Synthesis, characterization, and chiral properties of CoIII2AgI3 pentanuclear, CoIII4ZnII4 octanuclear, and CoIII mononuclear complexes with aza-capped hexadentate-N3S3 thiolate ligands: crystal structures of.

PubMed

Tokuda, K; Okamoto, K; Konno, T

2000-01-24

The reaction of an S-bridged Co2(III)Ag3(I) pentanuclear complex, [Ag3[Co(aet)3]2][BF4]3 (aet = NH2CH2CH2S-), with paraformaldehyde in basic acetonitrile, followed by adding aqueous ammonia, produced an aza-capped Co2(III)-Ag3(I) complex, [Ag3[Co(L)]2]3+ ([1]3+) (L = N(CH2NHCH2CH2S-)3). The crystal structure of [1]3+ was determined by X-ray crystallography. [1][PF6]3 x H2O, empirical formula C18H44Ag3Co2F18N8OP3S6, crystallizes in the tetragonal space group 142m with a = 13.012(1) A, c = 24.707(2) A, and Z = 4. In [1]3+ the two aza-capped [Co(L)] units are linked by three Ag(I) atoms, such that the two Co(III) atoms are encapsulated in a macrobicyclic metallocage, [Ag3(I)(L)2]3-. [1]3+ was converted to an aza-capped Co4(III)Zn4(II) octanuclear complex, [Zn4O[Co(L)]4]6+ ([2]6+), by reaction with I- in the presence of Zn2+ and ZnO in water. The crystal structure of [2]6+ was also determined by X-ray crystallography. [2][PF6]6 x 8H2O, empirical formula C36H100Co4F36N16O9P6S12Zn4, crystallizes in the monoclinic space group P2(1/n) with a = 14.33(7) A, b = 25.67(10) A, c = 24.83(6) A, beta = 101.3(3) degrees , and Z = 4. In [2]6+ each of four [Co(L)] units is bound to each trigonal Zn3(II) face of the tetrahedral [Zn4(II)O]6+ core, such that each Co(III) atom is encapsulated in a macrobicyclic [Zn4(II)O(L)] fragment. Treatment of [2]6+ with a basic aqueous solution resulted in a cleavage of the Zn-S bonds to produce an aza-capped Co(III) mononuclear complex, [Co(L)] ([3]), from which [1]3+ is readily reproduced by the reaction with Ag+ in water. All the reactions were found to proceed with retention of the absolute configuration (delta or lambda) of the Co(III) chiral centers; deltadelta-[1]3+, deltadeltadeltadelta-[2]6+, and A-[3] were derived from deltadelta-[Ag3[Co(aet)3]2]3+. The contributions to circular dichroism (CD) from the triple helicity in [1]3+, besides from the asymmetric N and S donor atoms and the Co(III) chiral centers in [1]3+ and [2]6+, were estimated by comparing the CD spectra of deltadelta-[1]3+, deltadeltadeltadelta-[2]6+, and delta-[3].

Hg-sensitized photolysis of diethylamine in the absence and presence of O/sub 2/ or N/sub 2/O

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

DeStefano, G.; Heicklen, J.

1986-09-11

The Hg-sensitized photolysis of diethylamine (DEA) was studied in the absence and presence of O/sub 2/ or N/sub 2/O at room temperature. In the absence of foreign gases, the products were H/sub 2/, CH/sub 3/CH=NC/sub 2/H/sub 5/ and N,N'-diethylbutane-2,3-diamine (III), with respective quantum yields of 1.0, 1.0, and similarly ordered 0.02. Thus CH/sub 3/CHNHC/sub 2/H/sub 5/ radicals are produced exclusively and they are removed by self reaction: 2CH/sub 3/CHNHC/sub 2/H/sub 5/ ..-->.. DEA + CH/sub 3/CH=NC/sub 2/H/sub 5/ (4a) and 2CH/sub 3/CHNHC/sub 2/H/sub 5/ ..-->.. diamine III (4b), with k/sub 4a//k/sub 4b/ = 47.0 +/- 5.6. In the presence ofmore » O/sub 2/ the radicals are scavenged exclusively by abstraction of the H atom on the nitrogen to give the imine CH/sub 3/CH=NC/sub 2/H/sub 5/ as the exclusive product: (CH/sub 3/CHNHC/sub 2/H/sub 5/ + O/sub 2/ ..-->.. CH/sub 3/CH=NC/sub 2/H/sub 5/ + HO/sub 2/ (5). The Hg-sensitized photolysis of N/sub 2/O gives O(/sup 3/P) atoms, which in the presence of DEA react to give the imine and (C/sub 2/H/sub 5/)/sub 2/NOH (DEHA) as products in concerted parallel steps: O(/sup 3/P) + (C/sub 2/H/sub 5/)/sub 2/NH ..-->.. CH/sub 3/CH=NC/sub 2/H/sub 5/ + H/sub 2/O (9a) and O(/sup 3/P) + (C/sub 2/H/sub 5/)/sub 2/NH ..-->.. (C/sub 2/H/sub 5/)/sub 2/NOH (9b), with k/sub 9a//k/sub 9b/ similarly ordered 9.5 +/- 1.7.« less

Two binuclear cyanide-bridged Cr(III)-Mn(III) complexes based-on [Cr(2,2'-bipy)(CN)4]- building block: synthesis, crystal structures and magnetic properties.

