. During the same year, mean emission rates at the irrigated, fertilised and rotationally-grazed site were 7.0 (± 0.89) nmol CH4 m-2 s-1 and 0.57 (± 0.019) nmol N2O m-2 s-1. At this site, the N2O emissions amounted to 1.19 (± 0.15) % of the

Residual waste from Hanford tanks 241-C-203 and 241-C-204. 2. Contaminant release model.

PubMed

Cantrell, Kirk J; Krupka, Kenneth M; Deutsch, William J; Lindberg, Michael J

2006-06-15

Release of U and 99Tc from residual sludge in Hanford waste tanks 241-C-203 and 241-C-204 atthe U.S. Department of Energy's (DOE) Hanford Site in southeastern Washington state was quantified by water-leaching, selective extractions, empirical solubility measurements, and thermodynamic modeling. A contaminant release model was developed based on these experimental results and solid-phase characterization results presented elsewhere. Uranium release was determined to be controlled by two phases and occurred in three stages. In the first stage, U release is controlled by the solubility of tejkaite, which is suppressed by high concentrations of sodium released from the dissolution of NaNO3 in the residual sludges. Equilibrium solubility calculations indicate the U released during this stage will have a maximum concentration of 0.021 M. When all the NaNO3 has dissolved from the sludge, the solubility of the remaining cejkaite will increase to 0.28 M. After cejkaite has completely dissolved, the majority of the remaining U is in the form of poorly crystalline Na2U2O7 [or clarkeite Na[(UO2)O(OH)](H20)0-1]. In contact with Hanford groundwater this phase is not stable, and becquerelite becomes the U solubility controlling phase, with a calculated equilibrium concentration of 1.2 x 10(-4) M. For Tc, a significant fraction of its concentration in the residual sludge was determined to be relatively insoluble (20 wt % for C-203 and 80 wt % for C-204). Because of the low concentrations of Tc in these sludge materials, the characterization studies did not identify any discrete Tc solids phases. Release of the soluble fraction of Tc was found to occur concomitantly with NO3-. It was postulated that a NaNO3-NaTcO4 solid solution could be responsible for this behavior. The Tc release concentrations for the soluble fraction were estimated to be 2.4 x 10-6 M for C-203 and 2.7 x 10(-5) M for C-204. Selective extraction results indicated that the recalcitrant fraction of Tc was

Reactions of CH3SH and CH3SSCH3 with gas-phase hydrated radical anions (H2O)n(•-), CO2(•-)(H2O)n, and O2(•-)(H2O)n.

PubMed

Höckendorf, Robert F; Hao, Qiang; Sun, Zheng; Fox-Beyer, Brigitte S; Cao, Yali; Balaj, O Petru; Bondybey, Vladimir E; Siu, Chi-Kit; Beyer, Martin K

2012-04-19

The chemistry of (H(2)O)(n)(•-), CO(2)(•-)(H(2)O)(n), and O(2)(•-)(H(2)O)(n) with small sulfur-containing molecules was studied in the gas phase by Fourier transform ion cyclotron resonance mass spectrometry. With hydrated electrons and hydrated carbon dioxide radical anions, two reactions with relevance for biological radiation damage were observed, cleavage of the disulfide bond of CH(3)SSCH(3) and activation of the thiol group of CH(3)SH. No reactions were observed with CH(3)SCH(3). The hydrated superoxide radical anion, usually viewed as major source of oxidative stress, did not react with any of the compounds. Nanocalorimetry and quantum chemical calculations give a consistent picture of the reaction mechanism. The results indicate that the conversion of e(-) and CO(2)(•-) to O(2)(•-) deactivates highly reactive species and may actually reduce oxidative stress. For reactions of (H(2)O)(n)(•-) with CH(3)SH as well as CO(2)(•-)(H(2)O)(n) with CH(3)SSCH(3), the reaction products in the gas phase are different from those reported in the literature from pulse radiolysis studies. This observation is rationalized with the reduced cage effect in reactions of gas-phase clusters. © 2012 American Chemical Society

Combining two complementary micrometeorological methods to measure CH4 and N2O fluxes over pasture

NASA Astrophysics Data System (ADS)

Laubach, Johannes; Barthel, Matti; Fraser, Anitra; Hunt, John E.; Griffith, David W. T.

2016-03-01

New Zealand's largest industrial sector is pastoral agriculture, giving rise to a large fraction of the country's emissions of methane (CH4) and nitrous oxide (N2O). We designed a system to continuously measure CH4 and N2O fluxes at the field scale on two adjacent pastures that differed with respect to management. At the core of this system was a closed-cell Fourier transform infrared (FTIR) spectrometer, which measured the mole fractions of CH4, N2O and carbon dioxide (CO2) at two heights at each site. In parallel, CO2 fluxes were measured using eddy-covariance instrumentation. We applied two different micrometeorological ratio methods to infer the CH4 and N2O fluxes from their respective mole fractions and the CO2 fluxes. The first is a variant of the flux-gradient method, where it is assumed that the turbulent diffusivities of CH4 and N2O equal that of CO2. This method was reliable when the CO2 mole-fraction difference between heights was at least 4 times greater than the FTIR's resolution of differences. For the second method, the temporal increases of mole fractions in the stable nocturnal boundary layer, which are correlated for concurrently emitted gases, are used to infer the unknown fluxes of CH4 and N2O from the known flux of CO2. This method was sensitive to "contamination" from trace gas sources other than the pasture of interest and therefore required careful filtering. With both methods combined, estimates of mean daily CH4 and N2O fluxes were obtained for 56 % of days at one site and 73 % at the other. Both methods indicated both sites as net sources of CH4 and N2O. Mean emission rates for 1 year at the unfertilised, winter-grazed site were 8.9 (±0.79) nmol CH4 m-2 s-1 and 0.38 (±0.018) nmol N2O m-2 s-1. During the same year, mean emission rates at the irrigated, fertilised and rotationally grazed site were 8.9 (±0.79) nmol CH4 m-2 s-1 and 0.58 (±0.020) nmol N2O m-2 s-1. At this site, the N2O emissions amounted to 1.21 (±0.15) % of the nitrogen

The Rotation-Torsion Spectrum of CH_2DOH

NASA Astrophysics Data System (ADS)

Hilali, A. El; Coudert, L. H.; Margulès, L.; Motiyenko, R.; Klee, S.

2010-06-01

Due to the asymmetry of the CH_2D group, the internal rotation problem in the partially deuterated species of methanol CH_2DOH is a complicated one as, unlike in the normal species CH_3OH, the inertia tensor depends on the angle of internal rotation. The CH_2DOH species also displays a dense far infrared torsional spectrum difficult to assign. Recently 38 torsional subbands of CH_2DOH have been identified, but for most of them there is neither an assignment nor an analysis of their rotational structure. In this paper an analysis of the rotation-torsion spectrum of CH_2DOH will be presented. The rotational structure of 23 torsional subbands have been assigned. These subbands are Δ v_t &ge 1 perpendicular subbands with a value of v'_t up to 10b and values of K' and K'' ranging from 0 to 9. For all subbands, the Q-branch was assigned, for 3 subbands, the R- and P-branches could also be found. The results of the rotational analysis with an expansion in J(J+1) of the new subbands and of already observed ones will be presented. When available, microwave lines within the lower torsional level, recorded in this work or already measured, were added to the data set. A theoretical approach aimed at calculating the rotation-torsion energy levels has also been developed. It is based on an expansion in terms of rotation-torsion operators with C_s symmetry and accounts for the dependence of the inertia tensor on the angle of internal rotation. This approach will be used to carry out a preliminary global analyses of the wavenumbers and of the frequencies. Lauvergnat, Coudert, Klee, and Smirnov, J. Mol. Spec. 256 (2009) 204. Quade, Liu, Mukhopadhyay, and Su, J. Mol. Spec. 192 (1998) 378; Mukhopadhyay, J. Mol. Struct. 695-696 (2004) 357. Liu and Quade, J. Mol. Spec. 146 (1991) 252 Mukhopadhyay et al., J. Chem. Phys. 116 (2002) 3710.

Hanford's Supplemental Treatment Project: Full-Scale Integrated Testing of In-Container-Vitrification and a 10,000-Liter Dryer

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

Witwer, K.S.; Dysland, E.J.; Garfield, J.S.

2008-07-01

The GeoMelt{sup R} In-Container Vitrification{sup TM} (ICV{sup TM}) process was selected by the U.S. Department of Energy (DOE) in 2004 for further evaluation as the supplemental treatment technology for Hanford's low-activity waste (LAW). Also referred to as 'bulk vitrification', this process combines glass forming minerals, LAW, and chemical amendments; dries the mixture; and then vitrifies the material in a refractory-lined steel container. AMEC Nuclear Ltd. (AMEC) is adapting its GeoMelt ICV{sup TM} technology for this application with technical and analytical support from Pacific Northwest National Laboratory (PNNL). The DVBS project is funded by the DOE Office of River Protection andmore » administered by CH2M HILL Hanford Group, Inc. The Demonstration Bulk Vitrification Project (DBVS) was initiated to engineer, construct, and operate a full-scale bulk vitrification pilot-plant to treat up to 750,000 liters of LAW from Waste Tank 241-S-109 at the DOE Hanford Site. Since the beginning of the DBVS project in 2004, testing has used laboratory, crucible-scale, and engineering-scale equipment to help establish process limitations of selected glass formulations and identify operational issues. Full-scale testing has provided critical design verification of the ICV{sup TM} process before operating the Hanford pilot-plant. In 2007, the project's fifth full-scale test, called FS-38D, (also known as the Integrated Dryer Melter Test, or IDMT,) was performed. This test had three primary objectives: 1) Demonstrate the simultaneous and integrated operation of the ICV{sup TM} melter with a 10,000- liter dryer, 2) Demonstrate the effectiveness of a new feed reformulation and change in process methodology towards reducing the production and migration of molten ionic salts (MIS), and, 3) Demonstrate that an acceptable glass product is produced under these conditions. Testing was performed from August 8 to 17, 2007. Process and analytical results demonstrated that the primary

Electron-spin-resonance studies of 12CH3F + , 13CH3F + , and 12CH2DF + in neon matrices at 4 K: Comparison with theoretical calculations

NASA Astrophysics Data System (ADS)

Knight, Lon B., Jr.; Gregory, Brian W.; Hill, Devon W.; Arrington, C. A.; Momose, Takamasa; Shida, Tadamasa

1991-01-01

Various isotopic forms of the methyl fluoride cation 12CH3F+, 13CH3F+, and 12CH2DF+ have been generated by photoionization at 16.8 eV and separately by electron bombardment at 50 eV. The first electron-spin-resonance (ESR) results are reported for this radical cation which was isolated in neon matrices at 4 K. The measured A tensors or nuclear hyperfine parameters were compared with the results obtained from various computational approaches. Surprising observations were the large amounts of spin density on the methyl group, especially the hydrogen atoms, and the extreme differences in the deuterated spectra compared to the nondeuterated case. The presence of a single D atom apparently acts to prevent dynamic Jahn-Teller averaging which makes the methyl hydrogens equivalent on the ESR time scale. Such a dramatic Jahn-Teller effect has been previously observed for the similar methane cations CH+4 and CH2D+2. The magnetic parameters for CH2DF+ in neon at 4 K are gX=2.0032(5), gY=2.0106(8), and gZ=2.0120(5); for H: AX = 483(1), AY=476(1), and AZ=483(1) MHz; for D: ‖AX‖=5.0(3), ‖AY‖<3, and ‖AZ‖=7.1(3) MHz; for 19F : AX=965(1), AY=-130(2), and AZ=-166(1) MHz. For CH3F+, the g tensor and 19F A tensor were similar to those above but the H atoms were equivalent with values of AX=317(1), AY=323(2), and AZ=312 MHz.

Hanford Quarter Seismic Report - 98C Seismicity On and Near the Hanford Site, Pasco Basin, Washington: April 1, 1998 Through June 30, 1998

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

DC Hartshorn, SP Reidel, AC Rohay

1998-10-23

Hanford Seismic Monitoring provides an uninterrupted collection of high-quality raw and processed seismic data from the Hanford Seismic Network (HSN) for the U.S. Department of Energy and its contractors. The staff also locates aud identifies sources of seismic activity and monitors changes in the hi~orical pattern of seismic activity at the Hanford Site. The data are. compiled archived, and published for use by the Hanford Site for waste management Natural Phenomena Hazards assessments, and engineering design and construction. In addition, the seismic monitoring organization works with the Hanford Site Emergency Services Organization to provide assistance in the event of zinmore » earthquake on the Hanford Site. The HSN and Ihe Eastern Washington Regional Network (EN/RN) consist-of 42 individual sensor sites and 15 radio relay sites maintained by the Hanford Seismic Monitoring staff. The operational rate for the third quarter of FY 1998 for stations in the HSN was 99.99%. The operational rate for the third quarter of FY 1998 for stations of the EWRN was 99.95%. For the third quarter of FY 1998, the acquisition computer triggered 133 times. Of these triggers 11 were local earthquakes: 5 (45Yo) in the Columbia River Basalt Group, 2(1 8%) in the pre-basalt sediments, and 4 (36%) in the crystalline basement. The geologic and tectonic environments where these earthquakes occurred are discussed in this report.« less

Hanford Quarter Seismic Report - 98C Seismicity On and Near the Hanford Site, Pasco Basin, Washington: April 1, 1998 Through June 30, 1998

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

DC Hartshorn, SP Reidel, AC Rohay.

1998-10-23

Hanford Seismic Monitoring provides an uninterrupted collection of high-quality raw and processed seismic data from the Hanford Seismic Network (HSN) for the U.S. Department of Energy and its contractors. The staff also locates aud identifies sources of seismic activity and monitors changes in the hi orical pattern of seismic activity at the Hanford Site. The data are. compiled archived, and published for use by the Hanford Site for waste management Natural Phenomena Hazards assessments, and engineering design and construction. In addition, the seismic monitoring organization works with the Hanford Site Emergency Services Organization to provide assistance in the event ofmore » zin earthquake on the Hanford Site. The HSN and Ihe Eastern Washington Regional Network (EN/RN) consist-of 42 individual sensor sites and 15 radio relay sites maintained by the Hanford Seismic Monitoring staff. The operational rate for the third quarter of FY 1998 for stations in the HSN was 99.99%. The operational rate for the third quarter of FY 1998 for stations of the EWRN was 99.95%. For the third quarter of FY 1998, the acquisition computer triggered 133 times. Of these triggers 11 were local earthquakes: 5 (45Yo) in the Columbia River Basalt Group, 2(1 8%) in the pre-basalt sediments, and 4 (36%) in the crystalline basement. The geologic and tectonic environments where these earthquakes occurred are discussed in this report.« less

Identification of non-classical C-H···M interactions in early and late transition metal complexes containing the CH(ArO)3 ligand.

PubMed

Lein, Matthias; Harrison, John A; Nielson, Alastair J

2013-08-14

The fully optimised DFT structure of the d(0) complex [{CH(ArO)3}Ti(NEt2)] (2) at the B3LYP level compares well with the distorted tetrahedral geometry shown by the X-ray crystal structure. QTAIM analysis of the electron density associated with the C-H···Ti interaction shows a well defined bond critical point, a bond path between the hydrogen and titanium centres and a negative value for the energy density indicative of covalency. A natural bond orbital (NBO) picture of the interaction shows that the C-H σ bond electron density donates to a d hybrid orbital on the metal in a linear fashion. Calculated IR and NMR data for the components of the interaction are consistent with experiment. The computed structures for [{CH(ArO)3}Ti(OPh)] (3), [{CH(ArO)3}Zr(NEt2)] (4), [{CH(ArO)3}Hf(NEt2)] (5), show tetrahedral geometries and QTAIM and NBO properties similar to (2). [{CH(ArO)3}Mo(NEt2)] (6) shows distortion of the tripodal ligand and a reduced C-H···M bond angle with properties more consistent with a C-H···M side-on donor interaction. In [{CH(ArO)3}Fe(NEt2)] (7) the C-H···M bond angle is linear and involves a donor interaction. An energy minimised structure maintaining the three fold coordination to the tripodal ligand was not obtained for [{CH(ArO)3}Ni(NEt2)](2-) but changing from a diethyl amide ligand to phenolato gave energy minimised [{CH(ArO)3}Ni(OPh)](2-) (8). This structure shows a distorted square planar geometry with a substantially bent phenoxo ligand and a near linear C-H···M covalent interaction with donor and back bonding properties. The work shows that linear C-H···M interactions can have both agostic and weak hydrogen bond-like covalency.

The vacuum-ultraviolet photoelectron spectra of CH2F2 and CH2Cl2 revisited

NASA Astrophysics Data System (ADS)

Tuckett, Richard; Harvey, Jonelle; Hemberger, Patrick; Bodi, Andras

2015-09-01

The threshold photoelectron spectrum (TPES) of difluoromethane and dichloromethane has been recorded at the Swiss Light Source with a resolution of 2 meV or 16 cm-1. Electronic and vibronic transitions are simulated and assigned with the help of Franck-Condon (FC) calculations based on coupled cluster electronic structure calculations for the equilibrium geometries and harmonic vibrational frequencies of the neutrals, and of the ground and excited electronic states of the cations. Notwithstanding a high-resolution pulsed-field ionisation study on CH2F2 (Forysinski et al., 2010) in which a number of transitions to the X∼+ state have been recorded with unprecedented accuracy, we report the first complete vibrationally resolved overview of the low-lying electronic states of CH2X2+, X = F or Cl. Hydrogen atom loss from CH2F2+ occurs at low energy, making the ground state rather anharmonic and interpretation of the X∼+ band challenging in the harmonic approximation. By Franck-Condon fits, the adiabatic ionisation energies to the A∼+ 2B2, C∼+ 2A2 and D∼+ 2B2 states have been determined as 14.3 ± 0.1, 15.57 ± 0.01 and 18.0 ± 0.1 eV, respectively. The first band in the CH2Cl2 TPES is complex for a different reason, as it is the result of two overlapping ionic states, X∼+ 2B2 and A∼+ 2B1, with derived ionisation energies of 11.0 ± 0.2 and 11.317 ± 0.006 eV, and dominated by an extended progression in the CCl2 bend (in X∼+) and a short progression in the CCl2 symmetric stretch (in A∼+), respectively. Furthermore, even though Koopmans' approximation holds for the vertical ionisations, the X∼+ state of CH2Cl2+ is stabilized by geometry relaxation and corresponds to ionisation from the (HOMO-1) orbital. That is, the first two vertical ionisation energies are in the same order as the negative of the orbital energies of the highest occupied orbitals, but the adiabatic ionisation energy corresponding to electron removal from the (HOMO-1) is lower than the

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.

Magnetic behavior control in niccolite structural metal formate frameworks [NH2(CH3)2][Fe(III)M(II)(HCOO)6] (M = Fe, Mn, and Co) by varying the divalent metal ions.

PubMed

Zhao, Jiong-Peng; Hu, Bo-Wen; Lloret, Francesc; Tao, Jun; Yang, Qian; Zhang, Xiao-Feng; Bu, Xian-He

2010-11-15

By changing template cation but introducing trivalent iron ions in the known niccolite structural metal formate frameworks, three complexes formulated [NH(2)(CH(3))(2)][Fe(III)M(II)(HCOO)(6)] (M = Fe for 1, Mn for 2, and Co for 3) were synthesized and magnetically characterized. The variation in the compositions of the complexes leads to three different complexes: mixed-valent complex 1, heterometallic but with the same spin state complex 2, and heterometallic heterospin complex 3. The magnetic behaviors are closely related to the divalent metal ions used. Complex 1 exhibits negative magnetization assigned as Néel N-Type ferrimagnet, with an asymmetric magnetization reversal in the hysteresis loop, and complex 2 is an antiferromagnet with small spin canting (α(canting) ≈ 0.06° and T(canting) = 35 K), while complex 3 is a ferrimagnet with T(N) = 32 K.

Classification of Blood-Group Antibodies as β2M or γ Globulin

PubMed Central

Adinolfi, M.; Polley, Margaret J.; Hunter, Denise A.; Mollison, P. L.

1962-01-01

Thirty selected blood-group antibodies (excluding anti-A and anti-B) have been classified as β2M (19S γ) globulin, γ (7S γ) globulin or mixtures, using the following three methods: fractionation on a DEAE-cellulose column; indirect anti-globulin tests, using specific anti-β2M-globulin and anti-γ-globulin sera; and treatment with 2-mercapto-ethanol. With only minor exceptions, results obtained with the three methods were in agreement. Most blood-group antibodies within the Le, MNSs and P systems appear to be `naturally occurring' and these were found to be β2M globulin. Blood-group antibodies within the Rh, K and Jk systems, which had arisen after an antigenic stimulus, were usually γ globulin but were occasionally β2M globulin. Antibodies composed of β2M globulin usually behave as agglutinins but may behave as incomplete antibodies (e.g. some examples of anti-Jka); conversely, antibodies composed of γ globulin usually behave as incomplete antibodies but may behave as agglutinins (e.g. an example of anti-M). The ability to bind complement seems to be related more to the blood-group specificity of the particular antibody than to its molecular size. For example, anti-Jka, when composed either of γ or β2M globulin, seems invariably to bind complement, whereas potent anti-M or anti-Rh, whether composed of γ or β2M globulin, do not bind complement. PMID:14011076

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.

Algorithm development for the TIR bands of GOSAT-2/TANSO-FTS-2: lessons from GOSAT/TANSO-FTS TIR CO2 and CH4 measurement

NASA Astrophysics Data System (ADS)

Saitoh, N.; Yamada, A.; Itatsu, T.; Imasu, R.; Shiomi, K.; Niwa, Y.

2017-12-01

Greenhouse Gases Observing Satellite-2 (GOSAT-2), the successor of GOSAT, is planned to be launched in a year or so later. Thermal and Near Infrared Sensor for Carbon Observation (TANSO)-Fourier Transform Spectrometer-2 (FTS-2) on board the GOSAT-2 has two bands in the thermal infrared (TIR) region from 5.6 to 14.3 μm. We have developed an algorithm to retrieve CO2 and CH4 vertical profiles from the GOSAT/TANSO-FTS TIR band [Saitoh et al., 2009; 2016] and performed validation analysis for the TANSO-FTS TIR CO2 and CH4 products. Saitoh et al. [2016, 2017] showed that TANSO-FTS TIR V1 CO2 data had a seasonal- and regional-dependent negative bias in the upper troposphere and lower stratosphere and a consistent negative bias in the lower and middle troposphere. Holl et al. [2016], Zou et al. [2016], and Olsen et al. [2017] evaluated the data quality of the TANSO-FTS TIR V1 CH4 product through intercomparisons between TANSO-FTS and other satellite-borne and ground-based instruments; their results were generally consistent with comparison results of the V1 CH4 product with aircraft CH4 data [Saitoh et al., in preparation]. GOSAT/TANSO-FTS TIR N2O data, a by-product of the TIR V1 CH4 data, captured enhancement of N2O concentrations over the Mediterranean Sea associated with Asian monsoon circulation in spite of low signal-to-noise ratio (SNR) of TANSO-FTS 7-μm CH4 band [Kangah et al., 2017]. The SNR of the TIR bands of GOSAT-2/TANSO-FTS-2 are expected to be larger than that of TANSO-FTS especially at the 7-μm CH4 band. Based on the TANSO-FTS TIR V1 algorithm, we are now developing a retrieval algorithm for CO2, CH4, and other trace gases from the two TIR bands of GOSAT-2/TANSO-FTS-2. We have performed retrieval simulations using outputs from the Nonhydrostatic Icosahedral Atmospheric Model (NICAM)-based Transport Model (TM) [Niwa et al., 2011; 2017], which will be used as a priori data for the retrieval processing of GOSAT-2/TANSO-FTS-2.

Second Quarter Hanford Seismic Report for Fiscal Year 2009

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

Rohay, Alan C.; Sweeney, Mark D.; Hartshorn, Donald C.

2009-07-31

The Hanford Seismic Assessment Program (HSAP) provides an uninterrupted collection of high-quality raw and processed seismic data from the Hanford Seismic Network for the U.S. Department of Energy and its contractors. The HSAP is responsible for locating and identifying sources of seismic activity and monitoring changes in the historical pattern of seismic activity at the Hanford Site. The data are compiled, archived, and published for use by the Hanford Site for waste management, natural phenomena hazards assessments, and engineering design and construction. In addition, the HSAP works with the Hanford Site Emergency Services Organization to provide assistance in the eventmore » of a significant earthquake on the Hanford Site. The Hanford Seismic Network and the Eastern Washington Regional Network consist of 44 individual sensor sites and 15 radio relay sites maintained by the Hanford Seismic Assessment Team. The Hanford Seismic Network recorded over 800 local earthquakes during the second quarter of FY 2009. Nearly all of these earthquakes were detected in the vicinity of Wooded Island, located about eight miles north of Richland just west of the Columbia River. Most of the events were considered minor (magnitude (Mc) less than 1.0) with 19 events in the 2.0-2.9 range. The estimated depths of the Wooded Island events are shallow (averaging less than 1.0 km deep) with a maximum depth estimated at 1.9 km. This places the Wooded Island events within the Columbia River Basalt Group (CRBG). The low magnitude and the shallowness of the Wooded Island events have made them undetectable to most area residents. However, some Hanford employees working within a few miles of the area of highest activity, and individuals living in homes directly across the Columbia River from the swarm center, have reported feeling some movement. The Hanford SMA network was triggered numerous times by the Wooded Island swarm events. The maximum acceleration values recorded by the SMA network

Progress in Hanford's Double-Shell Tank Integrity Project

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

Bryson, D.C.; Washenfelder, D.J.; Boomer, K.D.

2008-07-01

The U.S. Department of Energy's Office of River Protection has an extensive integrity assessment program for the Hanford Site Double-Shell Tank System. The DOE Orders and environmental protection regulations provide the guidelines for the activities used to inspect and maintain 28 double-shell tanks (DSTs), the waste evaporator, and ancillary equipment that compose this system. This program has been reviewed by oversight and regulatory bodies and found to comply with the established guidelines. The basis for the DOE Order 435.1-1 for tank integrity comes from the Tank Structural Integrity Panel led by Brookhaven National Laboratory during the late 1990's. These guidelinesmore » established criteria for performing Non-Destructive Examination (NDE), for acceptance of the NDE results, for waste chemistry control, and for monitoring the tanks. The environmental regulations mirror these requirements and allow for the tank integrity program to provide compliant storage of the tanks. Both sets of requirements provide additional guidance for the protection of ancillary equipment. CH2M HILL uses two methods of NDE: visual inspection and Ultrasonic Testing (UT). The visual inspection program examines the primary tank and secondary liner of the DST. The primary tank is examined both on the interior surface above the waste in the tank and on the exterior surface facing the annulus of the DST. The interior surface of the tank liner is examined at the same time as the outer surface of the primary tank. The UT program examines representative areas of the primary tank and secondary liner by deploying equipment in the annulus of the tank. Both programs have led to the development of new equipment for remote inspection of the tanks. Compact camera and enhanced lighting systems have been designed and deployed through narrow access ports (called risers) into the tanks. The UT program has designed two generations of crawlers and equipment for deployment through risers into the

Temperature-Dependent Kinetics Studies of the Reactions Br((sup 2)P(sub 3/2)) + CH3SCH3 reversible reaction CH3SCH2 + HBr. Heat of Formation of the CH3SCH2 Radical

NASA Technical Reports Server (NTRS)

Jefferson, A.; Nicovich, J. M.; Wine, P. H.

1997-01-01

Time-resolved resonance fluorescence detection of Br((sup 2)P(sub 3/2)) atom disappearance or appearance 266 nm laser flash photolysis of CF2Br2/CH3SCH3/H2/N2 and Cl2CO/CH2SCH3/HBr/H2/N2 mixtures has been employed to study the kinetics of the reactions Br((sup 2)P(sub 3/2)) + CH3SCH3 reversible reaction HBr + CH3SCH2 (1,-1) as a function of temperature over the range 386-604 K. Arrhenius expressions in units of cu cm/molecule which describe the results are k3= (9.0 +/- 2.9) x 10 (exp -11) exp[(-2386 +/- 151)/T]; errors are 2 sigma and represent precision only. To our knowledge, these are the first kinetic data reported for each of the two reactions studied. Second and third law analyses of the equilibrium data for reactions 1 and -1 have been employed to obtain the following enthalpies of reaction in units of kcal/mol: Delta-H(298) = 6.11 +/- 1.37 and Delta-H(0) = 5.37 +/- 1.38. Combining the above enthalpies of reaction with the well-known heats of formation of Br, HBr, CH3SCH3 gives the following heats of formation of the CH3SCH2 radical in units of kcal/mol: Delta-H(sub(f,298)) = 32.7 +/- 1.4 and Delta-H(sub (f,0)) = 35.3 +/- 1.4; errors are 2 sigma and represent estimates of absolute accuracy. The C-H bond dissociation energy in CH3SCH3 obtained from our data, 93.7 +/- 1.4 kcal/mol at 298 K and 92.0 +/- 1.4 kcal at 0 k, agrees well with a recent molecular beam photofragmentaion study but is 3 kcal/mol lower than the value obtained from an iodination kinetics study.

Silicon nitride and silicon etching by CH{sub 3}F/O{sub 2} and CH{sub 3}F/CO{sub 2} plasma beams

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

Kaler, Sanbir S.; Lou, Qiaowei; Donnelly, Vincent M., E-mail: vmdonnelly@uh.edu

2016-07-15

Silicon nitride (SiN, where Si:N ≠ 1:1) films low pressure-chemical vapor deposited on Si substrates, Si films on Ge on Si substrates, and p-Si samples were exposed to plasma beams emanating from CH{sub 3}F/O{sub 2} or CH{sub 3}F/CO{sub 2} inductively coupled plasmas. Conditions within the plasma beam source were maintained at power of 300 W (1.9 W/cm{sup 3}), pressure of 10 mTorr, and total gas flow rate of 10 sccm. X-ray photoelectron spectroscopy was used to determine the thicknesses of Si/Ge in addition to hydrofluorocarbon polymer films formed at low %O{sub 2} or %CO{sub 2} addition on p-Si and SiN. Polymer film thickness decreasedmore » sharply as a function of increasing %O{sub 2} or %CO{sub 2} addition and dropped to monolayer thickness above the transition point (∼48% O{sub 2} or ∼75% CO{sub 2}) at which the polymer etchants (O and F) number densities in the plasma increased abruptly. The C(1s) spectra for the polymer films deposited on p-Si substrates appeared similar to those on SiN. Spectroscopic ellipsometry was used to measure the thickness of SiN films etched using the CH{sub 3}F/O{sub 2} and CH{sub 3}F/CO{sub 2} plasma beams. SiN etching rates peaked near 50% O{sub 2} addition and 73% CO{sub 2} addition. Faster etching rates were measured in CH{sub 3}F/CO{sub 2} than CH{sub 3}F/O{sub 2} plasmas above 70% O{sub 2} or CO{sub 2} addition. The etching of Si stopped after a loss of ∼3 nm, regardless of beam exposure time and %O{sub 2} or %CO{sub 2} addition, apparently due to plasma assisted oxidation of Si. An additional GeO{sub x}F{sub y} peak was observed at 32.5 eV in the Ge(3d) region, suggesting deep penetration of F into Si, under the conditions investigated.« less

Measuring the Impact of Rising CO2 and CH4 on the Surface Energy Balance

NASA Astrophysics Data System (ADS)

Feldman, D.; Collins, W.; Biraud, S.; Turner, D. D.; Mlawer, E. J.; Gero, P. J.; Xie, S.; Shippert, T.; Torn, M. S.

2015-12-01

We use observations at the North Slope of Alaska (NSA) and Southern Great Plains (SGP) ARM sites to improve understanding both of the distribution of CO2 and CH4and their influence on the surface energy balance. We use aircraft and ground-based in situ data to characterize the temporal distribution of these greenhouse gases, and spectroscopic observations to derive their collocated surface radiative forcing. The spectroscopically-measured surface radiative forcing from rising CO2 is 0.2 W/m2/decade at both sites, with a seasonal cycle of 0.2 W/m2. This finding is largely consistent with theoretical predictions, providing robust evidence of radiative perturbations to the Earth's surface energy budget due to anthropogenic influences. The contribution from CH4 to the surface energy balance is more spatially and temporally heterogeneous. The ground-based measurements of CH4 at NSA and SGP indicate rising atmospheric concentrations except for a hiatus from 1995-2005, while more recent aircraft profiles indicate that concentrations in the boundary layer and free troposphere are correlated at NSA and decorrelated at SGP. The probability density functions of boundary layer concentrations of CH4 at NSA show little skew, but at SGP show positive skewness, which increased with the introduction of nearby fossil-fuel extraction. The correlated increases in atmospheric measurements of C2H6 and CH4that only occur at SGP are consistent with an anthropogenic influence there. Time-series of spectroscopically-measured CH4 surface radiative forcing at SGP and NSA also indicate positive trends of 0.1 W/m2/decade associated with the end of the hiatus, marked seasonal cycles, and little skew at NSA and a positive skew at SGP. The combination of in situ and spectroscopic measurements at these sites enables the quantification of surface radiative forcing from anthropogenic CH4. Implications are discussed for how advanced spectroscopic remote sensing measurements of CH4 can be used to

Optical emission spectroscopic studies and comparisons of CH{sub 3}F/CO{sub 2} and CH{sub 3}F/O{sub 2} inductively coupled plasmas

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

Lou, Qiaowei; Kaler, Sanbir; Donnelly, Vincent M., E-mail: vmdonnelly@uh.edu

2015-03-15

A CH{sub 3}F/CO{sub 2} inductively coupled plasma (ICP), sustained in a compact plasma reactor, was investigated as a function of power (5–400 W) and feed gas composition, at a pressure of 10 mTorr, using optical emission spectroscopy and rare gas actinometry. Number densities of H, F, and O increased rapidly between 74% and 80% CO{sub 2}, ascribed to the transition from polymer-covered to polymer-free reactor walls, similar to that found previously in CH{sub 3}F/O{sub 2} ICPs at 48% O{sub 2}. Below 40% O{sub 2} or CO{sub 2}, relative emission intensity ratios were almost identical for most key species in CH{sub 3}F/O{submore » 2} and CH{sub 3}F/CO{sub 2} ICPs except for higher OH/Xe (a qualitative measure of OH and H{sub 2}O densities) over the full range of CH{sub 3}F/O{sub 2} composition. The number density of H, F, and O increased with power in CH{sub 3}F/CO{sub 2} (20%/80%) plasmas (polymer-free walls), reaching 4.0, 0.34, and 1.6 × 10{sup 13}/cm{sup 3}, respectively, at 300 W. The CO number density increased with power and was estimated, based on self-actinometry, to be 8.8 × 10{sup 13}/cm{sup 3} at 300 W. The CO{sub 2} number density was independent of power below 40 W (where very little decomposition occurred), and then decreased rapidly with increasing power, reaching 2.8 × 10{sup 13}/cm{sup 3} at 300 W, corresponding to 83% dissociation. Films deposited on p-Si, 10 cm from the open, downstream end of the plasma reactor, were analyzed by x-ray photoelectron spectroscopy. Between 10% and 40% CO{sub 2} or O{sub 2} addition to CH{sub 3}F, film deposition rates fell and O content in the films increased. Faster deposition rates in CH{sub 3}F/CO{sub 2} plasmas were ascribed mainly to a larger thermodynamic driving force to form solid carbon, compared with CH{sub 3}F/O{sub 2} plasmas. Oxygen content in the films increased with increasing CO{sub 2} or O{sub 2} addition, but for the same deposition rate, no substantial differences

Proceedings of the First Hanford Separation Science Workshop

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

Not Available

1993-05-01

The First Hanford Separation Science Workshop, sponsored by PNL had two main objectives: (1) assess the applicability of available separation methods for environmental restoration and for minimization, recovery, and recycle of mixed and radioactive mutes; and (2) identify research needs that must be addressed to create new or improved technologies. The information gathered at this workshop not only applies to Hanford but could be adapted to DOE facilities throughout the nation as well. These proceedings have been divided into three components: Background and Introduction to the Problem gives an overview of the history of the Site and the cleanup mission,more » including waste management operations, past disposal practices, current operations, and plans for the future. Also included in this section is a discussion of specific problems concerning the chemistry of the Hanford wastes. Separation Methodologies contains the papers given at the workshop by national experts in the field of separation science regarding the state-of-the-art of various methods and their applicability/adaptability to Hanford. Research Needs identifies further research areas developed in working group sessions. Individual papers are indexed separately.« less

Hanford`s innovations for science education

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

Carter, D.