PubMed

Zhanga, Daopeng; Kong, Lingqian; Zhang, Hongyan

2015-01-01

Tetracyanide building block [Cr(2,2'-bipy)(CN)(4)]- and two bicompartimental Schiff-base based manganese(III) compounds have been employed to assemble cyanide-bridged heterometallic complexes, resulting in two cyanide-bridged CrIII-MnIII complexes: [Mn(L(1))(H(2)O)][Cr(2,2'-bipy)(CN)(4)]·CH(3)OH·2.5H(2)O (1) and [Mn(L(2))(H(2)O)][Cr(2,2'-bipy)(CN)(4)]·CH(3)OH·(3)H(2)O (2) (L1 = N,N'-(1,3-propylene)-bis(3-methoxysalicylideneiminate), L2 = N,N'-ethylene-bis(3-ethoxysalicylideneiminate)). Single X-ray diffraction analysis shows their similar cyanide-bridged binuclear structures, in which the cyanide precursor acting as monodentate ligand connects the manganese(III) ion. The binuclear complexes are self-complementary through coordinated aqua ligand and the free O4 compartment from the neighboring complex, giving H-bond linking dimer structure. Investigation over magnetic properties reveals the antiferromagnetic magnetic coupling between the cyanide-bridged Cr(III) and Mn(III) ions. A best-fit to the magnetic susceptibilities of these two complexes leads to the magnetic coupling constants J = -5.95 cm(-1), j = -0.61 cm(-1) (1) and J = -4.15 cm(-1), j = -0.57 cm(-1) (2), respectively.

Synthesis,and structural characterization of [(CH3(C5H4N))Ga(SCH2(CO)O)]-[(4-MepyH)]+, a novel Ga(III) five coordinate complex.

NASA Technical Reports Server (NTRS)

Banger, Kulbinder K.; Duraj, Stan A.; Fanwic, Phillp E.; Hepp, Aloysius F.; Martuch, Robert A.

2003-01-01

The synthesis and structural characterization of a novel ionic Ga(III) five coordinate complex [{CH3(C5H4N)}Ga(SCH2(CO)O)2]-[(4-MepyH)]+, (4-Mepy = CH3(C5H5N)) from the reaction between Ga2Cl4 with sodium mercapto-acetic acid in 4-methylpyridine is described. Under basic reaction conditions the mercapto ligand is found to behave as a 2e- bidentate ligand. Single crystal X-ray diffraction studies show the complex to have a distorted square pyramidal geometry with the [(-SCH2(CO)CO-)] ligands in a trans conformation. The compound crystallizes in the P2(sub 1)/c (No. 14) space group with a = 7.7413(6) A, b = 16.744(2) A, c = 14.459(2) A, V = 1987.1(6) A(sup 3), R(F) = 0.032 and R(sub w) = 0.038.

High-pressure LOX/hydrocarbon preburners and gas generators

NASA Technical Reports Server (NTRS)

Huebner, A. W.

1981-01-01

The objective of the program was to conduct a small scale hardware test program to establish the technology base required for LOX/hydrocarbon preburners and gas generators. The program consisted of six major tasks; Task I reviewed and assessed the performance prediction models and defined a subscale test program. Task II designed and fabricated this subscale hardware. Task III tested and analyzed the data from this hardware. Task IV analyzed the hot fire results and formulated a preliminary design for 40K preburner assemblies. Task V took the preliminary design and detailed and fabricated three 40K size preburner assemblies, one each fuel-rich LOX/CH, and LOX/RP-1 and one oxidizer rich LOX/CH4. Task VI delivered these preburner assemblies to MSFC for subsequent evaluation.

Absorption spectral analysis of 4f-4f transitions for the complexation of Pr(III) and Nd(III) with thiosemicarbazide in absence and presence of Zn(II) in aqueous and organic solvents

NASA Astrophysics Data System (ADS)

Anita, K.; Rajmuhon Singh, N.

2011-10-01

The complexation of thiosemicarbazide with Pr(III) and Nd(III) in absence and presence of Zn(II), a soft metal ion in aqueous and organic solvents like CH 3OH,CH 3CN, dioxane (C 4H 8O 2) and DMF (C 3H 7NO) and their equimolar mixtures are discussed by employing absorption difference and comparative absorption spectrophotometry. Complexation of thiosemicarbazide with Pr(III) and Nd(III) is indicated by the changes in the absorption intensity following the subsequent changes in the oscillator strength of different 4f-4f bands and Judd-Ofelt intensity ( Tλ) parameters. The other spectral parameters like energy interaction parameters namely Slater-Condon ( Fk), Racah ( Ek), Lande ( ξ4f), Nephelauxetic ratio ( β) and bonding parameters ( b1/2) are further computed to explain the nature of complexation. The difference in the energy parameters with respect to donor atoms and solvents reveal that the chemical environment around the lanthanide ions has great impact on f-f transition and any change in the environment result in modification of the spectra. Various solvents and their equimolar mixtures are also used to discuss the participation of solvents in the complexation.

Three series of heterometallic NiII-LnIII Schiff base complexes: synthesis, crystal structures and magnetic characterization.