1996-12-31

In recognition of declining science literacy in the United States and a projected shortfall of scientists, engineers and technologists to address environmental problems nationally and internationally during the 21st century, Westinghouse Hanford Company has launched several innovative science education projects at the US Department of Energy Hanford Site. The Hanford Site is very rich in resources that can be brought to bear on the problem: world-class technical experts, state of the art facilities and equipment, and the largest environmental laboratory in the world. During the past two years, several innovative science education initiatives have been conceived and pursued at themore » secondary education level including the International Academy for the Environment (residential high school with an environmental theme), Environmental BATTmobile Program (mobile middle school science education program), and Multicultural Experiences in Math and Science (education program based on cultural contributions to math and science). Hanford scientists, engineers and administrators have worked with the education community (K-12 and college-university) to develop innovative approaches to science education.« less

Ice chemistry of acetaldehyde reveals competitive reactions in the first step of the Strecker synthesis of alanine: formation of HO-CH(CH3)-NH2 vs. HO-CH(CH3)-CN

NASA Astrophysics Data System (ADS)

Fresneau, Aurélien; Danger, Grégoire; Rimola, Albert; Duvernay, Fabrice; Theulé, Patrice; Chiavassa, Thierry

2015-08-01

The understanding of compound formation in laboratory simulated astrophysical environments is an important challenge in obtaining information on the chemistry occurring in these environments. We here investigate by means of both laboratory experiments and quantum chemical calculations the ice-based reactivity of acetaldehyde (CH3CHO) with ammonia (NH3) and hydrogen cyanide (HCN) in excess of water (H2O) promoted by temperature. A priori, this study should give information on alanine (2HN-CH(CH3)-COOH) formation (the simplest chiral amino acid detected in meteorites), since these reactions concern the first steps of its formation through the Strecker synthesis. However, infrared spectroscopy, mass spectrometry with HC14N or HC15N isotopologues and B3LYP-D3 results converge to indicate that an H2O-dominated ice containing CH3CHO, NH3 and HCN not only leads to the formation of α-aminoethanol (2HN-CH(CH3)-OH, the product compound of the first step of the Strecker mechanism) and its related polymers (2HN-(CH(CH3)-O)n-H) due to reaction between CH3CHO and NH3, but also to the 2-hydroxypropionitrile (HO­-CH(CH3)-CN) and its related polymers (H-(O-CH(CH3))n-CN) from direct reaction between CH3CHO and HCN. The ratio between these two species depends on the initial NH3/HCN ratio in the ice. Formation of α-aminoethanol is favoured when the NH3 concentration is larger than HCN. We also show that the presence of water is essential for the formation of HO­-CH(CH3)-CN, contrarily to 2HN-CH(CH3)-OH whose formation also takes place in absence of H2O ice. As in astrophysical ices NH3 is more abundant than HCN, formation of α-aminoethanol should consequently be favoured compared to 2-hydroxypropionitrile, thus pointing out α-aminoethanol as a plausible intermediate species for alanine synthesis through the Strecker mechanism in astrophysical ices.

Thermodynamic properties of seven gaseous halogenated hydrocarbons from acoustic measurements: CHClFCF3, CHF2 CF3, CF3 CH3, CHF2CH3, CF3CHFCHF2, CF3CH2CF3, and CHF2CF2CH2F

NASA Astrophysics Data System (ADS)

Gillis, K. A.

1997-01-01

Measurements of the speed of sound in seven halogenated hydrocarbons are presented. The compounds in this study are 1-chloro-1,2,2,2-tetrafluoroethane (CHClFCF3 or HCFC-124), pentafluoroethane (CHF2 CF3 or HFC-125), 1,1,1-trifluoroethane (CF3CH3 or HFC-143a), 1,1-difluoroethane (CHF2CH3 or HFC-152a), 1,1,1,2,3,3-hexafluoropropane (CF3CHFCHF2 or HFC-236ea), 1,1,1,3,3,3-hexafluoropropane (CF3CH2CF3 or HFC-236fa), and 1,1,2,2,3-pentafluoropropane (CHF2CF2CH2F or HFC-245ca). The measurements were performed with a cylindrical resonator at temperatures between 240 and 400 K and at pressures up to 1.0 MPa. Ideal-gas heat capacities and acoustic virial coefficients were directly deduced from the data. The ideal-gas heat capacity of HFC-125 from this work differs from spectroscopic calculations by less than 0.2% over the measurement range. The coefficients for virial equations of state were obtained from the acoustic data and hard-core square-well intermolecular potentials. Gas densities that were calculated from the virial equations of state for HCFC-124 and HFC-125 differ from independent density measurements by at most 0.15%, for the ranges of temperature and pressure over which both acoustic and Burnett data exist. The uncertainties in the derived properties for the other five compounds are comparable to those for HCFC-124 and HFC-125.

Third Quarter Hanford Seismic Report for Fiscal Year 2009

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

Rohay, Alan C.; Sweeney, Mark D.; Hartshorn, Donald C.

2009-09-30

The Hanford Seismic Assessment Program (HSAP) provides an uninterrupted collection of high-quality raw and processed seismic data from the Hanford Seismic Network for the U.S. Department of Energy and its contractors. The HSAP is responsible for locating and identifying sources of seismic activity and monitoring changes in the historical pattern of seismic activity at the Hanford Site. The data are compiled, archived, and published for use by the Hanford Site for waste management, natural phenomena hazards assessments, and engineering design and construction. In addition, the HSAP works with the Hanford Site Emergency Services Organization to provide assistance in the eventmore » of a significant earthquake on the Hanford Site. The Hanford Seismic Network and the Eastern Washington Regional Network consist of 44 individual sensor sites and 15 radio relay sites maintained by the Hanford Seismic Assessment Team. The Hanford Seismic Network recorded 771 local earthquakes during the third quarter of FY 2009. Nearly all of these earthquakes were detected in the vicinity of Wooded Island, located about eight miles north of Richland just west of the Columbia River. The Wooded Island events recorded this quarter is a continuation of the swarm events observed during the January – March 2009 time period and reported in the previous quarterly report (Rohay et al, 2009). The frequency of Wooded Island events has subsided with 16 events recorded during June 2009. Most of the events were considered minor (magnitude (Mc) less than 1.0) with 25 events in the 2.0-3.0 range. The estimated depths of the Wooded Island events are shallow (averaging less than 1.0 km deep) with a maximum depth estimated at 2.2 km. This places the Wooded Island events within the Columbia River Basalt Group (CRBG). The low magnitude of the Wooded Island events has made them undetectable to all but local area residents. However, some Hanford employees working within a few miles of the area of highest

A theoretical investigation on Cu/Ag/Au bonding in XH2P⋯MY(X = H, CH3, F, CN, NO2; M = Cu, Ag, Au; Y = F, Cl, Br, I) complexes

NASA Astrophysics Data System (ADS)

Wang, Zhaoxu; Liu, Yi; Zheng, Baishu; Zhou, Fengxiang; Jiao, Yinchun; Liu, Yuan; Ding, XunLei; Lu, Tian

2018-05-01

Intermolecular interaction of XH2P...MY (X = H, CH3, F, CN, NO2; M = Cu, Ag, Au; Y = F, Cl, Br, I) complexes was investigated by means of an ab initio method. The molecular interaction energies are in the order Ag < Cu < Au and increased with the decrease of RP...M. Interaction energies are strengthened when electron-donating substituents X connected to XH2P, while electron-withdrawing substituents produce the opposite effect. The strongest P...M bond was found in CH3H2P...AuF with -70.95 kcal/mol, while the weakest one was found in NO2H2P...AgI with -20.45 kcal/mol. The three-center/four-electron (3c/4e) resonance-type of P:-M-:Y hyperbond was recognized by the natural resonance theory and the natural bond orbital analysis. The competition of P:M-Y ↔ P-M:Y resonance structures mainly arises from hyperconjugation interactions; the bond order of bP-M and bM-Y is in line with the conservation of the idealized relationship bP-M + bM-Y ≈ 1. In all MF-containing complexes, P-M:F resonance accounted for a larger proportion which leads to the covalent characters for partial ionicity of MF. The interaction energies of these Cu/Ag/Au complexes are basically above the characteristic values of the halogen-bond complexes and close to the observed strong hydrogen bonds in ionic hydrogen-bonded species.

Real-time observation of formation and relaxation dynamics of NH4 in (CH3OH)m(NH3)n clusters.

PubMed

Yamada, Yuji; Nishino, Yoko; Fujihara, Akimasa; Ishikawa, Haruki; Fuke, Kiyokazu

2009-03-26

The formation and relaxation dynamics of NH4(CH3OH)m(NH3)n clusters produced by photolysis of ammonia-methanol mixed clusters has been observed by a time-resolved pump-probe method with femtosecond pulse lasers. From the detailed analysis of the time evolutions of the protonated cluster ions, NH4(+)(CH3OH)m(NH3)n, the kinetic model has been constructed, which consists of sequential three-step reaction: ultrafast hydrogen-atom transfer producing the radical pair (NH4-NH2)*, the relaxation process of radical-pair clusters, and dissociation of the solvated NH4 clusters. The initial hydrogen transfer hardly occurs between ammonia and methanol, implying the unfavorable formation of radical pair, (CH3OH2-NH2)*. The remarkable dependence of the time constants in each step on the number and composition of solvents has been explained by the following factors: hydrogen delocalization within the clusters, the internal conversion of the excited-state radical pair, and the stabilization of NH4 by solvation. The dependence of the time profiles on the probe wavelength is attributed to the different ionization efficiency of the NH4(CH3OH)m(NH3)n clusters.

Precipitation of nitrate-cancrinite in Hanford Tank Sludge.

PubMed

Buck, E C; McNamara, B K

2004-08-15

The chemistry of underground storage tanks containing high-level waste at the Hanford Site in Washington State is an area of continued research interest. Thermodynamic models have predicted the formation of analcime and clinoptilolite in Hanford tanks, rather than cancrinite; however, these predictions were based on carbonate-cancrinite. We report the first observation of a nitrate-cancrinite [possibly Na8(K,Cs)(AlSiO4)6(NO3)2 x nH2O] extracted from a Hanford tank 241-AP-101 sample that was evaporated to 6, 8, and 10 M NaOH concentrations. The nitrate-cancrinite phase formed spherical aggregates (4 microm in diameter) that consisted of platy hexagonal crystals (approximately 0.2 microm thick). Cesium-137 was concentrated in these aluminosilicate structures. These phases possessed a morphology identical to that of nitrate-cancrinite synthesized using simulant tests of nonradioactive tank waste, supporting the contention that it is possible to develop nonradioactive artificial sludges. This investigation points to the continued importance of understanding the solubility of NO3-cancrinite and related phases. Knowledge of the detailed structure of actual phases in the tank waste helps with thermodynamic modeling of tank conditions and waste processing.

Direct observation of unimolecular decay of CH 3 CH 2 CHOO Criegee intermediates to OH radical products

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

Fang, Yi; Liu, Fang; Klippenstein, Stephen J.

2016-07-28

The unimolecular decay of carbonyl oxide intermediates, known as Criegee intermediates, produced in alkene ozonolysis is a significant source of OH radicals in the troposphere. Here, the rate of appearance of OH radical products is examined directly in the time-domain for a prototypical alkyl-substituted Criegee intermediate, CH3CH2CHOO, following vibrational activation under collision-free conditions. Complementary statistical Rice-Ramsperger-Kassel-Marcus calculations of the microcanonical unimolecular decay rate for CH3CH2CHOO are also carried out at energies in the vicinity of the barrier for 1,4 hydrogen atom transfer that leads to OH products. Tunneling through the barrier, derived from high level electronic structure calculations, contributes significantlymore » to the decay rate. Infrared transitions of CH3CH2CHOO are identified in the CH stretch overtone region, which are detected by ultraviolet laser-induced fluorescence of the resultant OH products. The features observed are attributed to CH vibrational excitations and conformational forms utilizing insights from theory. Both experiment and theory yield unimolecular decay rates for CH3CH2CHOO of ca. 10(7) s(-1), which are slower than those obtained for syn-CH3CHOO or (CH3)(2)COO reported previously [Fang et al., J. Chem. Phys. 144, 061102 (2016)] at similar energies. Master equation modeling is also utilized to predict the thermal decay rate of CH3CH2CHOO under atmospheric conditions, giving a rate of 279 s(-1) at 298 K.« less

In situ Investigation of Methane Dry Reforming on M-CeO 2(111) {M= Co, Ni, Cu} Surfaces: Metal-Support Interactions and the activation of C-H bonds at Low Temperature

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

Rodriguez, Jose A.; Liu, Zongyuan; Lustemberg, Pablo

Studies with a series of M-CeO 2(111) {M= Co, Ni, Cu} surfaces indicate that metal-oxide interactions can play a very important role for the activation of methane and its reforming with CO 2 at relatively low temperatures (600-700 K). Among the systems examined, Co-CeO 2(111) exhibits the best performance and Cu-CeO 2(111) has negligible activity. Experiments using ambient pressure XPS indicate that methane dissociates on Co-CeO2(111), at temperatures as low as 300 K, generating CH x and CO x species on the catalyst surface. The results of density-functional calculations show a reduction in the methane activation barrier from 1.07 eVmore » on Co(0001) to 0.87 eV on Co 2+/CeO 2(111), and to only 0.05 eV on Co 0/CeO 2-x(111). At 700 K, under methane dry reforming conditions, CO 2 dissociates on the oxide surface and a catalytic cycle is established without coke deposition. In conclusion, a significant part of the CH x formed on the Co 0/CeO 2-x (111) catalyst recombines to yield ethane or ethylene.« less

In situ Investigation of Methane Dry Reforming on M-CeO 2(111) {M= Co, Ni, Cu} Surfaces: Metal-Support Interactions and the activation of C-H bonds at Low Temperature

DOE PAGES

Rodriguez, Jose A.; Liu, Zongyuan; Lustemberg, Pablo; ...

2017-08-16

Studies with a series of M-CeO 2(111) {M= Co, Ni, Cu} surfaces indicate that metal-oxide interactions can play a very important role for the activation of methane and its reforming with CO 2 at relatively low temperatures (600-700 K). Among the systems examined, Co-CeO 2(111) exhibits the best performance and Cu-CeO 2(111) has negligible activity. Experiments using ambient pressure XPS indicate that methane dissociates on Co-CeO2(111), at temperatures as low as 300 K, generating CH x and CO x species on the catalyst surface. The results of density-functional calculations show a reduction in the methane activation barrier from 1.07 eVmore » on Co(0001) to 0.87 eV on Co 2+/CeO 2(111), and to only 0.05 eV on Co 0/CeO 2-x(111). At 700 K, under methane dry reforming conditions, CO 2 dissociates on the oxide surface and a catalytic cycle is established without coke deposition. In conclusion, a significant part of the CH x formed on the Co 0/CeO 2-x (111) catalyst recombines to yield ethane or ethylene.« less

Constraining the Molecular Complexity in the Interstellar Medium—The Formation of Ethyl Methyl Ether (CH3OCH2CH3) in Star-forming Regions

NASA Astrophysics Data System (ADS)

Bergantini, Alexandre; Frigge, Robert; Kaiser, Ralf I.

2018-05-01

We report the first confirmed synthesis of ethyl methyl ether (EME, CH3CH2OCH3) within astrophysical model ices containing water (H2O) and methane (CH4) exposed to ionizing radiation at ultra-low temperatures of 5 K. EME (also known as methoxyethane), was recently observed toward Orion KL and currently is the largest confirmed oxygen-bearing molecule found in the interstellar medium. Exploiting isomer-selective photoionization (PI) of the subliming molecules in the temperature-programmed desorption phase at 10.49, 9.92, and 9.70 eV, coupled with reflectron time-of-flight mass spectrometry and isotopic substitution experiments (H2 18O–CH4), the detection of fragment ions of EME at m/z = 45 (C2H5O+) and m/z = 59 (C3H7O+), and probing the proton transfer in subliming ethanol–EME complexes via m/z = 61 (C3H9O+), the present study reveals that EME can be formed from suprathermal reactions initiated by cosmic rays and secondary electrons generated within astrophysical ices. The detection of EME in our experiments represents a significant advance in the understanding of formation pathways of complex organic molecules present in hot cores and helps to constrain astrochemical models on the formation of such species within molecular clouds.