PubMed

Jiang, Lin; Liu, Yue; Liu, Xin; Tian, Jinlei; Yan, Shiping

2017-09-26

Three series of Ni II -Ln III complexes were synthesized with the general formulae [(μ 3 -CO 3 ) 2 {Ni(HL)(CH 3 -CH 2 OH)Ln(CH 3 COO)} 2 ]·2CH 3 CH 2 OH (1-6) (Ln = Tb (1), Dy (2), Ho (3), Er (4), Tm (5), Yb (6); H 3 L = N,N'-bis(3-methoxysalicylidene)-1,3-diamino-2-prop-anol), [Ni(HL)Ln(dbm) 3 ]·CH 3 OH 2 ·2CH 2 Cl 2 (7-10) (Ln = Tb (7), Eu (8), Gd (9), Ho (10); Hdbm = 1,3-diphenyl-1,3-propanedione) and [Ni(HL)(H 2 O)(tfa)Ln(hfac) 2 ] (11-15) (Ln = Tb (11), Dy (12), Eu (13), Gd (14), Ho (15); Hhfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione, tfa - = trifluoroacetate) using compartmental Schiff base ligands in conjunction with auxiliary ligands. For the NiLn series, the tetranuclear structure could be considered as two Ni II -Ln III dinuclear subunits bridged by two carbonates derived from atmospheric carbon dioxide. The Ln III ions of complexes 1-6 were octa-coordinated with distorted triangular dodecahedral geometry, while the Ln III ions of the dinuclear complexes 7-15 were nona-coordinated with distorted muffin geometry. The magnetic properties of the three series complexes were studied using dc and ac magnetic measurements. For the Ni II -Gd III complexes, the dc magnetic susceptibility measurements suggested the existence of the anticipated ferromagnetic interaction between Ni II and Gd III ions. The fitting of the χ M T vs. T data processed by PHI software provided the parameters g = 2.08 (J = +0.87 cm -1 ) for 9 and g = 2.02 (J = +1.83 cm -1 ) for 14. The interaction exchange was magneto-structurally correlated to the Ni-O-Gd angle (α) and Ni(μ-O)Gd dihedral angle (β). With an applied dc field, complexes 1 (Tb), 2 (Dy), 7 (Tb) and 12 (Dy) exhibited single magnetic relaxation with SMM parameters of U eff /k = 13.60 K, 11.52 K, 7.69 K and 5.14 K, respectively. Analysis of the Cole-Cole plots for complexes 2 and 7 suggested that a single relaxation process was mainly involved in the relaxation process, with α values in the range of 0.37-0.17 and 0.14-0.11, respectively.

Observations on the methane oxidation capacity of landfill soils.

PubMed

Chanton, Jeffrey; Abichou, Tarek; Langford, Claire; Spokas, Kurt; Hater, Gary; Green, Roger; Goldsmith, Doug; Barlaz, Morton A

2011-05-01

The objective of this study was to determine the role of CH(4) loading to a landfill cover in the control of CH(4) oxidation rate (gCH(4)m(-2)d(-1)) and CH(4) oxidation efficiency (% CH(4) oxidation) in a field setting. Specifically, we wanted to assess how much CH(4) a cover soil could handle. To achieve this objective we conducted synoptic measurements of landfill CH(4) emission and CH(4) oxidation in a single season at two Southeastern USA landfills. We hypothesized that percent oxidation would be greatest at sites of low CH(4) emission and would decrease as CH(4) emission rates increased. The trends in the experimental results were then compared to the predictions of two differing numerical models designed to simulate gas transport in landfill covers, one by modeling transport by diffusion only and the second allowing both advection and diffusion. In both field measurements and in modeling, we found that percent oxidation is a decreasing exponential function of the total CH(4) flux rate (CH(4) loading) into the cover. When CH(4) is supplied, a cover's rate of CH(4) uptake (gCH(4)m(-2)d(-2)) is linear to a point, after which the system becomes saturated. Both field data and modeling results indicate that percent oxidation should not be considered as a constant value. Percent oxidation is a changing quantity and is a function of cover type, climatic conditions and CH(4) loading to the bottom of the cover. The data indicate that an effective way to increase the % oxidation of a landfill cover is to limit the amount of CH(4) delivered to it. Copyright © 2010 Elsevier Ltd. All rights reserved.

CO2 and CH4 exchange by Phragmites australis under different climates

NASA Astrophysics Data System (ADS)

Serrano Ortiz, Penélope; Chojnickic, Bogdan H.; Sánchez-Cañete, Enrique P.; Kowalska, Natalia; López-Ballesteros, Ana; Fernández, Néstor; Urbaniak, Marek; Olejnik, Janusz; Kowalski, Andrew S.

2015-04-01

The key role of wetlands regarding global warming is the resulting balance between net CO2 assimilation, via photosynthesis, and CO2 and CH4 emissions, given the potential to release stored carbon, because of the high temperature sensitivity of heterotrophic soil respiration and anoxic conditions. However, it is still unknown whether wetlands will convert from long-term carbon sinks to sources as a result of climate change and other anthropogenic effects such as land use changes. Phragmites australis is one of the most common species found in wetlands and is considered the most globally widespread and productive plant species in this type of ecosystem. In this context, the main objective of this study is to analyse the GHG exchange (CO2 and CH4) of two wetlands with Phragmites australis as the dominant species under different climates using the eddy covariance (EC) technique. The first site, Padul, is located in southern Spain, with a sub-humid warm climate, characterised by a mean annual temperature of 16°C and annual precipitation of ca. 470 mm, with a very dry summer. The second site, Rzecin is located in Poland with a mean annual temperature of 8°C, and annual precipitation around 600mm with no dry season. The Padul EC station is equipped with two infrared gas analysers to measure CO2 and CH4 fluxes (LI-7200 and LI-7700 respectively) while the Rzecin EC station has the same CH4 sensor as Padul, but also a sensor measuring both GHG fluxes (DLT-100 Fast Methane Analyser, Los Gatos). In this study, we present: i) the results of a CH4 analyser inter-comparison campaign (LI-7700 vs. Los Gatos), ii) a comparative analysis of the functional behaviour of respiration and photosynthesis in both sites testing relationships between CO2 fluxes measured with the EC technique and meteorological variables such as temperature and direct or diffuse radiation and iii) the CH4 dynamicsat both sites by identifying, when possible, annual, seasonal and diurnal patterns.

Isolation and Characterization of a Dihydroxo-Bridged Iron(III,III)(μ-OH)2 Diamond Core Derived from Dioxygen

PubMed Central

Coggins, Michael K.; Toledo, Santiago; Kovacs, Julie A.

2013-01-01

Dioxygen addition to coordinatively unsaturated [Fe(II)(OMe2N4(6-Me-DPEN))](PF6) (1) is shown to afford a complex containing a dihydroxo-bridged Fe(III)2(μ-OH)2 diamond core, [FeIII(OMe2N4(6-Me-DPEN))]2(μ-OH)2(PF6)2•(CH3CH2CN)2 (2). The diamond core of 2 resembles the oxidized methane monooxygenase (MMOox) resting state, as well as the active site product formed following H-atom abstraction from Tyr-OH by ribonucleotide reductase (RNR). The Fe-OH bond lengths of 2 are comparable with those of the MMOHox suggesting that MMOHox contains a Fe(III)2(μ-OH)2 as opposed to Fe(III)2(μ-OH)(μ-OH2) diamond core as had been suggested. Isotopic labeling experiments with 18O2 and CD3CN indicate that the oxygen and proton of the μ-OH bridges of 2 are derived from dioxygen and acetonitrile. Deuterium incorporation (from CD3CN) suggests that an unobserved intermediate capable of abstracting a H-atom from CH3CN forms en route to 2. Given the high C–H bond dissociation energy (BDE= 97 kcal/mol) of acetonitrile, this indicates that this intermediate is a potent oxidant, possibly a high-valent iron oxo. Consistent with this, iodosylbenzene (PhIO) also reacts with 1 in CD3CN to afford the deuterated Fe(III)2(μ-OD)2 derivative of 2. Intermediates are not spectroscopically observed in either reaction (O2 and PhIO) even at low-temperatures (−80 °C), indicating that this intermediate has a very short life-time, likely due to its highly reactive nature. Hydroxo-bridged 2 was found to stoichiometrically abstract hydrogen atoms from 9,10-dihydroanthracene (C-H BDE= 76 kcal/mol) at ambient temperatures. PMID:24229319

Transition-Metal Derivatives of a Functionalized Cyclopentadienyl Ligand. 15. Synthesis and Structures of Amino Cyclopentadienyl Derivatives of Rhodium(I) and Rhodium(III) Including Water-Soluble Compounds.

PubMed

Philippopoulos, Athanassios I.; Hadjiliadis, Nick; Hart, Claire E.; Donnadieu, Bruno; Mc Gowan, Patrick C.; Poilblanc, René

1997-04-23

The synthesis of monometallic rhodium(III) and rhodium(I) derivatives of dialkylamino-functionalized cyclopentadienyl using the corresponding cyclopentadiene as starting material is facilitated by the presence of the basic amino group. This procedure affords the chloro salts of the substituted rhodicinium cation [(eta(5)-C(5)H(4)(CH(2))(2)NMe(2)H)(2)Rh(III)](3+) ([1][Cl](3)) from the reaction of the [2-(dimethylamino)ethyl]cyclopentadiene with Na(3)Rh(III)Cl(6). 12H(2)O. Similarly the cationic half-sandwich complexes [(eta(5)-C(5)H(4)(CH(2))(n)()NMe(2)H)Rh(I)(cod)](+) (n = 2, [2][Cl], n = 3, [5][Cl]) are obtained from the reaction of the corresponding dialkylamino cyclopentadiene with [RhCl(cod)](2). These types of cationic complexes, 1, 2, and 5, bear pendant ammonium groups. The most classical procedure, starting from the lithium or more efficiently from the sodium cyclopentadienide salt, was used to synthesize neutral complexes [(eta(5)-C(5)H(4)(CH(2))(n)()NMe(2))Rh(I)(cod)] (n = 2, 3; n = 3, 4). The structure of the chloride bis(hexafluorophosphate) salt, [(eta(5)-C(5)H(4)(CH(2))(2)NMe(2)H)(2)Rh(III)](3+)(Cl(-))(PF(6)(-))(2), ([1][Cl][PF(6)](2)) was solved in the triclinic space group P&onemacr; with one molecule in the unit cell, the dimensions of which are a = 6.617(2) Å, b= 7.436(2) Å, c = 13.965(3) Å, alpha = 76.39(2) degrees, beta = 82.31(3) degrees, gamma = 87.26(2) degrees, and V = 661.8(3) Å(3). The noncentrosymmetric character of this solid is attributed to the chloride ion. The tetrafluoroborate salt [(eta(5)-C(5)H(4)(CH(2))(2)NMe(2)H)Rh(I)(cod)](+)(BF(4)(-)) ([2][BF(4)]) crystallizes in the tetragonal space group P4(2)/n with eight molecules in the unit cell, the dimensions of which are a= 21.183(2) Å, b = 21.179(3) Å, c= 8.324(2) Å, and V = 3734(1) Å(3). Least squares refinement leads to values for the conventional R index of [1][Cl][PF(6)](2) (0.0484 for 2191 reflections used) and of [2][BF(4)] (0.0525 for 1083 reflections used); in both cases I > 3sigma(I). As expected, compounds like [2][Cl](3,) [1][Cl][PF(6)](2), [2][Cl], [2][BF(4)], [5][Cl], and [5][BF(4)] are soluble in water.