Atmospheric lifetimes and ozone depletion potentials of methyl bromide (CH3Br) and dibromomethane (CH2Br2)

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

Mellouki, A.; Talukdar, R.K.; Schmoltner, A.

The rate coefficients for the reactions of OH radical with CH3Br and CH2Br2 were measured as functions of temperature using the laser photolysis - laser induced fluorescence method. This data was incorporated into a semiempirical model (Solomon et al., 1992) and a 2D model to calculate the steady-state ozone depletion potentials (ODP) and atmospheri lifetimes, tau, with greatly improved accuracy as compared to earlier studies. The calculated ODPs and tau are 0.65 and 1.7 years and 0.17 and 0.41 years for CH3Br and CH2Br2, respectively, using the semiempirical model. These lifetimes agree well with those calculated using a 2D model.more » This study better quantifies the ODPs and tau of these species which are needed inputs for discussion of possible regulation of human emissions currently under international considerations. 29 refs.« less

Mathematical Modelling of Arctic Polygonal Tundra with Ecosys: 2. Microtopography Determines How CO2 and CH4 Exchange Responds to Changes in Temperature and Precipitation

NASA Astrophysics Data System (ADS)

Grant, R. F.; Mekonnen, Z. A.; Riley, W. J.; Arora, B.; Torn, M. S.

2017-12-01

Differences of surface elevation in arctic polygonal landforms cause spatial variation in soil water contents (θ), active layer depths (ALD), and thereby in CO2 and CH4 exchange. Here we test hypotheses in ecosys for topographic controls on CO2 and CH4 exchange in trough, rim, and center features of low- and flat-centered polygons (LCP and FCP) against chamber and eddy covariance (EC) measurements during 2013 at Barrow, Alaska. Larger CO2 influxes and CH4 effluxes were measured with chambers and modeled with ecosys in LCPs than in FCPs and in lower features (troughs) than in higher (rims) within LCPs and FCPs. Spatially aggregated CO2 and CH4 fluxes from ecosys were significantly correlated with EC flux measurements. Lower features were modeled as C sinks (52-56 g C m-2 yr-1) and CH4 sources (4-6 g C m-2 yr-1), and higher features as near C neutral (-2-15 g C m-2 yr-1) and CH4 neutral (0.0-0.1 g C m-2 yr-1). Much of the spatial and temporal variations in CO2 and CH4 fluxes were modeled from topographic effects on water and snow movement and thereby on θ, ALD, and soil O2 concentrations. Model results forced with meteorological data from 1981 to 2015 indicated increasing net primary productivity in higher features and CH4 emissions in some lower and higher features since 2008, attributed mostly to recent rises in precipitation. Small-scale variation in surface elevation causes large spatial variation of greenhouse gas (GHG) exchanges and therefore should be considered in estimates of GHG exchange in polygonal landscapes.

Direct dynamics simulation of dioxetane formation and decomposition via the singlet .O-O-CH2-CH2. biradical: Non-RRKM dynamics

NASA Astrophysics Data System (ADS)

Sun, Rui; Park, Kyoyeon; de Jong, Wibe A.; Lischka, Hans; Windus, Theresa L.; Hase, William L.

2012-07-01

Electronic structure calculations and direct chemical dynamics simulations are used to study the formation and decomposition of dioxetane on its ground state singlet potential energy surface. The stationary points for 1O2 + C2H4, the singlet .O-O-CH2-CH2. biradical, the transition state (TS) connecting this biradical with dioxetane, and the two transition states and gauche .O-CH2-CH2-O. biradical connecting dioxetane with the formaldehyde product molecules are investigated at different levels of electronic structure theory including UB3LYP, UMP2, MRMP2, and CASSCF and a range of basis sets. The UB3LYP/6-31G* method was found to give representative energies for the reactive system and was used as a model for the simulations. UB3LYP/6-31G* direct dynamics trajectories were initiated at the TS connecting the .O-O-CH2-CH2. biradical and dioxetane by sampling the TS's vibrational energy levels, and rotational and reaction coordinate energies, with Boltzmann distributions at 300, 1000, and 1500 K. This corresponds to the transition state theory model for trajectories that pass the TS. The trajectories were directed randomly towards both the biradical and dioxetane. A small fraction of the trajectories directed towards the biradical recrossed the TS and formed dioxetane. The remainder formed 1O2 + C2H4 and of these ˜ 40% went directly from the TS to 1O2 + C2H4 without getting trapped and forming an intermediate in the .O-O-CH2-CH2. biradical potential energy minimum, a non-statistical result. The dioxetane molecules which are formed dissociate to two formaldehyde molecules with a rate constant two orders of magnitude smaller than that predicted by Rice-Ramsperger-Kassel-Marcus theory. The reaction dynamics from dioxetane to the formaldehyde molecules do not follow the intrinsic reaction coordinate or involve trapping in the gauche .O-CH2-CH2-O. biradical potential energy minimum. Important non-statistical dynamics are exhibited for this reactive system.

Intercomparison of six ambient [CH2O] measurement techniques

NASA Astrophysics Data System (ADS)

Gilpin, Tim; Apel, Eric; Fried, Alan; Wert, Bryan; Calvert, Jack; Genfa, Zhang; Dasgupta, Purnendu; Harder, Jerry W.; Heikes, Brian; Hopkins, Brian; Westberg, Hal; Kleindienst, Tad; Lee, Yin-Nan; Zhou, Xianliang; Lonneman, William; Sewell, Scott

1997-09-01

From May 29 to June 3, 1995 a blind intercomparison of six ambient formaldehyde measurement techniques took place at a field site near the National Center for Atmospheric Research in Boulder, Colorado. The continuous measurement methods intercompared were tunable diode laser absorption spectroscopy, (TDLAS); coil/2,4-dinitrophenylhydrazine, (CDNPH); 1,3-cyclohexanedione-diffusion scrubber (CHDDS); and the coil enzyme method (CENZ). In addition, two different cartridge methods were compared: silica gel-2,4-dinitrophenylhydrazine (DPNH) systems and a C-18-DNPH system. The intercomparison was conducted with spiked zero air (part 1) and ambient air (part 2). The CH2O standards for part 1 were calibrated by several independent methods and delivered to participants via a common glass manifold with potential trace gas interférants common to ambient air (O3, SO2, NO2, isoprene, H2O). The TDLAS system was used to confirm the absolute accuracy of the standards and served as a mission reference for part 1. The ambient phase lasted 44 hours with all participants sampling from a common glass tower. Differences between the ambient [CH2O] observed by the TDLAS and the other continuous methods were significant in some cases. For matched ambient measurement times the average ratios (±1σ) [CH2O]measured/[CH2O]TDLAS were: 0.89±0.12 (CDNPH); 1.30±0.02 (CHDDS); 0.63±0.03 (CENZ). The methods showed similar variations but different absolute values and the divergences appeared to result largely from calibration differences (no gas phase standards were used by groups other than NCAR). When the regressions of the participant [CH2O] values versus the TDLAS values, (measured in part 1), were used to normalize all of the results to the common gas phase standards of the NCAR group, the average ratios (±1σ), [CH2O]corrected/[CH2O]TDLAS for the first measurement period were much closer to unity: 1.04±0.14 (CDNPH), 1.00±0.11 (CHDDS), and 0.82±0.08 (CENZ). With the continuous methods

HỖ TRỢ CỦA GIA ĐÌNH ĐỐI VỚI NAM TIÊM CHÍCH MA TÚY NHIỄM HIV TẠI HÀ NỘI

PubMed Central

Ngọc, Lùng Bích; Ly, An Thanh; Hòa, Trần Thị; Giang, Lê Minh

2016-01-01

Nghiên cứu định tính nhằm mô tả hỗ trợ của gia đình trong chăm sóc sức khỏe, đặc biệt trong điều trị HIV và nghiện chắt của nam tiêm chích ma túy nhiễm HIV tại Hà Nội. Kết quả phân tích cho thấy gia đình chủ yếu hỗ trợ tài chính, tinh thần và chăm sóc sức khỏe trong khi các hỗ trợ thông tin liên quan đến điều trị HIV và nghiện chất cho nam tiêm chích ma túy nhiễm HIV của gia đình còn khá hạn chế. Hỗ trợ của gia đình cho nam tiêm chích ma túy nhiễm HIV khác nhau giữa các giai đoạn sử dụng ma túy, nhiễm HIV, điều trị HIV và điều trị nghiện chất. Đáng chú ý là việc tiết lộ tình trạng nhiễm HIV đã giúp các nam tiêm chích ma túy nhận được nhiều hơn sự hỗ trợ từ gia đình. Các can thiệp nhằm nâng cao hiệu quả điều trị HIV và điều trị nghiện chất cho nam tiêm chích ma túy nhiễm HIV cần tính đến sự tham gia hỗ trợ của gia đình. PMID:28393100

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.

Scaled Hartree-Fock force field calculations for organothallium compounds: Normal-mode analysis for TlCH sub 3 Tl(CH sub 3 ) sub 2 sup + , Tl(CH sub 3 ) sub 3 , Tl(CH sub 3 ) sub 2 Br, and Tl(CH sub 3 ) sub 4 sup minus

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

Schwerdtfeger, P.; Bowmaker, G.A.; Boyd, P.D.W.

1990-02-01

In a recent paper we presented Hartree-Fock (HF) calculations for aliphatic organothallium compounds. The diagonal HF force constants obtained from a Fletcher-Powell geometry optimization are now used for a normal-mode analysis of TlCH{sub 3}, Tl(CH{sub 3}){sub 2}{sup +}, Tl(CH{sub 3}){sub 3}, Tl(CH{sub 3}){sub 2}Br, and Tl(CH{sub 3}){sub 4}{sup {minus}}. In order to calculate frequencies comparable to experimental values, the HF force field has been scaled by using scaling factors obtained from experimental infrared and Raman measurements on Tl(CH{sub 3}){sub 2}{sup +} and TlBr. The vibrational spectra of Tl(CH{sub 3}){sub 2}{sup +} were remeasured (infrared and Raman) in order to obtainmore » an accurate force field. Predictions are made for the vibrational spectrum of the as yet undetected TlCH{sub 3} molecule. Experimental infrared and Raman results for Tl(CH{sub 3}){sub 3} compare reasonably well with our calculated frequencies. Relativistic and correlation effects are analyzed for the vibrational frequencies of Tl(CH{sub 3}){sub 2}{sup +}.« less

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.

Managing Waste Inventory and License Limits at the Perma-Fix Northwest Facility to Meet CH2M Hill Plateau Remediation Company (CHPRC) American Recovery and Reinvestment Act (ARRA) Deliverables - 12335

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

Moak, Don J.; Grondin, Richard L.; Triner, Glen C.

CH2M Hill Plateau Remediation Company (CHRPC) is a prime contractor to the U.S. Department of Energy (DOE) focused on the largest ongoing environmental remediation project in the world at the DOE Hanford Site Central Plateau, i.e. the DOE Hanford Plateau Remediation Contract. The East Tennessee Materials and Energy Corporation (M and EC); a wholly owned subsidiary of Perma-Fix Environmental Services, Inc. (PESI), is a small business team member to CHPRC. Our scope includes project management; operation and maintenance of on-site storage, repackaging, treatment, and disposal facilities; and on-site waste management including waste receipt from generators and delivery to on-site andmore » off-site treatment, storage, and disposal facilities. As part of this scope, M and EC staffs the centralized Waste Support Services organization responsible for all waste characterization and acceptance required to support CHPRC and waste generators across the Hanford Site. At the time of the CHPRC contract award (August 2008) slightly more than 9,000 cubic meters (m{sup 3}) of legacy waste was defined as 'no-path-forward waste'. A significant portion of this waste (7,650 m{sup 3}) comprised wastes with up to 50 grams of special nuclear materials (SNM) in oversized packages recovered during retrieval operations and large glove boxes removed from the Plutonium Finishing Plant (PFP). Through a collaborative effort between the DOE, CHPRC, and Perma-Fix Environmental Services, Inc. (PESI), pathways for these problematic wastes were developed that took advantage of commercial treatment capabilities at a nearby vendor facility, Perma-Fix Northwest (PFNW). In the spring of 2009, CHPRC initiated a pilot program under which they began shipping large package, low gram suspect TRU (<15 g SNM per container), and large package contact and remote handled MLLW to the off-site PFNW facility for treatment. PFNW is restricted by the SNM limits set for the total quantity of SNM allowed at the

Infrared absorption of 2-hydroxyethyl (HOCH2CH2) in solid Ar

NASA Astrophysics Data System (ADS)

Kuo, Yu-Ping; Wann, Gwo-Huei; Lee, Yuan-Pern

1993-09-01

An argon matrix containing C2H4 and H2O2 was irradiated at 12 K with the 248 nm emission of a KrF excimer laser; IR spectra were recorded after various periods of photolysis. In addition to lines ascribed to ethylene oxide, acetaldehyde, and vinyl alcohol, absorptions at 2991.0, 2842.7, 1355.4, 1172.5, and 1040.1 cm-1 have been assigned to HOCH2CH2; weaker lines at 3625.8, 2922.4, and 873.9 cm-1 may also be due to HOCH2CH2. Corresponding lines at 2970.6, 2829.3, 1346.5, 1171.3, and 1020.5 (and probably 3625.8, 2915.1, and 860.7) cm-1 were observed for HO13CH2 13CH2. The results are consistent with ab initio calculations.

Mathematical Modelling of Arctic Polygonal Tundra with Ecosys: 2. Microtopography Determines How CO 2 and CH 4 Exchange Responds to Changes in Temperature and Precipitation

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

Grant, R. F.; Mekonnen, Z. A.; Riley, W. J.

Differences of surface elevation in arctic polygonal landforms cause spatial variation in soil water contents (θ), active layer depths (ALD), and thereby in CO 2 and CH 4 exchange. In this paper, we test hypotheses in ecosys for topographic controls on CO 2 and CH 4 exchange in trough, rim, and center features of low- and flat-centered polygons (LCP and FCP) against chamber and eddy covariance (EC) measurements during 2013 at Barrow, Alaska. Larger CO 2 influxes and CH 4 effluxes were measured with chambers and modeled with ecosys in LCPs than in FCPs and in lower features (troughs) thanmore » in higher (rims) within LCPs and FCPs. Spatially aggregated CO 2 and CH 4 fluxes from ecosys were significantly correlated with EC flux measurements. Lower features were modeled as C sinks (52–56 g C m -2 yr -1) and CH 4 sources (4–6 g C m -2 yr -1), and higher features as near C neutral (-2–15 g C m -2 yr -1) and CH 4 neutral (0.0–0.1 g C m -2 yr -1). Much of the spatial and temporal variations in CO 2 and CH 4 fluxes were modeled from topographic effects on water and snow movement and thereby on θ, ALD, and soil O 2 concentrations. Model results forced with meteorological data from 1981 to 2015 indicated increasing net primary productivity in higher features and CH 4 emissions in some lower and higher features since 2008, attributed mostly to recent rises in precipitation. Finally, small-scale variation in surface elevation causes large spatial variation of greenhouse gas (GHG) exchanges and therefore should be considered in estimates of GHG exchange in polygonal landscapes.« less

Mathematical Modelling of Arctic Polygonal Tundra with Ecosys: 2. Microtopography Determines How CO 2 and CH 4 Exchange Responds to Changes in Temperature and Precipitation

DOE PAGES

Grant, R. F.; Mekonnen, Z. A.; Riley, W. J.; ...

2017-11-17

Differences of surface elevation in arctic polygonal landforms cause spatial variation in soil water contents (θ), active layer depths (ALD), and thereby in CO 2 and CH 4 exchange. In this paper, we test hypotheses in ecosys for topographic controls on CO 2 and CH 4 exchange in trough, rim, and center features of low- and flat-centered polygons (LCP and FCP) against chamber and eddy covariance (EC) measurements during 2013 at Barrow, Alaska. Larger CO 2 influxes and CH 4 effluxes were measured with chambers and modeled with ecosys in LCPs than in FCPs and in lower features (troughs) thanmore » in higher (rims) within LCPs and FCPs. Spatially aggregated CO 2 and CH 4 fluxes from ecosys were significantly correlated with EC flux measurements. Lower features were modeled as C sinks (52–56 g C m -2 yr -1) and CH 4 sources (4–6 g C m -2 yr -1), and higher features as near C neutral (-2–15 g C m -2 yr -1) and CH 4 neutral (0.0–0.1 g C m -2 yr -1). Much of the spatial and temporal variations in CO 2 and CH 4 fluxes were modeled from topographic effects on water and snow movement and thereby on θ, ALD, and soil O 2 concentrations. Model results forced with meteorological data from 1981 to 2015 indicated increasing net primary productivity in higher features and CH 4 emissions in some lower and higher features since 2008, attributed mostly to recent rises in precipitation. Finally, small-scale variation in surface elevation causes large spatial variation of greenhouse gas (GHG) exchanges and therefore should be considered in estimates of GHG exchange in polygonal landscapes.« less

Engineered antibody CH2 domains binding to nucleolin: Isolation, characterization and improvement of aggregation.

PubMed

Li, Dezhi; Gong, Rui; Zheng, Jun; Chen, Xihai; Dimitrov, Dimiter S; Zhao, Qi

2017-04-01

Smaller recombinant antibody fragments are now emerging as alternatives of conventional antibodies. Especially, immunoglobulin (Ig) constant CH2 domain and engineered CH2 with improved stability are promising as scaffolds for selection of specific binders to various antigens. We constructed a yeast display library based on an engineered human IgG1 CH2 scaffold with diversified loop regions. A group of CH2 binders were isolated from this yeast display library by panning against nucleolin, which is a tumor-associated antigen involved in cell proliferation, tumor cell growth and angiogenesis. Out of 20 mutants, we selected 3 clones exhibiting relatively high affinities to nucleolin on yeasts. However, recombinant CH2 mutants aggregated when they were expressed. To find the mechanism of the aggregation, we employed computational prediction approaches through structural homology models of CH2 binders. The analysis of potential aggregation prone regions (APRs) and solvent accessible surface areas (ASAs) indicated two hydrophobic residues, Val 264 and Leu 309 , in the β-sheet, in which replacement of both charged residues led to significant decrease of the protein aggregation. The newly identified CH2 binders could be improved to use as candidate therapeutics or research reagents in the future. Copyright © 2017 Elsevier Inc. All rights reserved.