Mitochondria As Sources and Targets of Methane.

PubMed

Mészáros, András Tamás; Szilágyi, Ágnes Lilla; Juhász, László; Tuboly, Eszter; Érces, Dániel; Varga, Gabriella; Hartmann, Petra

2017-01-01

This review summarizes the current knowledge on the role of mitochondria in the context of hypoxic cell biology, while providing evidence of how these mechanisms are modulated by methane (CH 4 ). Recent studies have unambiguously confirmed CH 4 bioactivity in various in vitro and in vivo experimental models and established the possibility that CH 4 can affect many aspects of mitochondrial physiology. To date, no specific binding of CH 4 to any enzymes or receptors have been reported, and it is probable that many of its effects are related to physico-chemical properties of the non-polar molecule. (i) Mitochondria themselves can be sources of endogenous CH 4 generation under oxido-reductive stress conditions; chemical inhibition of the mitochondrial electron transport chain with site-specific inhibitors leads to increased formation of CH 4 in eukaryote cells, in plants, and in animals. (ii) Conventionally believed as physiologically inert, studies cited in this review demonstrate that exogenous CH 4 modulates key events of inflammation. The anti-apoptotic effects of exogenously administered CH 4 are also recognized, and these properties also suggest that CH 4 -mediated intracellular signaling is closely associated with mitochondria. (iii) Mitochondrial substrate oxidation is coupled with the reduction of molecular oxygen, thus providing energy for cellular metabolism. Interestingly, recent in vivo studies have shown improved basal respiration and modulated mitochondrial oxidative phosphorylation by exogenous CH 4 . Overall, these data suggest that CH 4 liberation and effectiveness in eukaryotes are both linked to hypoxic events and redox regulation and support the notion that CH 4 has therapeutic roles in mammalian pathophysiologies.

Mitochondria As Sources and Targets of Methane

PubMed Central

Mészáros, András Tamás; Szilágyi, Ágnes Lilla; Juhász, László; Tuboly, Eszter; Érces, Dániel; Varga, Gabriella; Hartmann, Petra

2017-01-01

This review summarizes the current knowledge on the role of mitochondria in the context of hypoxic cell biology, while providing evidence of how these mechanisms are modulated by methane (CH4). Recent studies have unambiguously confirmed CH4 bioactivity in various in vitro and in vivo experimental models and established the possibility that CH4 can affect many aspects of mitochondrial physiology. To date, no specific binding of CH4 to any enzymes or receptors have been reported, and it is probable that many of its effects are related to physico-chemical properties of the non-polar molecule. (i) Mitochondria themselves can be sources of endogenous CH4 generation under oxido-reductive stress conditions; chemical inhibition of the mitochondrial electron transport chain with site-specific inhibitors leads to increased formation of CH4 in eukaryote cells, in plants, and in animals. (ii) Conventionally believed as physiologically inert, studies cited in this review demonstrate that exogenous CH4 modulates key events of inflammation. The anti-apoptotic effects of exogenously administered CH4 are also recognized, and these properties also suggest that CH4-mediated intracellular signaling is closely associated with mitochondria. (iii) Mitochondrial substrate oxidation is coupled with the reduction of molecular oxygen, thus providing energy for cellular metabolism. Interestingly, recent in vivo studies have shown improved basal respiration and modulated mitochondrial oxidative phosphorylation by exogenous CH4. Overall, these data suggest that CH4 liberation and effectiveness in eukaryotes are both linked to hypoxic events and redox regulation and support the notion that CH4 has therapeutic roles in mammalian pathophysiologies. PMID:29181377

Comparative 4f-4f absorption spectral study for the interactions of Nd(III) with some amino acids: Preliminary thermodynamics and kinetic studies of interaction of Nd(III):glycine with Ca(II)

NASA Astrophysics Data System (ADS)

Moaienla, T.; Bendangsenla, N.; David Singh, Th.; Sumitra, Ch.; Rajmuhon Singh, N.; Indira Devi, M.

2012-02-01

Spectral analysis of Nd(III) complexes with some amino acids viz.; glycine, L-alanine, L-phenylalanine and L-aspartic acid in the presence and absence of Ca 2+ was carried out in some organic solvents; CH 3OH, CH 3CN, DMF and dioxane using comparative absorption spectra of 4f-4f transitions. The study was carried out by evaluating various energy interaction parameters like Slator-Condon ( Fk), Lande factor ( ξ4f), nephelauxetic ratio ( β), bonding parameter ( b1/2), percent-covalency ( δ) by applying partial and multiple regression analysis. The values of oscillator strength ( Pobs) and Judd-Ofelt electric dipole intensity parameter Tλ ( λ = 2, 4, 6) for different 4f-4f transitions have been calculated. On analysis of the variation of the various energy interaction parameters as well as the changes in the oscillator strength ( Pobs) and Tλ values, reveal the mode of binding with the different ligands. Kinetic studies for the complexation of Nd(III):glycine:Ca(II) have also been discussed at different temperatures in DMF medium and from it the values of activation energy ( Ea) and thermodynamic parameters like Δ H°, Δ S° and Δ G° for the complexation are evaluated.

Effects of rare earth element lanthanum on rumen methane and volatile fatty acid production and microbial flora in vitro.