[(CH3)3NCH2CH2NH3]SnI4: a layered perovskite with quaternary/primary ammonium dications and short interlayer iodine-iodine contacts.

PubMed

Xu, Zhengtao; Mitzi, David B; Medeiros, David R

2003-03-10

The organic-inorganic hybrid [(CH(3))(3)NCH(2)CH(2)NH(3)]SnI(4) presents a layered perovskite structure, templated by an organic dication containing both a primary and a quaternary ammonium group. Due to the high charge density and small size of the organic cation, the separation of the perovskite layers is small and short iodine-iodine contacts of 4.19 A are formed between the layers. Optical thin-film measurements on this compound indicate a significant red shift of the exciton peak (630 nm) associated with the band gap, as compared with other SnI(4)(2)(-)-based layered perovskite structures.

Overview of Phosphate-Based Remediation Technologies At The Hanford Site, Richland Washington

NASA Astrophysics Data System (ADS)

Thompson, K. M.; Fruchter, J. S.

2009-12-01

Laboratory. CH2M Hill Plateau Remediation Company is implementing the technologies in the field, with support from the Laboratory. An overview of the technologies and results to date are presented.

The Band of CH_3CH_2D from 770-880 wn

NASA Astrophysics Data System (ADS)

Daly, Adam M.; Drouin, Brian; Pearson, John; Groner, Peter; Sung, Keeyoon; Brown, Linda; Mantz, Arlan; Smith, Mary Ann H.

2015-06-01

To extend the ethane database we recorded a 0.0028 wn resolution spectrum of CH_3CH_2D from 650 to 1500 wn using a Bruker IFS-125HR at the Jet Propulsion Laboratory. The 98% deuterium-enriched sample was contained in the 0.2038 m absorption cell; one scan was taken with the sample cryogenically cooled to 130 K and another at room temperature. From the cold data, we retrieved line positions and intensities of 8704 individual absorption features from 770 - 880 wn using a least squares curve fitting algorithm. From this set of measurements, we assigned 5041 transitions to the νb{17} fundamental at 805.3427686(234) wn; this band is a c-type vibration, with A and E components arising from internal rotation. The positions were modeled using a 22 term torsional Hamiltonian using SPFIT producing the A and E energy splitting of 5.409(25)x10-3 wn (162.2(8) MHz) with a standard deviation of 7x10-4 wn (21 MHz). The calculated line intensities at 130 K agree very well with retrieved intensities. To predict line intensities at different temperatures, the partition function value was determined at eight temperatures between 9.8 and 300 K by summing individual energy levels up to J = 99 and Ka = 99 for the six states up through νb{17} at 805 wn. The resulting prediction of singly-deuterated ethane absorption at 12.5 μm enables its detection in planetary atmospheres, including those of Titan and exoplanets.

a Theoretical Characterization of Electronic States of CH2IOO and CH2OO Radicals Relevant to the Near IR Region

NASA Astrophysics Data System (ADS)

Dawes, Richard; Lolur, Phalgun; Huang, Meng; Kline, Neal; Miller, Terry A.

2015-06-01

Criegee intermediates (R1R2COO or CIs) arise from ozonolysis of biogenic and anthropogenic alkenes, which is an important process in the atmosphere. Recent breakthroughs in producing them in the gas phase have resulted in a flurry of experimental and theoretical studies. Producing the simplest CI (CH2OO) in the lab via photolysis of CH2I2 in the presence of O2 yields both CH2OO and CH2IOO with pressure dependent branching. As discussed in the preceding talk, both species might be expected to have electronic transitions in the near IR (NIR). Here we discuss electronic structure calculations used to characterize the electronic states of both systems in the relevant energy range. Using explicitly-correlated multireference configuration interaction (MRCI-F12) and coupled-cluster (UCCSD(T)-F12b) calculations we were first able to exclude CH2OO as the carrier of the observed NIR spectrum. Next, by computing frequencies and relaxed full torsional scans for the ~A and ~X states, we were able to aid in analysis and assignment of the NIR spectrum attributed to CH2IOO.

Manganese-catalyzed selective oxidation of aliphatic C-H groups and secondary alcohols to ketones with hydrogen peroxide.

PubMed

Dong, Jia Jia; Unjaroen, Duenpen; Mecozzi, Francesco; Harvey, Emma C; Saisaha, Pattama; Pijper, Dirk; de Boer, Johannes W; Alsters, Paul; Feringa, Ben L; Browne, Wesley R

2013-09-01

An efficient and simple method for selective oxidation of secondary alcohols and oxidation of alkanes to ketones is reported. An in situ prepared catalyst is employed based on manganese(II) salts, pyridine-2-carboxylic acid, and butanedione, which provides good-to-excellent conversions and yields with high turnover numbers (up to 10 000) with H2 O2 as oxidant at ambient temperatures. In substrates bearing multiple alcohol groups, secondary alcohols are converted to ketones selectively and, in general, benzyl C-H oxidation proceeds in preference to aliphatic C-H oxidation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lessons Learned from the 200 West Pump and Treatment Facility Construction Project at the US DOE Hanford Site - A Leadership for Energy and Environmental Design (LEED) Gold-Certified Facility - 13113

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

Dorr, Kent A.; Freeman-Pollard, Jhivaun R.; Ostrom, Michael J.

CH2M Hill Plateau Remediation Company (CHPRC) designed, constructed, commissioned, and began operation of the largest groundwater pump and treatment facility in the U.S. Department of Energy's (DOE) nationwide complex. This one-of-a-kind groundwater pump and treatment facility, located at the Hanford Nuclear Reservation Site (Hanford Site) in Washington State, was built to an accelerated schedule with American Recovery and Reinvestment Act (ARRA) funds. There were many contractual, technical, configuration management, quality, safety, and Leadership in Energy and Environmental Design (LEED) challenges associated with the design, procurement, construction, and commissioning of this $95 million, 52,000 ft groundwater pump and treatment facility tomore » meet DOE's mission objective of treating contaminated groundwater at the Hanford Site with a new facility by June 28, 2012. The project team's successful integration of the project's core values and green energy technology throughout design, procurement, construction, and start-up of this complex, first-of-its-kind Bio Process facility resulted in successful achievement of DOE's mission objective, as well as attainment of LEED GOLD certification (Figure 1), which makes this Bio Process facility the first non-administrative building in the DOE Office of Environmental Management complex to earn such an award. (authors)« less

Automated CO2, CH4 and N2O Fluxes from Tree Stems and Soils: Magnitudes, Temporal Patterns and Drivers

NASA Astrophysics Data System (ADS)

Barba, J.; Poyatos, R.; Vargas, R.

2017-12-01

The emissions of the main greenhouse gases (GHG; CO2, CH4 and N2O) through tree stems are still an uncertain component of the total GHG balance of forests. Despite that stem CO2 emissions have been studied for several decades, it is still unclear the drivers and spatiotemporal patterns of CH4 and N2O stem emissions. Additionally, it is unknown how stem emissions could be related to soil physiological processes or environmental conditions. We measured CO2, CH4 and N2O emissions hourly from April to July 2017 at two different heights (75 [LStem] and 150cm [HStem]) of bitternut hickory (Carya cordiformis) trees and adjacent soil locations in a forested area in the Mid Atlantic of the USA. We designed an automated system to continuously measure the three greenhouse gases (GHG) in stems and soils. Stem and soil CO2 emissions showed similar seasonal patterns with an average of 6.56±0.09 (soil), 3.72±0.05 (LStem) and 2.47±0.04 µmols m-2 s-1 (HStem) (mean±95% CI). Soil temperature controlled CO2 fluxes at both daily and seasonal scales (R2>0.5 for all cases), but there was no clear effect of soil moisture. The stems were a clear CH4 source with emissions decreasing with height (0.35±0.02 and 0.25±0.01 nmols m-2 s-1 for LStem and HStem, respectively) with no apparent seasonal pattern, and no clear relationship with environmental drivers (e.g., temperature, moisture). In contrast, soil was a CH4 sink throughout the experiment (-0.55±0.02 nmols m-2 s-1) and its seasonal pattern responded to moisture changes. Despite soil and stem N2O emissions did not show a seasonal pattern or apparent dependency on temperature or moisture, they showed net N2O emissions with a decrease in emissions with stem height (0.29±0.05 for soil, 0.38±0.06 for LStem and 0.28±0.05 nmols m-2 s-1 for HStem). The three GHG emissions decreased with stem height at similar rates (33%, 28% and 27% for CO2, CH4 and N2O, respectively). These results suggest that the gases were not produced in the stem

In-plane chemical pressure essential for superconductivity in BiCh2-based (Ch: S, Se) layered structure

PubMed Central

Mizuguchi, Yoshikazu; Miura, Akira; Kajitani, Joe; Hiroi, Takafumi; Miura, Osuke; Tadanaga, Kiyoharu; Kumada, Nobuhiro; Magome, Eisuke; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

2015-01-01

BiCh2-based compounds (Ch: S, Se) are a new series of layered superconductors, and the mechanisms for the emergence of superconductivity in these materials have not yet been elucidated. In this study, we investigate the relationship between crystal structure and superconducting properties of the BiCh2-based superconductor family, specifically, optimally doped Ce1−xNdxO0.5F0.5BiS2 and LaO0.5F0.5Bi(S1−ySey)2. We use powder synchrotron X-ray diffraction to determine the crystal structures. We show that the structure parameter essential for the emergence of bulk superconductivity in both systems is the in-plane chemical pressure, rather than Bi-Ch bond lengths or in-plane Ch-Bi-Ch bond angle. Furthermore, we show that the superconducting transition temperature for all REO0.5F0.5BiCh2 superconductors can be determined from the in-plane chemical pressure. PMID:26447333

Annual Hanford Seismic Report for Fiscal Year 2009

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

Rohay, Alan C.; Sweeney, Mark D.; Hartshorn, Donald C.

2009-12-31

The Hanford Seismic Assessment Program (HSAP) provides an uninterrupted collection of high-quality raw and processed seismic data from the Hanford Seismic Network for the U.S. Department of Energy and its contractors. The HSAP is responsible for locating and identifying sources of seismic activity and monitoring changes in the historical pattern of seismic activity at the Hanford Site. The data are compiled, archived, and published for use by the Hanford Site for waste management, natural phenomena hazards assessments, and engineering design and construction. In addition, the HSAP works with the Hanford Site Emergency Services Organization to provide assistance in the eventmore » of a significant earthquake on the Hanford Site. The Hanford Seismic Network and the Eastern Washington Regional Network consist of 44 individual sensor sites and 15 radio relay sites maintained by the Hanford Seismic Assessment Team. During FY 2009, the Hanford Seismic Network recorded nearly 3000 triggers on the seismometer system, which included over 1700 seismic events in the southeast Washington area and an additional 370 regional and teleseismic events. There were 1648 events determined to be local earthquakes relevant to the Hanford Site. Nearly all of these earthquakes were detected in the vicinity of Wooded Island, located about eight miles north of Richland just west of the Columbia River. Recording of the Wooded Island events began in January with over 250 events per month through June 2009. The frequency of events decreased starting in July 2009 to approximately 10-15 events per month through September 2009. Most of the events were considered minor (coda-length magnitude [Mc] less than 1.0) with 47 events in the 2.0-3.0 range. The estimated depths of the Wooded Island events are shallow (averaging less than 1.0 km deep) with a maximum depth estimated at 2.3 km. This places the Wooded Island events within the Columbia River Basalt Group (CRBG). The highest-magnitude event (3

X-ray diffraction analysis of 4- and 4'-substituted C n H2 n + 1O-C6H3(OH)-CH=N-C6H4-C m H2 m + 1 ( n/ m = 2/1 and 3/4) salicylideneanilines

NASA Astrophysics Data System (ADS)

Kuz'mina, L. G.; Navasardyan, M. A.; Mikhailov, A. A.

2017-11-01

X-ray diffraction study of two crystalline modifications of C2H5O-C6H3(OH)-CH=N-C6H4-CH3 ( 1a, sp. gr. P21/ n, and 1b, sp. gr. C2/c) and C3H7O-C6H3(OH)-CH=N-C6H4-C4H9 ( 2, sp. gr. P212121) has been performed. The 1a crystal structure contains two independent molecules. The molecules are conformationally nonrigid with respect to the mutual rotation of benzene rings; the dihedral angles between their planes are 29.19° and 26.00° in the independent molecules of 1a, 18.72° in the molecule of 1b, and 50.35° in the molecule of 2. The crystal packing of the compounds is discussed.

Determination of an Environmental Background Level of Sr-90 in Urine for the Hanford Bioassay Program Determination of an Environmental Background Level of Sr-90 in Urine for the Hanford Bioassay Program

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

Antonio, Cheryl L.; Rivard, James W.

2009-11-01

During the decommissioning and maintenance of some of the facilities at the U.S. Department of Energy Hanford Site in Washington State, workers have potential for a 90Sr intake. However, because of worldwide radioactive fallout, 90Sr is present in our environment, and can be detectable in routine urine bioassay samples. It is important for the Hanford Site bioassay program to discern an occupational intake from a non-occupational environmental one. A detailed study of the background 90Sr in the urine of unexposed Hanford workers was performed. A survey of the Hanford Site bioassay database found 128 Hanford workers who were hired betweenmore » 1997 and 2002 and who had a very low potential for an occupational exposure prior to the baseline strontium urinalysis. Each urinalysis sample represented excretion during an approximate 24-hr period. The arithmetic mean value for the 128 pre-exposure baselines was 3.6 ± 5.1 mBq d-1. The 90Sr activities in urine varied from -12 to 20 mBq. The 99th percentile result was 16.4 mBqd-1, which was interpreted to mean that 1% of Hanford workers not occupationally exposed to strontium might exceed 16.4 mBq d-1.« less

Two-wavelength single laser CH and CH(4) imaging in a lifted turbulent diffusion flame.

PubMed

Namazian, M; Schmitt, R L; Long, M B

1988-09-01

A new technique has been developed which allows simultaneous 2-D mapping of CH and CH 4 in a turbulent methane flame. A flashlamp-pumped dye laser using two back mirrors produces output at 431.5 and 444 nm simultaneously. The 431.5-nm line is used to excite the (0, 0) band of the A(2)Delta-X(2)Pi system of CH, and the fluorescence of the (0, 1) transition is observed at 489 nm. Coincidentally, the spontaneous Raman scattering from CH(4) also occurs near 489 nm for a 431.5-nm excitation. To separate the CH(4) and CH contributions, the 444-nm line is used to produce a spontaneous Raman signal from CH(4) that is spectrally separated from the CH fluorescence. Subtraction of the signals generated by the 431.5- and 444-nm wavelength beams yields separate measurements of CH(4) and CH. Raman-scattered light records the instantaneous distribution of the fuel, and simultaneously the CH fluorescence indicates the location of the flame zone. The resulting composite images provide important insight on the interrelationship between fuel-air mixing and subsequent combustion.M. Namazian is with Altex Technologies Corporation, 109 Via De Tesoros, Los Gatos, California 95030; R. L. Schmitt is with Sandia National Laboratories, Combustion Research Facility, Livermore, California 94550; and M. B. Long is with Yale University, Department of Mechanical Engineering, New Haven, Connecticut 06520.

Unveiling the chemistry of interstellar CH. Spectroscopy of the 2 THz N = 2 ← 1 ground state line

NASA Astrophysics Data System (ADS)

Wiesemeyer, H.; Güsten, R.; Menten, K. M.; Durán, C. A.; Csengeri, T.; Jacob, A. M.; Simon, R.; Stutzki, J.; Wyrowski, F.

2018-04-01

Context. The methylidyne radical CH is commonly used as a proxy for molecular hydrogen in the cold, neutral phase of the interstellar medium. The optical spectroscopy of CH is limited by interstellar extinction, whereas far-infrared observations provide an integral view through the Galaxy. While the HF ground state absorption, another H2 proxy in diffuse gas, frequently suffers from saturation, CH remains transparent both in spiral-arm crossings and high-mass star forming regions, turning this light hydride into a universal surrogate for H2. However, in slow shocks and in regions dissipating turbulence its abundance is expected to be enhanced by an endothermic production path, and the idea of a "canonical" CH abundance needs to be addressed. Aim. The N = 2 ← 1 ground state transition of CH at λ149 μm has become accessible to high-resolution spectroscopy thanks to the German Receiver for Astronomy at Terahertz Frequencies (GREAT) aboard the Stratospheric Observatory for Infrared Astronomy (SOFIA). Its unsaturated absorption and the absence of emission from the star forming regions makes it an ideal candidate for the determination of column densities with a minimum of assumptions. Here we present an analysis of four sightlines towards distant Galactic star forming regions, whose hot cores emit a strong far-infrared dust continuum serving as background signal. Moreover, if combined with the sub-millimeter line of CH at λ560 μm , environments forming massive stars can be analyzed. For this we present a case study on the "proto-Trapezium" cluster W3 IRS5. Methods: While we confirm the global correlation between the column densities of HF and those of CH, both in arm and interarm regions, clear signposts of an over-abundance of CH are observed towards lower densities. However, a significant correlation between the column densities of CH and HF remains. A characterization of the hot cores in the W3 IRS5 proto-cluster and its envelope demonstrates that the sub

78 FR 9902 - DOE Response to Recommendation 2012-2 of the Defense Nuclear Facilities Safety Board, Hanford...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-02-12

... DEPARTMENT OF ENERGY DOE Response to Recommendation 2012-2 of the Defense Nuclear Facilities Safety Board, Hanford Tank Farms Flammable Gas Safety Strategy; Correction AGENCY: Department of Energy... Facilities Safety Board, Hanford Tank Farms Flammable Gas Safety Strategy. This document corrects an error in...