PubMed

Zhang, T T; Zhao, G Y; Zheng, W S; Niu, W J; Wei, C; Lin, S X

2015-06-01

The objectives of the trial were to study the effects of rare earth element (REE) lanthanum (La) on the in vitro rumen methane (CH4 ) and volatile fatty acid (VFA) production and the microbial flora of feeds. Four feed mixtures with different levels of neutral detergent fibre (NDF), that is 20.0% (I), 31.0% (II), 41.9% (III) and 52.7% (IV), were formulated as substrates. Five levels of LaCl3 , that is 0, 0.4, 0.6, 0.8 and 1.0 mmol/kg dry matter (DM), were added to the feed mixtures, respectively, as experimental treatments in a two-factor 5 × 4 randomized design. The in vitro incubation lasted for 24 h. The results showed that supplementing LaCl3 increased the total gas (p < 0.001) production and tended to increase the total VFA production (p = 0.072) and decreased the CH4 production (p = 0.001) and the ratios of acetate/propionate (p = 0.019) and CH4 /total VFA (p < 0.001). Interactions between LaCl3 and NDF were significant in total gas production (p = 0.030) and tended to be significant in CH4 production (p = 0.071). Supplementing LaCl3 at the level of 0.8 mmol/g DM decreased the relative abundance of methanogens and protozoa in the total bacterial 16S rDNA analysed using the real-time PCR (p < 0.0001), increased F. succinogenes (p = 0.0003) and decreased R. flavefaciens (p < 0.0001) whereas did not affect R. albus and anaerobic fungi (p > 0.05). It was concluded that LaCl3 decreased the CH4 production without negatively affecting feed digestion through manipulating rumen microbial flora when feed mixtures with different levels of NDF were used as substrates. Journal of Animal Physiology and Animal Nutrition © 2014 Blackwell Verlag GmbH.

Single-molecule magnet behavior in an octanuclear dysprosium(iii) aggregate inherited from helical triangular Dy3 SMM-building blocks.

PubMed

Zhang, Li; Zhang, Peng; Zhao, Lang; Wu, Jianfeng; Guo, Mei; Tang, Jinkui

2016-06-28

An unprecedented octanuclear dysprosium(iii) cluster with the formula [Dy8L6(μ3-OH)4(μ2-CH3O)2(CH3OH)6(H2O)2]·6H2O·10CH3OH·2CH3CN () based on a nonlinearly tritopic aroylhydrazone ligand H3L has been isolated, realizing the successful linking of pairwise interesting triangular Dy3 SMMs. It is noteworthy that two enantiomers (Λ and Δ configurations) individually behaving as a coordination-induced chirality presented in the Dy3 helicate are connected in the meso Dy8 cluster. Remarkably, alternating-current magnetic susceptibility measurements revealed that the Dy8 cluster shows typical SMM behavior inherited from its Dy3 helical precursor. It is one of the rare polynuclear Lnn SMMs (n > 7) under zero dc field.

Demonstrating Hund's Rule in Action by Exploring the Magnetic Properties of Metal Complexes with 3D[superscript n] and 4F[superscript n] Configurations

ERIC Educational Resources Information Center

Natoli, Sean N.; McMillin, David R.

2018-01-01

Students collect magnetic susceptibility data to verify that Hund's rule correctly predicts electronic configurations. Systems examined include three commercially available lanthanide(III)-containing complexes of the form M(acac)[subscript 3](H[subscript 2]O)[subscript 2] (where M = La(III), Nd(III), and Gd(III), and acac denotes the [CH[subscript…

Rhombus-shaped tetranuclear [Ln4] complexes [Ln = Dy(III) and Ho(III)]: synthesis, structure, and SMM behavior.

PubMed

Chandrasekhar, Vadapalli; Hossain, Sakiat; Das, Sourav; Biswas, Sourav; Sutter, Jean-Pascal

2013-06-03

The reaction of a new hexadentate Schiff base hydrazide ligand (LH3) with rare earth(III) chloride salts in the presence of triethylamine as the base afforded two planar tetranuclear neutral complexes: [{(LH)2Dy4}(μ2-O)4](H2O)8·2CH3OH·8H2O (1) and [{(LH)2Ho4}(μ2-O)4](H2O)8·6CH3OH·4H2O (2). These neutral complexes possess a structure in which all of the lanthanide ions and the donor atoms of the ligand remain in a perfect plane. Each doubly deprotonated ligand holds two Ln(III) ions in its two distinct chelating coordination pockets to form [LH(Ln)2](4+) units. Two such units are connected by four [μ2-O](2-) ligands to form a planar tetranuclear assembly with an Ln(III)4 core that possesses a rhombus-shaped structure. Detailed static and dynamic magnetic analysis of 1 and 2 revealed single-molecule magnet (SMM) behavior for complex 1. A peculiar feature of the χM" versus temperature curve is that two peaks that are frequency-dependent are revealed, indicating the occurrence of two relaxation processes that lead to two energy barriers (16.8 and 54.2 K) and time constants (τ0 = 1.4 × 10(-6) s, τ0 = 7.2 × 10(-7) s). This was related to the presence of two distinct geometrical sites for Dy(III) in complex 1.

Reduction of RuVI≡N to RuIII-NH3 by Cysteine in Aqueous Solution.

PubMed

Wang, Qian; Man, Wai-Lun; Lam, William W Y; Yiu, Shek-Man; Tse, Man-Kit; Lau, Tai-Chu

2018-05-21

The reduction of metal nitride to ammonia is a key step in biological and chemical nitrogen fixation. We report herein the facile reduction of a ruthenium(VI) nitrido complex [(L)Ru VI (N)(OH 2 )] + (1, L = N, N'-bis(salicylidene)- o-cyclohexyldiamine dianion) to [(L)Ru III (NH 3 )(OH 2 )] + by l-cysteine (Cys), an ubiquitous biological reductant, in aqueous solution. At pH 1.0-5.3, the reaction has the following stoichiometry: [(L)Ru VI (N)(OH 2 )] + + 3HSCH 2 CH(NH 3 )CO 2 → [(L)Ru III (NH 3 )(OH 2 )] + + 1.5(SCH 2 CH(NH 3 )CO 2 ) 2 . Kinetic studies show that at pH 1 the reaction consists of two phases, while at pH 5 there are three distinct phases. For all phases the rate law is rate = k 2 [1][Cys]. Studies on the effects of acidity indicate that both HSCH 2 CH(NH 3 + )CO 2 - and - SCH 2 CH(NH 3 + )CO 2 - are kinetically active species. At pH 1, the reaction is proposed to go through [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (2a), [(L)Ru III (NH 2 SCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (3), and [(L)Ru IV (NH 2 )(OH 2 )] + (4) intermediates. On the other hand, at pH around 5, the proposed intermediates are [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 )(OH 2 )] + (2b) and [(L)Ru IV (NH 2 )(OH 2 )] + (4). The intermediate ruthenium(IV) sulfilamido species, [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (2a) and the final ruthenium(III) ammine species, [(L)Ru III (NH 3 )(MeOH)] + (5) (where H 2 O was replaced by MeOH) have been isolated and characterized by various spectroscopic methods.

Computational Study of Pincer Iridium Catalytic Systems: C-H, N-H, and C-C Bond Activation and C-C Coupling Reactions

NASA Astrophysics Data System (ADS)

Zhou, Tian

Computational chemistry has achieved vast progress in the last decades in the field, which was considered to be only experimental before. DFT (density functional theory) calculations have been proven to be able to be applied to large systems, while maintaining high accuracy. One of the most important achievements of DFT calculations is in exploring the mechanism of bond activation reactions catalyzed by organometallic complexes. In this dissertation, we discuss DFT studies of several catalytic systems explored in the lab of Professor Alan S. Goldman. Headlines in the work are: (1) (R4PCP)Ir alkane dehydrogenation catalysts are highly selective and different from ( R4POCOP)Ir catalysts, predicting different rate-/selectivity-determining steps; (2) The study of the mechanism for double C-H addition/cyclometalation of phenanthrene or biphenyl by (tBu4PCP)Ir(I) and ( iPr4PCP)Ir illustrates that neutral Ir(III) C-H addition products can undergo a very facile second C-H addition, particularly in the case of sterically less-crowded Ir(I) complexes; (3) (iPr4PCP)Ir pure solid phase catalyst is highly effective in producing high yields of alpha-olefin products, since the activation enthalpy for dehydrogenation is higher than that for isomerization via an allyl pathway; higher temperatures favor the dehydrogenation/isomerization ratio; (4) (PCP)Ir(H)2(N2H4) complex follows a hydrogen transfer mechanism to undergo both dehydrogenation to form N 2 and H2, as well as hydrogen transfer followed by N-N bond cleavage to form NH3, N2, and H2; (5) The key for the catalytic effect of solvent molecule in CO insertion reaction for RMn(CO)5 is hydrogen bond assisted interaction. The basicity of the solvent determines the strength of the hydrogen bond interaction during the catalytic path and determines the catalytic power of the solvent; and (6) Dehydrogenative coupling of unactivated C-H bonds (intermolecular vinyl-vinyl, intramolecular vinyl-benzyl) is catalyzed by precursors of the (iPr4 PCP)Ir fragment. The key step for this mechanism is a Ir(III) vinyl hydride complex undergoing addition of a styrenyl ortho C-H bond to give an Ir(III) metalloindene plus H2.

Acetogenic microbial degradation of vinyl chloride

USGS Publications Warehouse

Bradley, P.M.; Chapelle, F.H.

2000-01-01

Under methanogenic conditions, microbial degradation of [1,2-14C]vinyl chloride (VC) resulted in significant (14 ?? 3% maximum recovery) but transient recovery of radioactivity as 14C-acetate. Subsequently, 14C- acetate was degraded to 14CH4 and 14CO2 (18 ?? 2% and 54 ?? 3% final recoveries, respectively). In contrast, under 2-bromoethanesulfonic acid (BES) amended conditions, 14C-acetate recovery remained high (27 ?? 1% maximum recovery) throughout the study, no 14CH4 was produced, and the final recovery of 14CO2 was only 35 ?? 4%. These results demonstrate that oxidative acetogenesis may be an important mechanism for anaerobic VC biodegradation. Moreover, these results (1) demonstrate that microbial degradation of VC to CH4 and CO2 may involve oxidative acetogenesis followed by acetotrophic methanogenesis and (2) suggest that oxidative acetogenesis may be the initial step in the net oxidation of VC to CO2 reported previously under Fe(III)-reducing, SO4-reducing, and humic acids- reducing conditions.Under methanogenic conditions, microbial degradation of [1,2-14C]vinyl chloride (VC) resulted in significant (14 ?? 3% maximum recovery) but transient recovery of radioactivity as 14C-acetate. Subsequently, 14C-acetate was degraded to 14CH4 and 14CO2 (18 ?? 2% and 54 ?? 3% final recoveries respectively). In contrast, under 2-bromoethanesulfonic acid (BES) amended conditions, 14C-acetate recovery remained high (27 ?? 1% maximum recovery) throughout the study, no 14CH4 was produced, and the final recovery of 14CO2 was only 35 ?? 4%. These results demonstrate that oxidative acetogenesis may be an important mechanism for anaerobic VC biodegradation. Moreover, these results (1) demonstrate that microbial degradation of VC to CH4 and CO2 may involve oxidative acetogenesis followed by acetotrophic methanogenesis and (2) suggest that oxidative acetogenesis may be the initial step in the net oxidation of VC to CO2 reported previously under Fe(III)-reducing, SO4-reducing, and humic acids-reducing conditions.