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).

Hanford Site Environmental Report 1999

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

TM Poston; RW Hanf; RL Dirkes

This Hanford Site environmental report is prepared annually to summarize environmental data and information, to describe environmental management performance, to demonstrate the status of compliance with environmental regulations, and to highlight major environmental programs and efforts. The report is written to meet requirements and guidelines of the U.S. Department of Energy (DOE) and to meet the needs of the public. This summary has been written with a minimum of technical terminology. Individual sections of the report are designed to: (1) describe the Hanford Site and its mission; (2) summarize the status of compliance with environmental regulations; (3) describe the environmentalmore » programs at the Hanford Site; (4) discuss the estimated radionuclide exposure to the public from 1999 Hanford Site activities; (5) present the effluent monitoring, environmental surveillance, groundwater protection and monitoring information; and (6) discuss the activities to ensure quality.« less

Greenhouse gas budget (CO2, CH4 and N2O) of intensively managed grassland following restoration.

PubMed

Merbold, Lutz; Eugster, Werner; Stieger, Jacqueline; Zahniser, Mark; Nelson, David; Buchmann, Nina

2014-06-01

The first full greenhouse gas (GHG) flux budget of an intensively managed grassland in Switzerland (Chamau) is presented. The three major trace gases, carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O) were measured with the eddy covariance (EC) technique. For CO2 concentrations, an open-path infrared gas analyzer was used, while N2O and CH4 concentrations were measured with a recently developed continuous-wave quantum cascade laser absorption spectrometer (QCLAS). We investigated the magnitude of these trace gas emissions after grassland restoration, including ploughing, harrowing, sowing, and fertilization with inorganic and organic fertilizers in 2012. Large peaks of N2O fluxes (20-50 nmol m(-2) s(-1) compared with a <5 nmol m(-2) s(-1) background) were observed during thawing of the soil after the winter period and after mineral fertilizer application followed by re-sowing in the beginning of the summer season. Nitrous oxide (N2O) fluxes were controlled by nitrogen input, plant productivity, soil water content and temperature. Management activities led to increased variations of N2O fluxes up to 14 days after the management event as compared with background fluxes measured during periods without management (<5 nmol m(-2) s(-1)). Fluxes of CO2 remained small until full plant development in early summer 2012. In contrast, methane emissions showed only minor variations over time. The annual GHG flux budget was dominated by N2O (48% contribution) and CO2 emissions (44%). CH4 flux contribution to the annual budget was only minor (8%). We conclude that recently developed multi-species QCLAS in an EC system open new opportunities to determine the temporal variation of N2O and CH4 fluxes, which further allow to quantify annual emissions. With respect to grassland restoration, our study emphasizes the key role of N2O and CO2 losses after ploughing, changing a permanent grassland from a carbon sink to a significant carbon source. © 2014 John Wiley & Sons Ltd.

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

Group 6 metal pentacarbonyl complexes of air-stable primary, secondary, and tertiary ferrocenylethylphosphines.

PubMed

Rabiee Kenaree, Amir; Sauvé, Ethan R; Ragogna, Paul J; Gilroy, Joe B

2016-02-21

The synthesis and characterization of a series of Group 6 metal pentacarbonyl complexes of air stable primary, secondary, and tertiary phosphines containing ferrocenylethyl substituents are reported [M(CO)5L: M = Cr, Mo, W; L = PH2(CH2CH2Fc), PH(CH2CH2Fc)2, P(CH2CH2Fc)3]. The structure and composition of the complexes were confirmed by multinuclear NMR spectroscopy, IR and UV-Vis absorption spectroscopy, mass spectrometry, X-ray crystallography, and elemental analysis. The solid-state structural data reported revealed trends in M-C and M-P bond lengths that mirrored those of the atomic radii of the Group 6 metals involved. UV-Vis absorption spectroscopy and cyclic voltammetry highlighted characteristics consistent with electronically isolated ferrocene units including wavelengths of maximum absorption between 435 and 441 nm and reversible one-electron (per ferrocene unit) oxidation waves between 10 and -5 mV relative to the ferrocene/ferrocenium redox couple. IR spectroscopy confirmed that the σ donating ability of the phosphines increased as ferrocenylethyl substituents were introduced and that the tertiary phosphine ligand described is a stronger σ donor than PPh3 and a weaker σ donor than PEt3, respectively.

Electrocatalytic Oxidation of Formate by [Ni(P R 2N R' 2) 2(CH 3CN)] 2+ Complexes

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

Galan, Brandon R.; Schöffel, Julia; Linehan, John C.

2011-08-17

[Ni(P R 2N R' 2) 2(CH 3CN)] 2+ complexes with R = Ph, R' = 4-MeOPh or R = Cy, R' = Ph , and a mixed-ligand [Ni(P R 2N R' 2)(P R" 2N R' 2)(CH 3CN)] 2+ with R = Cy, R' = Ph, R" = Ph, have been synthesized and characterized by single-crystal X-ray crystallography. These and previously reported complexes are shown to be electrocatalysts for the oxidation of formate in solution to produce CO 2, protons, and electrons, with rates that are first-order in catalyst and formate at formate concentrations below ~0.04 M (34 equiv). At concentrationsmore » above ~0.06 M formate (52 equiv), catalytic rates become nearly independent of formate concentration. For the catalysts studied, maximum observed turnover frequencies vary from <1.1 to 15.8 s –1 at room temperature, which are the highest rates yet reported for formate oxidation by homogeneous catalysts. These catalysts are the only base-metal electrocatalysts as well as the only homogeneous electrocatalysts reported to date for the oxidation of formate. An acetate complex demonstrating an η 1-OC(O)CH 3 binding mode to nickel has also been synthesized and characterized by single-crystal X-ray crystallography. Based on this structure and the electrochemical and spectroscopic data, a mechanistic scheme for electrocatalytic formate oxidation is proposed which involves formate binding followed by a rate-limiting proton and two-electron transfer step accompanied by CO 2 liberation. Finally, the pendant amines have been demonstrated to be essential for electrocatalysis, as no activity toward formate oxidation was observed for the similar [Ni(depe) 2] 2+ (depe = 1,2-bis(diethylphosphino)ethane) complex.« less

Electrocatalytic oxidation of formate by [Ni(P(R)2N(R')2)2(CH3CN)]2+ complexes.

PubMed

Galan, Brandon R; Schöffel, Julia; Linehan, John C; Seu, Candace; Appel, Aaron M; Roberts, John A S; Helm, Monte L; Kilgore, Uriah J; Yang, Jenny Y; DuBois, Daniel L; Kubiak, Clifford P

2011-08-17

[Ni(P(R)(2)N(R')(2))(2)(CH(3)CN)](2+) complexes with R = Ph, R' = 4-MeOPh or R = Cy, R' = Ph , and a mixed-ligand [Ni(P(R)(2)N(R')(2))(P(R''(2))N(R'(2)))(CH(3)CN)](2+) with R = Cy, R' = Ph, R'' = Ph, have been synthesized and characterized by single-crystal X-ray crystallography. These and previously reported complexes are shown to be electrocatalysts for the oxidation of formate in solution to produce CO(2), protons, and electrons, with rates that are first-order in catalyst and formate at formate concentrations below ∼0.04 M (34 equiv). At concentrations above ∼0.06 M formate (52 equiv), catalytic rates become nearly independent of formate concentration. For the catalysts studied, maximum observed turnover frequencies vary from <1.1 to 15.8 s(-1) at room temperature, which are the highest rates yet reported for formate oxidation by homogeneous catalysts. These catalysts are the only base-metal electrocatalysts as well as the only homogeneous electrocatalysts reported to date for the oxidation of formate. An acetate complex demonstrating an η(1)-OC(O)CH(3) binding mode to nickel has also been synthesized and characterized by single-crystal X-ray crystallography. Based on this structure and the electrochemical and spectroscopic data, a mechanistic scheme for electrocatalytic formate oxidation is proposed which involves formate binding followed by a rate-limiting proton and two-electron transfer step accompanied by CO(2) liberation. The pendant amines have been demonstrated to be essential for electrocatalysis, as no activity toward formate oxidation was observed for the similar [Ni(depe)(2)](2+) (depe = 1,2-bis(diethylphosphino)ethane) complex.

Greenhouse gas (CO2 and CH4) emissions from a high altitude hydroelectric reservoir in the tropics (Riogrande II, Colombia)

NASA Astrophysics Data System (ADS)

Guérin, Frédéric; Leon, Juan

2015-04-01

Tropical hydroelectric reservoirs are considered as very significant source of methane (CH4) and carbon dioxide (CO2), especially when flooding dense forest. We report emissions from the Rio Grande II Reservoir located at 2000 m.a.s.l. in the Colombian Andes. The dam was built at the confluence of the Rio Grande and Rio Chico in 1990. The reservoir has a surface of 12 km2, a maximum depth of 40m and a residence time of 2.5 month. Water quality (temperature, oxygen, pH, conductivity), nitrate, ammonium, dissolved and particulate organic carbon (DOC and POC), CO2 and CH4 were monitored bi-monthly during 1.5 year at 9 stations in the reservoir. Diffusive fluxes of CO2 and CH4 and CH4 ebullition were measured at 5 stations. The Rio grande II Reservoir is weakly stratified thermally with surface temperature ranging from 20 to 24°C and a constant bottom temperature of 18°C. The reservoir water column is well oxygenated at the surface and usually anoxic below 10m depth. At the stations close to the tributaries water inputs, the water column is well mixed and oxygenated from the surface to the bottom. As reported for other reservoirs located in "clear water" watersheds, the concentrations of nutrients are low (NO3-<0.1ppm, NH4+<0.2ppm), the concentrations of DOC are high (2-8 mg L-1) and POC concentrations are low (< 3 mg L-1). Surface CH4 concentrations at the central stations of the reservoirs are 0.5 μmol L-1 (0.07-2.14 μmol L-1) and 3 times higher at the stations close to the tributaries inputs (up to 7 μmol L-1). In the hypolimnion, CH4 concentration is <100 μmol L-1 in the wet season and can reach up to 400 μmol L-1 in the dry season. The spatial and temporal variability are lower for CO2. Surface CO2 concentration was on average 72 μmol L-1 (up to 300) and hypolimnic concentration ranged between 250 and 1000 μmol L-1. The CO2 diffusive flux is 517±331 mmol m-2 d-1 with little seasonal and spatial variations. At the center of the reservoir, the median

Ion energy distributions and the density of CH3 radicals in a low pressure inductively coupled CH4/H2 plasma used for nanocrystalline diamond deposition

NASA Astrophysics Data System (ADS)

Okada, Katsuyuki; Komatsu, Shojiro; Matsumoto, Seiichiro

2003-11-01

Ion energy distributions (IEDs) and the density of CH3 radicals (n) in a 13.56 MHz radio frequency (rf) low pressure inductively coupled CH4/H2 plasma used for nanocrystalline diamond deposition have been investigated with a quadrupole mass spectrometer. The energy distributions of positive ions were measured in a CH4/H2 plasma with 50 mTorr of the gas pressure at 500 W of the plasma input power, and were compared with those of an Ar plasma. We have found that the IEDs of Ar+, CH4+, and C2H5+ have a nearly monoenergetic peak, and a hump due to a small degree of capacitive coupling. The plasma potentials obtained from the peaks are consistent with the previously reported values measured with a Langmuir probe. On the other hand, the IEDs of H+, H2+, and H3+ have a clear asymmetric double peak due to the modulation of rf driven glow discharge. The n monotonously increases with increasing pressure. The n indicates that CH3 radicals are main precursors for the growth of nanocrystalline diamond. The estimated sticking coefficient of the CH3 radical is comparable with the reported value.

Speciated Monitoring of Gas-Phase Organic Peroxy Radicals by Chemical Ionization Mass Spectrometry: Cross-Reactions between CH3O2, CH3(CO)O2, (CH3)3CO2, and c-C6H11O2.

PubMed

Nozière, Barbara; Hanson, David R

2017-11-09

Organic peroxy radicals ("RO 2 ", with R organic) are key intermediates in most oxygen-rich systems, where organic compounds are oxidized (natural environment, flames, combustion engines, living organisms, etc). But, until recently, techniques able to monitor simultaneously and distinguish between RO 2 species ("speciated" detection) have been scarce, which has limited the understanding of complex systems containing these radicals. Mass spectrometry using proton transfer ionization has been shown previously to detect individual gas-phase RO 2 separately. In this work, we illustrate its ability to speciate and monitor several RO 2 simultaneously by investigating reactions involving CH 3 O 2 , CH 3 C(O)O 2 , c-C 6 H 11 O 2 , and (CH 3 ) 3 CO 2 . The detection sensitivity of each of these radicals was estimated by titration with NO to between 50 and 1000 Hz/ppb, with a factor from 3 to 5 of uncertainties, mostly due to the uncertainties in knowing the amounts of added NO. With this, the RO 2 concentration in the reactor was estimated between 1 × 10 10 and 1 × 10 12 molecules cm -3 . When adding a second radical species to the reactor, the kinetics of the cross-reaction could be studied directly from the decay of the first radical. The time-evolution of two and sometimes three different RO 2 was followed simultaneously, as the CH 3 O 2 produced in further reaction steps was also detected in some systems. The rate coefficients obtained are (in molecule -1 cm 3 s -1 ): k CH3O2+CH3C(O)O2 = 1.2 × 10 -11 , k CH3O2+t-butylO2 = 3.0 × 10 -15 , k c-hexylO2+CH3O2 = 1.2 × 10 -13 , k t-butylO2+CH3C(O)O2 = 3.7 × 10 -14 , and k c-hexylO2+t-butylO2 = 1.5 × 10 -15 . In spite of their good comparison with the literature and good reproducibility, large uncertainties (×5/5) are recommended on these results because of those in the detection sensitivities. This work is a first illustration of the potential applications of this technique for the investigation of organic radicals in

Interannual variability in CO2 and CH4 exchange in a brackish tidal marsh in Northern California

NASA Astrophysics Data System (ADS)

Knox, S. H.; Windham-Myers, L.; Anderson, F. E.; Bergamaschi, B. A.

2017-12-01

Carbon (C) cycling in coastal wetlands is difficult to measure and model due to extremely dynamic atmospheric and hydrologic fluxes, as well as sensitivities to dynamic land- and ocean-based drivers. To date, few studies have begun continuous measurements of net ecosystem CO2 exchange (NEE) in these systems, and as such our understanding of the key drivers of NEE in coastal wetlands remain poorly understood. Recent eddy covariance measurements of NEE in these environments show considerable variability both within and across sites, with daily CO2 uptake and annual net CO2 budgets varying by nearly an order of magnitude between years and across locations. Furthermore, measurements of CH4 fluxes in these systems are even more limited, despite the potential for CH4 emissions from brackish and freshwater coastal wetlands. Here we present 3 years of near-continuous eddy covariance measurements of CO2 and CH4 fluxes from a brackish tidal marsh in Northern California and explore the drivers of interannual variability in CO2 and CH4 exchange. CO2 fluxes showed significant interannual variability; net CO2 uptake was near-zero in 2014 (6 ± 26 g C-CO2 m-2 yr-1), while much greater uptake was observed in 2015 and 2016 (209 ± 27 g C- CO2 m-2 yr-1 and 243 ± 26 g C-CO2 m-2 yr-1, respectively). Conversely, annual CH4 emissions were small and consistent across years, with the wetland emitting on average 1 ± 0.1 g C-CH4 m-2 yr-1. With respect to the net atmospheric GHG budget (assuming a sustained global warming potential (SGWP) of 45, expressed in units of CO2 equivalents), the wetland was near neutral in 2014, but a net GHG sink of 706 ± 105 g CO2 eq m-2 yr-1 and 836 ± 83 g CO2 eq m-2 yr-1 in 2015 and 2016, respectively. The large interannual variability in CO2 exchange was driven by notable year-to-year differences in temperature and precipitation as California experienced a severe drought and record high temperatures from 2012 to 2015. The large interannual variability in

Regional Atmospheric Transport Code for Hanford Emission Tracking (RATCHET). Hanford Environmental Dose Reconstruction Project

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

Ramsdell, J.V. Jr.; Simonen, C.A.; Burk, K.W.

1994-02-01

The purpose of the Hanford Environmental Dose Reconstruction (HEDR) Project is to estimate radiation doses that individuals may have received from operations at the Hanford Site since 1944. This report deals specifically with the atmospheric transport model, Regional Atmospheric Transport Code for Hanford Emission Tracking (RATCHET). RATCHET is a major rework of the MESOILT2 model used in the first phase of the HEDR Project; only the bookkeeping framework escaped major changes. Changes to the code include (1) significant changes in the representation of atmospheric processes and (2) incorporation of Monte Carlo methods for representing uncertainty in input data, model parameters,more » and coefficients. To a large extent, the revisions to the model are based on recommendations of a peer working group that met in March 1991. Technical bases for other portions of the atmospheric transport model are addressed in two other documents. This report has three major sections: a description of the model, a user`s guide, and a programmer`s guide. These sections discuss RATCHET from three different perspectives. The first provides a technical description of the code with emphasis on details such as the representation of the model domain, the data required by the model, and the equations used to make the model calculations. The technical description is followed by a user`s guide to the model with emphasis on running the code. The user`s guide contains information about the model input and output. The third section is a programmer`s guide to the code. It discusses the hardware and software required to run the code. The programmer`s guide also discusses program structure and each of the program elements.« less

Hanford Soil Inventory Model (SIM-v2) Calculated Radionuclide Inventory of Direct Liquid Discharges to Soil in the Hanford Site's 200 Areas.

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

Nichols, William E.; Zaher, U.; Agnew, S.

The Hanford soil inventory model (SIM) provides the basic radionuclide and chemical soil inventories from historical liquid discharges to about 400 sites at the Hanford Site. Although liquid discharge inventory for chemicals is part of the SIM implementation, only radionuclide inventory is discussed here since the focus of this ECF is on providing radionuclides inputs for the composite analysis (CA) per DOE Order 435.1, Radioactive Waste Management, requirements. Furthermore, discharged inventories are only estimated for the soluble portions of the liquid discharges to waste sites/waste management areas located on the 200 Area of the Hanford Site (Central Plateau).

Hanford analytical sample projections FY 1998--FY 2002

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

Joyce, S.M.

1998-02-12

Analytical Services projections are compiled for the Hanford site based on inputs from the major programs for the years 1998 through 2002. Projections are categorized by radiation level, protocol, sample matrix and program. Analyses requirements are also presented. This document summarizes the Hanford sample projections for fiscal years 1998 to 2002. Sample projections are based on inputs submitted to Analytical Services covering Environmental Restoration, Tank Waste Remediation Systems (TWRS), Solid Waste, Liquid Effluents, Spent Nuclear Fuels, Transition Projects, Site Monitoring, Industrial Hygiene, Analytical Services and miscellaneous Hanford support activities. In addition, details on laboratory scale technology (development) work, Sample Management,more » and Data Management activities are included. This information will be used by Hanford Analytical Services (HAS) and the Sample Management Working Group (SMWG) to assure that laboratories and resources are available and effectively utilized to meet these documented needs.« less

Group 1 and group 2 metal complexes supported by a bidentate bulky iminopyrrolyl ligand: synthesis, structural diversity, and ε-caprolactone polymerization study.

PubMed

Kottalanka, Ravi K; Harinath, A; Rej, Supriya; Panda, Tarun K

2015-12-14

We report here a series of alkali and alkaline earth metal complexes, each with a bulky iminopyrrolyl ligand [2-(Ph3CN=CH)C4H3NH] (1-H) moiety in their coordination sphere, synthesized using either alkane elimination or silylamine elimination methods or the salt metathesis route. The lithium salt of molecular composition [Li(2-(Ph3CN=CH)C4H3N)(THF)2] (2) was prepared using the alkane elimination method, and the silylamine elimination method was used to synthesize the dimeric sodium and tetra-nuclear potassium salts of composition [(2-(Ph3CN=CH)C4H3N)Na(THF)]2 (3) and [(2-(Ph3CN=CH)C4H3N)K(THF)0.5]4 (4) respectively. The magnesium complex of composition [(THF)2Mg(CH2Ph){2-(Ph3CN=CH)C4H3N}] (5) was synthesized through the alkane elimination method, in which [Mg(CH2Ph)2(OEt2)2] was treated with the bulky iminopyrrole ligand 1-H in 1 : 1 molar ratio, whereas the bis(iminopyrrolyl)magnesium complex [(THF)2Mg{2-(Ph3CN=CH)C4H3N}2] (6) was isolated using the salt metathesis route. The heavier alkaline earth metal complexes of the general formula {(THF)nM(2-(Ph3CN=CH)C4H3N)2} [M = Ca (7), Sr (8), and n = 2; M = Ba (9), n = 3] were prepared in pure form using two synthetic methods: in the first method, the bulky iminopyrrole ligand 1-H was directly treated with the alkaline earth metal precursor [M{N(SiMe3)2}2(THF)n] (where M = Ca, Sr and Ba) in 2 : 1 molar ratio in THF solvent at ambient temperature. The complexes 7-9 were also obtained using the salt metathesis reaction, which involves the treatment of the potassium salt (4) with the corresponding metal diiodides MI2 (M = Ca, Sr and Ba) in 2 : 1 molar ratio in THF solvent. The molecular structures of all the metal complexes (1-H, 2-9) in the solid state were established through single-crystal X-ray diffraction analysis. The complexes 5-9 were tested as catalysts for the ring-opening polymerization of ε-caprolactone. High activity was observed in the heavier alkaline earth metal complexes 7-9, with a very

Direct observation of unimolecular decay of CH{sub 3}CH{sub 2}CHOO Criegee intermediates to OH radical products

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

Fang, Yi; Liu, Fang; Lester, Marsha I., E-mail: milester@sas.upenn.edu

2016-07-28

The unimolecular decay of carbonyl oxide intermediates, known as Criegee intermediates, produced in alkene ozonolysis is a significant source of OH radicals in the troposphere. Here, the rate of appearance of OH radical products is examined directly in the time-domain for a prototypical alkyl-substituted Criegee intermediate, CH{sub 3}CH{sub 2}CHOO, following vibrational activation under collision-free conditions. Complementary statistical Rice–Ramsperger–Kassel–Marcus calculations of the microcanonical unimolecular decay rate for CH{sub 3}CH{sub 2}CHOO are also carried out at energies in the vicinity of the barrier for 1,4 hydrogen atom transfer that leads to OH products. Tunneling through the barrier, derived from high level electronicmore » structure calculations, contributes significantly to the decay rate. Infrared transitions of CH{sub 3}CH{sub 2}CHOO are identified in the CH stretch overtone region, which are detected by ultraviolet laser-induced fluorescence of the resultant OH products. The features observed are attributed to CH vibrational excitations and conformational forms utilizing insights from theory. Both experiment and theory yield unimolecular decay rates for CH{sub 3}CH{sub 2}CHOO of ca. 10{sup 7} s{sup −1}, which are slower than those obtained for syn-CH{sub 3}CHOO or (CH{sub 3}){sub 2}COO reported previously [Fang et al., J. Chem. Phys. 144, 061102 (2016)] at similar energies. Master equation modeling is also utilized to predict the thermal decay rate of CH{sub 3}CH{sub 2}CHOO under atmospheric conditions, giving a rate of 279 s{sup −1} at 298 K.« less

Second Quarter Hanford Seismic Report for Fiscal Year 2010

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

Rohay, Alan C.; Sweeney, Mark D.; Hartshorn, Donald C.

2010-06-30

The Hanford Seismic Assessment Program (HSAP) provides an uninterrupted collection of high-quality raw and processed seismic data from the Hanford Seismic Network for the U.S. Department of Energy and its contractors. The HSAP is responsible for locating and identifying sources of seismic activity and monitoring changes in the historical pattern of seismic activity at the Hanford Site. The data are compiled, archived, and published for use by the Hanford Site for waste management, natural phenomena hazards assessments, and engineering design and construction. In addition, the HSAP works with the Hanford Site Emergency Services Organization to provide assistance in the eventmore » of a significant earthquake on the Hanford Site. The Hanford Seismic Network and the Eastern Washington Regional Network consist of 44 individual sensor sites and 15 radio relay sites maintained by the Hanford Seismic Assessment Team. The Hanford Seismic Network recorded 90 local earthquakes during the second quarter of FY 2010. Eighty-one of these earthquakes were detected in the vicinity of Wooded Island, located about eight miles north of Richland just west of the Columbia River. The Wooded Island events recorded this quarter were a continuation of the swarm events observed during the 2009 and 2010 fiscal years and reported in previous quarterly and annual reports (Rohay et al; 2009a, 2009b, 2009c, and 2010). Most of the events were considered minor (coda-length magnitude [Mc] less than 1.0) with only 1 event in the 2.0-3.0 range; the maximum magnitude event (3.0 Mc) occurred February 4, 2010 at depth 2.4 km. The average depth of the Wooded Island events during the quarter was 1.6 km with a maximum depth estimated at 3.5 km. This placed the Wooded Island events within the Columbia River Basalt Group (CRBG). The low magnitude of the Wooded Island events has made them undetectable to all but local area residents. The Hanford Strong Motion Accelerometer (SMA) network was triggered

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

(Phosphinoalkyl)silanes. 4.(1) Hydrozirconation as a Non-Photochemical Route to (Phosphinopropyl)silanes: Facile Assembly of the Bis(3-(diphenylphosphino)propyl)silyl ("biPSi") Ligand Framework. Access to the Related Poly(3-(dimethylsilyl)propyl)phosphines R(n)()P(CH(2)CH(2)CH(2)SiMe(2)H)(3)(-)(n)() (n = 1, R = Ph; n = 0).

PubMed

Zhou, Xiaobing; Stobart, Stephen R.; Gossage, Robert A.

1997-08-13

Treatment of SiEt(3)(CH=CH(2)) with ZrCp(2)HCl (Schwartz's reagent) followed by reaction with PPh(2)Cl provides a high-yield (75%) route to Ph(2)PCH(2)CH(2)SiEt(3), and accordingly hydrozirconation of CH(2)=CHCH(2)SiHMe(2) affords the intermediate ZrCp(2)(CH(2)CH(2)CH(2)SiHMe(2))Cl (2). The latter, which is very sensitive to hydrolysis and reacts with HCl forming SiHMe(2)Pr(n)() and with NBS or I(2) affording SiHMe(2)CH(2)CH(2)CH(2)X (X = Br (3), I (4)), behaves similarly with PPh(2)Cl, PPhCl(2), or PBr(3) undergoing cleavage to the known Ph(2)PCH(2)CH(2)CH(2)SiMe(2)H (i.e. chelH, A) and the novel bis- and tris(silylpropyl)phosphines PhP(CH(2)CH(2)CH(2)SiMe(2)H)(2) (5) and P(CH(2)CH(2)CH(2)SiMe(2)H)(3) (6), respectively, with concomitant formation of ZrCp(2)Cl(2). Corresponding hydroboration of allylsilanes is facile, but subsequent phosphine halide cleavage yields (phosphinoalkyl)silanes only as constituents of intractable mixtures. Hydrozirconation followed by phosphination with PPh(2)Cl also converts SiHMe(CH(2)CH=CH(2))(2) to SiHMe(CH(2)CH(2)CH(2)PPh(2))(2) (i.e. biPSiH, B) together with a propyl analogue Ph(2)PCH(2)CH(2)CH(2)SiMe(Pr(n)())H (7) of A (ca. 2:1 ratio), as well as SiH(CH(2)CH=CH(2))(3) to a mixture (ca. 5:2:1 ratio) of SiH(CH(2)CH(2)CH(2)PPh(2))(3) (i.e. triPSiH, C), a new analogue SiH(Pr(n)())(CH(2)CH(2)CH(2)PPh(2))(2) (8) of B, and a further analogue Ph(2)PCH(2)CH(2)CH(2)SiHPr(n)()(2) (9) of A. A further analogue SiH(2)(CH(2)CH(2)CH(2)PPh(2))(2) (10) of biPSiH (B) is obtained similarly starting from SiH(2)(CH(2)CH=CH(2))(2). Steric control of silylalkyl cleavage from 2 is indicated by the fact that, like PPh(2)Cl (which forms B), two further biPSiH analogues SiH(Me)[CH(2)CH(2)CH(2)P(n-hex)(2)](2) (11) and SiH(Me)(CH(2)CH(2)CH(2)PPhBz)(2) (12) were obtained using P(n-hex)(2)Cl (i.e. n-hex = CH(3)(CH(2))(4)CH(2)-) or PPhBzCl (i.e. Bz = -CH(2)C(6)H(5)), respectively, whereas neither PPr(i)(2)Cl nor PBu(t)(2)Cl led to (phosphinoalkyl)silane formation

Antibacterial, antifungal and anticoagulant activities of chicken PLA2 group V expressed in Pichia pastoris.

PubMed

Karray, Aida; Bou Ali, Madiha; Kharrat, Nedia; Gargouri, Youssef; Bezzine, Sofiane

2018-03-01

Secretory class V phospholipase A2 (PLA2-V) has been shown to be involved in inflammatory processes in cellular studies, but the biochemical and physical properties of this important enzyme have been unclear. As a first step towards understanding the structure, function and regulation of this PLA2, we report the expression and characterization of PLA2-V from chicken (ChPLA2-V). The ChPLA2-V cDNA was synthesized from chicken heart polyA mRNA by RT-PCR, and an expression construct containing the PLA2 was established. After expression in Pichia pastoris cells, the active enzyme was purified. The purified ChPLA2-V protein was biochemically and physiologically characterized. The recombinant ChPLA2-V has an absolute requirement for Ca 2+ for enzymatic activity. The optimum pH for this enzyme is pH 8.5 in Tris-HCl buffer with phosphatidylcholine as substrate. ChPLA2-V was found to display potent Gram-positive and Gram-negative bactericidal activity and antifungal activity in vitro. The purified enzyme ChPLA2-V with much stronger anticoagulant activity compared with the intestinal and pancreatic chicken PLA2-V was approximately 10 times more active. Chicken group V PLA2, like mammal one, may be considered as a future therapeutic agents against fungal and bacterial infections and as an anticoagulant agent. Copyright © 2017. Published by Elsevier B.V.

The apparent solubility of aluminum (III) in Hanford high-level waste.

PubMed

Reynolds, Jacob G

2012-01-01

The solubility of aluminum in Hanford nuclear waste impacts on the processability of the waste by a number of proposed treatment options. For many years, Hanford staff has anecdotally noted that aluminum appears to be considerably more soluble in Hanford waste than the simpler electrolyte solutions used as analogues. There has been minimal scientific study to confirm these anecdotal observations, however. The present study determines the apparent solubility product for gibbsite in 50 tank samples. The ratio of hydroxide to aluminum in the liquid phase for the samples is calculated and plotted as a function of total sodium molarity. Total sodium molarity is used as a surrogate for ionic strength, because the relative ratios of mono-, di- and trivalent anions are not available for all of the samples. These results were compared to the simple NaOH-NaAl(OH)(4)-H(2)O system, and the NaOH-NaAl(OH)(4)-NaCl-H(2)O system data retrieved from the literature. The results show that gibbsite is apparently more soluble in the samples than in the simple systems whenever the sodium molarity is greater than 2M. This apparent enhanced solubility cannot be explained solely by differences in ionic strength. The change in solubility with ionic strength in simple systems is small compared to the difference between aluminum solubility in Hanford waste and the simple systems. The reason for the apparent enhanced solubility is unknown, but could include kinetic or thermodynamic factors that are not present in the simple electrolyte systems. Any kinetic explanation would have to explain why the samples are always supersaturated whenever the sodium molarity is above 2M. Real waste characterization data should not be used to validate thermodynamic solubility models until it can be confirmed that the apparent enhanced gibbsite solubility is a thermodynamic effect and not a kinetic effect.

CH/sub 3/xxx/sup 13/CO/sub 2/ pairs in irradiated single crystals of CH/sub 3//sup 13/CO/sub 2/Lix2D/sub 2/0. [Gamma rays

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

Toriyama, K.; Iwasaki, M.

1976-10-01

The CH/sub 3/ radical trapped in irradiated single crystals of CH/sub 3//sup 13/CO/sub 2/Lix2D/sub 2/O has been found to interact with a /sup 13/CO/sub 2/ molecule, which is formed from the C--C bond breakage as a counterpart. The /sup 13/C superhyperfine coupling tensor was determined to be (-4.0, -3.3, -3.5) G. The /sup 13/CO/sub 2/ molecule is located in the direction of the unpaired electron orbital of CH/sub 3/ with the molecular axis perpendicular to it. The spectrum arising from the electron excess center CH/sub 3/ /sup 13/CO/sub 2//sup 2 -/ was also detected together with the CH/sub 3/ radical.more » Our results indicate that the CH/sub 3/xxx/sup 13/CO/sub 2/ pair is essentially a positive hole center formed from one electron loss followed by the C--C bond breakage. (AIP)« less

Satellite Boreal Measurements over Alaska and Canada During June-July 2004: Simultaneous Measurements of Upper Tropospheric CO, C2H6, HCN, CH3Cl, CH4, C2H2, CH2OH, HCOOH, OCS, and SF6 Mixing Ratios

NASA Technical Reports Server (NTRS)

Rinsland, Curtis P.; Dufour, Gaelle; Boone, Chris D.; Bernath, Peter F.; Chiou, Linda; Coheur, Pierre-Francois; Turquety, Solene; Clerbaux, Cathy

2007-01-01

Simultaneous ACE (Atmospheric Chemistry Experiment) upper tropospheric CO, C2H6, HCN, CH3Cl, CH4 , C2H2 , CH30H, HCOOH, and OCS measurements show plumes up to 185 ppbv (10 (exp -9) per unit volume) for CO, 1.36 ppbv for C2H6, 755 pptv (10(exp -12) per unit volume) for HCN, 1.12 ppbv for CH3C1, 1.82 ppmv, (10(exp -6) per unit volume) for CH4, 0.178 ppbv for C2H2, 3.89 ppbv for CH30H, 0.843 ppbv for HCOOH, and 0.48 ppbv for OCS in western Canada and Alaska at 50 deg N-68 deg N latitude between 29 June and 23 July 2004. Enhancement ratios and emission factors for HCOOH, CH30H, HCN, C2H6, and OCS relative to CO at 250-350 hPa are inferred from measurements of young plumes compared with lower mixing ratios assumed to represent background conditions based on a CO emission factor derived from boreal measurements. Results are generally consistent with the limited data reported for various vegetative types and emission phases measured in extratropical forests including boreal forests. The low correlation between fire product emission mixing ratios and the S176 mixing ratio is consistent with no significant SF6 emissions from the biomass fires.

Avian leukosis virus subgroup J induces its receptor--chNHE1 up-regulation.

PubMed

Feng, Weiguo; Meng, Wei; Cai, Liming; Cui, Xiyao; Pan, Zhifang; Wang, Guihua; Cheng, Ziqiang

2016-04-02

Avian leukosis virus subgroup J (ALV-J) is an oncogenic retrovirus which causes immunosuppression and neoplasia in meat-type and egg-type chickens. ALV-J infects host cells via specific interaction between the viral Env and the cell surface receptor -chicken sodium hydrogen exchanger type 1 (chNHE1). NHE1 involved in altering the cellular pH and playing a critical role in tumorigenesis. However, little is known about the other relationship between ALV-J and chNHE1. In ALV-J infected DF-1 cells, the mRNA level of chNHE1 was up-regulated with time-dependent manner tested by real time PCR, and accordingly, intracellular pH was increased tested by spectrofluorometer. In vivo, the mRNA level of chNHE1 was determined by real time PCR in ALV-J infected experimental chickens and field cases. The result showed that the mRNA level of chNHE1 was up-regulated after virus shedding, especially in continuous viremic shedders (CS group). However, no significant difference was found between non-shedding group (NS group) and control group. In field cases, mRNA level of chNHE1 was positively correlated with increasing ALV-J load in tumor bearing and immune tolerance chickens. Furthermore, immunohistochemistry results showed that the protein expression of chNHE1 was up-regulated in different organs of both experimental chickens and tumor bearing chickens compared with the control. Taken together, we conclude that ALV-J induces chNHE1 up-regulation in viremia and neoplasia chickens.

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).

Spectroscopic properties of morin in various CH3OH-H2O and CH3CN-H2O mixed solvents.

PubMed

Park, Hyoung-Ryun; Im, Seo-Eun; Seo, Jung-Ja; Kim, Bong-Gon; Yoon, Jin Ah; Bark, Ki-Min

2015-01-01

The specific fluorescence properties of morin (3,2',4',5,7-pentahydroxyflavone) were studied in various CH3OH-H2O and CH3CN-H2O mixed solvents. Although the dihedral angle is large in the S0 state, morin has an almost planar molecular structure in the S1 state owing to the very low rotational energy barrier around the interring bond between B and the A, C ring. The excited state intramolecular proton transfer (ESIPT) at the S1 state cannot occur immediately after excitation, S1 → S0 fluorescence can be observed. Two conformers, Morin A and B have been known. At the CH3OH-H2O, Morin B will be the principal species but at the CH3CN-H2O, Morin A is the principal species. At the CH3OH-H2O, owing to the large Franck-Condon (FC) factor for S2 → S1 internal convernal (IC) and flexible molecular structure, only S1 → S0 fluorescence was exhibited. At the CH3CN-H2O, as the FC factor for S2 → S1 IC is small and molecular structure is rigid, S2 → S0 and S1 → S0 dual fluorescence was observed. This abnormal fluorescence property was further supported by the small pK1 value, effective delocalization of the lone pair electrons of C(2')-OH to the A, C ring, and a theoretical calculation. © 2014 The American Society of Photobiology.

High-resolution spectroscopy of Saturn at 3 microns: CH 4, CH 3D, C 2H 2, C 2H 6, PH 3, clouds, and haze

NASA Astrophysics Data System (ADS)

Kim, Joo Hyeon; Kim, Sang J.; Geballe, Thomas R.; Kim, Sungsoo S.; Brown, Linda R.

2006-12-01

We report observation and analysis of a high-resolution 2.87-3.54 μm spectrum of the southern temperate region of Saturn obtained with NIRSPEC at Keck II. The spectrum reveals absorption and emission lines of five molecular species as well as spectral features of haze particles. The ν+ν band of CH 3D is detected in absorption between 2.87 and 2.92 μm; and we derived from it a mixing ratio approximately consistent with the Infrared Space Observatory result. The ν band of C 2H 2 also is detected in absorption between 2.95 and 3.05 μm; analysis indicates a sudden drop in the C 2H 2 mixing ratio at 15 mbar (130 km above the 1 bar level), probably due to condensation in the low stratosphere. The presence of the ν+ν+ν band of C 2H 6 near 3.07 μm, first reported by Bjoraker et al. [Bjoraker, G.L., Larson, H.P., Fink, U., 1981. Astrophys. J. 248, 856-862], is confirmed, and a C 2H 6 condensation altitude of 10 mbar (140 km) in the low stratosphere is determined. We assign weak emission lines within the 3.3 μm band of CH 4 to the ν band of C 2H 6, and derive a mixing ratio of 9±4×10 for this species. Most of the C 2H 6 3.3 μm line emission arises in the altitude range 460-620 km (at ˜μbar pressure levels), much higher than the 160-370 km range where the 12 μm thermal molecular line emission of this species arises. At 2.87-2.90 μm the major absorber is tropospheric PH 3. The cloud level determined here and at 3.22-3.54 is 390-460 mbar (˜30 km), somewhat higher than found by Kim and Geballe [Kim, S.J., Geballe, T.R., 2005. Icarus 179, 449-458] from analysis of a low resolution spectrum. A broad absorption feature at 2.96 μm, which might be due to NH 3 ice particles in saturnian clouds, is also present. The effect of a haze layer at about 125 km (˜12 mbar level) on the 3.20-3.54 μm spectrum, which was not apparent in the low resolution spectrum, is clearly evident in the high resolution data, and the spectral properties of the haze particles suggest that

Radical routes to interstellar glycolaldehyde. The possibility of stereoselectivity in gas-phase polymerization reactions involving CH(2)O and ˙CH(2)OH.

PubMed

Wang, Tianfang; Bowie, John H

2010-10-21

A previous report that the interstellar molecule glycolaldehyde (HOCH(2)CHO) can be made from hydroxymethylene (HOCH:) and formaldehyde has been revisited at the CCSD(T)/6-311++G(3df,2p)//MP2/6-311++G(3df,2p) level of theory. This reaction competes with the formation of acetic acid and methylformate, molecules which have also been detected in interstellar clouds. Other possible modes of formation of glycolaldehyde by radical/radical reactions have been shown to be viable theoretically as follows: HO˙+˙CH2CHO -->HOCH2CHO [ΔG(Γ)(298K)=-303kJ mol⁻¹] HOCH2˙+˙CHO-->HOCH2CHO (-259kJ mol⁻¹). The species in these two processes are known interstellar molecules. Key radicals ˙CH(2)CHO and ˙CH(2)OH in these sequences have been shown to be stable for the microsecond duration of neutralization/reionization experiments in the dual collision cells of a VG ZAB 2HF mass spectrometer. The polymerization reaction HOCH(2)CH˙OH + nCH(2)O → HOCH(2)[CH(OH)](n)˙CHOH (n = 1 to 3) has been studied theoretically and shown to be energetically feasible, as is the cyclization reaction of HOCH(2)[(CH(2)OH)(4)]˙CHOH (in the presence of one molecule of water at the reacting centre) to form glucose. The probability of such a reaction sequence is small even if polymerization were to occur in interstellar ice containing a significant concentration of CH(2)O. The large number of stereoisomers produced by such a reaction sequence makes the formation of a particular sugar, again for example glucose, an inefficient synthesis. The possibility of stereoselectivity occurring during the polymerization was investigated for two diastereoisomers of HOCH(2)[(CHOH)](2)˙CHOH. No significant difference was found in the transition state energies for addition of CH(2)O to these two diastereoisomers, but a barrier difference of 12 kJ mol(-1) was found for the H transfer reactions ˙OCH(2)[(CHOH)](2)CH(2)OH → HOCH(2)[(CHOH)(2)˙CHOH of the two diastereoisomers.

Diamidophosphines with six-membered chelates and their coordination chemistry with group 4 metals: development of a trimethylene-methane-tethered [PN2]-type "molecular claw".

PubMed

Batke, S; Kothe, T; Haas, M; Wadepohl, H; Ballmann, J

2016-02-28

The coordination chemistry of the phosphine-tethered diamidophosphine ligands PhP(CH2CH2CH2NHPh)2 (pr[NPN]H2) and PhP(1,2-CH2-C6H4-NHSiMe3)2 (bn[NPN]H2) featuring six-membered N–C3–P chelates was explored with group 4 metals, which allowed for the consecutive development of a new trimethylene-methane-tethered [PN2] scaffold. In the case of the propylene-linked system pr[NPN]H2, access to the sparingly soluble dibenzyl derivative pr[NPN]ZrBn2 (3-Zr) was gained, while thermally sensitive zirconium and hafnium diiodo complexes bn[NPN]MI2 (5-M, M = Zr, Hf) were isolated in the case of the benzylene-linked derivative bn[NPN]H2. Despite the related phosphine-tethered backbone architectures of both of these ligands, their group 4 complexes were found to exhibit either C1-symmetric (bn[NPN]MX2) or averaged CS-symmetric (pr[NPN]MX2) structures in solution. To restrain the overall flexibility of these systems and thereby control the properties of the resulting complexes without disrupting the six-membered chelates, the new trimethylene-methane-tethered N,N′-di-(tert-butyl)-substituted [PN2]H2 protioligand was designed. This tripodal ligand system was prepared on a gram scale and its CS-symmetric dichloro complexes [PN2]MCl2 (6-M, M = Ti, Zr, Hf) were isolated subsequently. The benzene-soluble dibenzyl derivative [PN2]ZrBn2 (7-Zr) was synthesised as well and characterised by X-ray diffraction. These results are discussed not only in conjunction with the known [NPN]-coordinated group 4 complexes incorporating five-membered chelates, but also in the context of “molecular claws” that are related to the new [PN2] tripod.

Determination of an environmental background level of 90Sr in urine for the Hanford bioassay program.

PubMed

Antonio, C L; Rivard, J W

2009-11-01

During the decommissioning and maintenance of some of the facilities at the U.S. Department of Energy Hanford Site in Washington State, workers have potential for a Sr intake. However, because of worldwide radioactive fallout, Sr is present in our environment and can be detectable in routine urine bioassay samples. It is important for the Hanford Site bioassay program to discriminate an occupational intake from a non-occupational environmental one. A detailed study of the background Sr in the urine of unexposed Hanford workers was performed. A survey of the Hanford Site bioassay database found 128 Hanford workers who were hired between 1997 and 2002 and who had a very low potential for an occupational exposure prior to the baseline strontium urinalysis. Each urinalysis sample represented excretion during an approximate 24-h period. The arithmetic mean value for the 128 pre-exposure baselines was 3.6 +/- 5.1 mBq d. The 99 percentile result was 17 mBq d, which was interpreted to mean that 1% of Hanford workers not occupationally exposed to strontium might exceed 17 mBq d.

Cesium migration in saturated silica sand and Hanford sediments as impacted by ionic strength.

PubMed

Flury, Markus; Czigány, Szabolcs; Chen, Gang; Harsh, James B

2004-07-01

Large amounts of 137Cs have been accidentally released to the subsurface from the Hanford nuclear site in the state of Washington, USA. The cesium-containing liquids varied in ionic strengths, and often had high electrolyte contents, mainly in the form of NaNO3 and NaOH, reaching concentrations up to several moles per liter. In this study, we investigated the effect of ionic strengths on Cs migration through two types of porous media: silica sand and Hanford sediments. Cesium sorption and transport was studied in 1, 10, 100, and 1000 mM NaCl electrolyte solutions at pH 10. Sorption isotherms were constructed from batch equilibrium experiments and the batch-derived sorption parameters were compared with column breakthrough curves. Column transport experiments were analyzed with a two-site equilibrium-nonequilibrium model. Cesium sorption to the silica sand in batch experiments showed a linear sorption isotherm for all ionic strengths, which matched well with the results from the column experiments at 100 and 1000 mM ionic strength; however, the column experiments at 1 and 10 mM ionic strength indicated a nonlinear sorption behavior of Cs to the silica sand. Transport through silica sand occurred under one-site sorption and equilibrium conditions. Cesium sorption to Hanford sediments in both batch and column experiments was best described with a nonlinear Freundlich isotherm. The column experiments indicated that Cs transport in Hanford sediments occurred under two-site equilibrium and nonequilibrium sorption. The effect of ionic strength on Cs transport was much more pronounced in Hanford sediments than in silica sands. Effective retardation factors of Cs during transport through Hanford sediments were reduced by a factor of 10 when the ionic strength increased from 100 to 1000 mM; for silica sand, the effective retardation was reduced by a factor of 10 when ionic strength increased from 1 to 1000 mM. A two order of magnitude change in ionic strength was needed in

Unusual reaction paths of SN2 nucleophile substitution reactions CH4 + H- → CH4 + H- and CH4 + F- → CH3F + H-: Quantum chemical calculations

NASA Astrophysics Data System (ADS)

Minyaev, Ruslan M.; Quapp, Wolfgang; Schmidt, Benjamin; Getmanskii, Ilya V.; Koval, Vitaliy V.

2013-11-01

Quantum chemical (CCSD(full)/6-311++G(3df,3pd), CCSD(T)(full)/6-311++G(3df,3pd)) and density function theory (B3LYP/6-311++G(3df,3pd)) calculations were performed for the SN2 nucleophile substitution reactions CH4 + H- → CH4 + H- and CH4 + F- → CH3F + H-. The calculated gradient reaction pathways for both reactions have an unusual behavior. An unusual stationary point of index 2 lies on the gradient reaction path. Using Newton trajectories for the reaction path, we can detect VRI point at which the reaction path branches.

Molecular structure and conformational preferences of 1-bromo-1-silacyclohexane, CH2(CH2CH2)2SiH-Br, as studies by gas-phase electron diffraction and quantum chemistry

NASA Astrophysics Data System (ADS)

Belyakov, A. V.; Baskakov, A. A.; Naraev, V. N.; Rykov, A. N.; Oberhammer, H.; Arnason, I.; Wallevik, S. O.

2012-10-01

The molecular structure of axial and equatorial conformer of the 1-bromo-1-silacyclohexane molecule, CH2(CH2CH2)2SiH-Br, as well as thermodynamic equilibrium between these species are investigated by means of gas-phase electron diffraction and quantum chemistry on the MP2(full)/SDB-AUG-cc-PVTZ level of theory. It is revealed that according to electron diffraction data, the compound exists in the gasphase as a mixture of conformers possessing the chair conformation of the six-membered ring and C s symmetry and differing in the axial and equatorial position of the Si-Br bond (ax. = 80(5) mol %, eq. = 20(7) mol %) at 352 K, that corresponds to the value of A = ( G {ax/○} - G {eq/○}) = -0.82(32) kcal/mol. It is found that observed data agree well with theoretical ones. Using Natural Bond Orbital (NBO) analysis it is revealed that axial conformer of 1-bromo-1-silacyclohexane molecule is an example of the stabilization of the form that is unfavorable from the point of view of steric effects and effects of conjugations. It is concluded that stabilization is achieved due to electrostatic interactions.

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

Poloski, Adam P.; Wells, Beric E.; Tingey, Joel M.

The U.S. Department of Energy (DOE) Office of River Protection’s Waste Treatment and Immobilization Plant (WTP) will process and treat radioactive waste that is stored in tanks at the Hanford Site. Piping, pumps, and mixing vessels have been selected to transport, store, and mix the high-level waste slurries in the WTP. This report addresses the analyses performed by the Rheology Working Group (RWG) and Risk Assessment Working Group composed of Pacific Northwest National Laboratory (PNNL), Bechtel National Inc. (BNI), CH2M HILL, DOE Office of River Protection (ORP) and Yasuo Onishi Consulting, LLC staff on data obtained from documented Hanford wastemore » analyses to determine a best-estimate of the rheology of the Hanford tank wastes and their settling behavior. The actual testing activities were performed and reported separately in referenced documentation. Because of this, many of the required topics below do not apply and are so noted.« less

Endohedral complexes of fullerene-like silica molecules with H2O, CH4, and CH3NH2 molecules

NASA Astrophysics Data System (ADS)

Filonenko, O. V.; Lobanov, V. V.

2013-07-01

The possibility of formation of (SiO2)60@H2O, (SiO2)60@CH4, and (SiO2)60@CH3NH2 endohedral complexes was studied by the density functional (DFT) method (B3LYP exchange correlation functional, 6-31G** basis). The penetration of these molecules into the cavity of fullerene-like silica molecules is hindered by high activation barriers, which ensures the stability of the complexes formed during the synthesis of these molecules.

Process for alkane group dehydrogenation with organometallic catalyst

DOEpatents

Kaska, W.C.; Jensen, C.M.

1998-07-14

An improved process is described for the catalytic dehydrogenation of organic molecules having a ##STR1## group to produce a ##STR2## group. The organic molecules are: ##STR3## wherein: A.sup.1, A.sup.2, A.sup.3, and A.sup.4 are each independently P, As or N: E.sup.2 is independently C or N; E.sup.3 is independently C, Si or Ge; E.sup.4 is independently C, Si, or Ge; and E.sup.5 is independently C, Si or Ge; M.sup.1, M.sup.2, M.sup.3, and M.sup.4 each is a metal atom independently selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum; Q.sup.1, Q.sup.2, Q.sup.3, and Q.sup.4 are each independently a direct bond, --CH.sub.2 --, --CH.sub.2 CH.sub.2 --, or CH.dbd.CH--; in structure I, structure II or structure IV, R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each independently selected from alkyl, alkenyl, cycloalkyl, and aryl, or R.sup.1 and R.sup.2 together and R.sup.3 and R.sup.4 together form a ring structure having from 4 to 10 carbon atoms, or in structure III, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are each independently selected from alkyl, alkenyl, cycloalkyl, and aryl, or R.sup.5 and R.sup.6 together and R.sup.7 and R.sup.8 together form a ring structure having from 4 to 10 carbon atoms, at a temperature of between about 100.degree. and 250.degree. C. for between about 1 hr and 300 days in the absence of N.sub.2. The surprisingly stable catalyst is a complex of an organic ligand comprising H, C, Si, N, P atoms, and a platinum group metal. The dehydrogenation is performed between about 100 to 200.degree. C., and has increased turnover.