Lanthanide Complexes with Multidentate Oxime Ligands as Single-Molecule Magnets and Atmospheric Carbon Dioxide Fixation Systems.

PubMed

Hołyńska, Małgorzata; Clérac, Rodolphe; Rouzières, Mathieu

2015-09-14

The synthesis, structure, and magnetic properties of five lanthanide complexes with multidentate oxime ligands are described. Complexes 1 and 2 (1: [La2 (pop)2 (acac)4 (CH3 OH)], 2: [Dy2 (pop)(acac)5 ]) are synthesized from the 2-hydroxyimino-N-[1-(2-pyridyl)ethylidene]propanohydrazone (Hpop) ligand, while 3, 4, and 5 (3: [Dy2 (naphthsaoH)2 (acac)4 H(OH)]⋅0.85 CH3 CN⋅1.58 H2 O; 4: [Tb2 (naphthsaoH)2 (acac)4 H(OH)]⋅0.52 CH3 CN⋅1.71 H2 O; 5: [La6 (CO3 )2 (naphthsao)5 (naphthsaoH)0.5 (acac)8 (CO3 )0.5 (CH3 OH)2.76 H5.5 (H2 O)1.24 ]⋅2.39 CH3 CN⋅0.12 H2 O) contain 1-(1-hydroxynaphthalen-2-yl)-ethanone oxime (naphthsaoH2 ). In 1-4, dinuclear [Ln2 ] complexes crystallize, whereas hexanuclear La(III) complex 5 is formed after fixation of atmospheric carbon dioxide. Dy(III) -based complexes 2 and 3 display single-molecule-magnet properties with energy barriers of 27 and 98 K, respectively. The presence of a broad and unsymmetrical relaxation mode observed in the ac susceptibility data for 3 suggest two different dynamics of the magnetization which might be a consequence of independent relaxation processes of the two different Dy(3+) ions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structure and magnetism of a Mn(III)-Mn(II)-Mn(II)-Mn(III) chain complex.

PubMed

Uhrecký, Róbert; Moncoľ, Ján; Koman, Marian; Titiš, Ján; Boča, Roman

2013-07-14

A novel tetranuclear manganese(II/III) complex with anions of pyridine-2,6-dicarboxylic acid (dipicolinic acid) has been synthesised and magneto-structurally characterised. The crystal structure of [Mn(II)2Mn(III)2(dipic)6(H2O)4]·2CH3OH·4H2O has been determined by single-crystal X-ray diffraction. The tetranuclear complex molecule [Mn(II)2Mn(III)2(dipic)6(H2O)4] is centrosymmetric and two manganese(II) and two manganese(III) atoms are bridged by four dipicolinate ligands. The complex molecules and uncoordinated water and methanol molecules are connected through hydrogen bonds and they form a 3D supramolecular hydrogen-bonding network.

Role of the ancillary ligand N,N-dimethylaminoethanol in the sensitization of Eu(III) and Tb(III) luminescence in dimeric beta-diketonates.

PubMed

Eliseeva, Svetlana V; Kotova, Oxana V; Gumy, Frédéric; Semenov, Sergey N; Kessler, Vadim G; Lepnev, Leonid S; Bünzli, Jean-Claude G; Kuzmina, Natalia P

2008-04-24

Two types of dimeric complexes [Ln2(hfa)6(mu2-O(CH2)2NHMe2)2] and [Ln(thd)2(mu2,eta2-O(CH2)2NMe2)]2 (Ln = YIII, EuIII, GdIII, TbIII, TmIII, LuIII; hfa- = hexafluoroacetylacetonato, thd- = dipivaloylmethanato) are obtained by reacting [Ln(hfa)3(H2O)2] and [Ln(thd)3], respectively, with N,N-dimethylaminoethanol in toluene and are fully characterized. X-ray single crystal analysis performed for the TbIII compounds confirms their dimeric structure. The coordination mode of N,N-dimethylaminoethanol depends on the nature of the beta-diketonate. In [Tb2(hfa)6(mu2-O(CH2)2NHMe2)2], eight-coordinate TbIII ions adopt distorted square antiprismatic coordination environments and are O-bridged by two zwitterionic N,N-dimethylaminoethanol ligands with a Tb1...Tb2 separation of 3.684(1) A. In [Tb(thd)2(mu2,eta2-O(CH2)2NMe2)]2, the N,N-dimethylaminoethanol acts as chelating-bridging O,N-donor anion and the TbIII ions are seven-coordinate; the Tb1...Tb1A separation amounts to 3.735(2) A within centrosymmetric dimers. The dimeric complexes are thermally stable up to 180 degrees C, as shown by thermogravimetric analysis, and their volatility is sufficient for quantitative sublimation under reduced pressure. The EuIII and TbIII dimers display metal-centered luminescence, particularly [Eu2(hfa)6(O(CH2)2NHMe2)2] (quantum yield Q(L)Ln = 58%) and [Tb(thd)2(O(CH2)2NMe2)]2 (32%). Consideration of energy migration paths within the dimers, based on the study of both pure and EuIII- or TbIII-doped (0.01-0.1 mol %) LuIII analogues, leads to the conclusion that both the beta-diketone and N,N-dimethylaminoethanol ligands contribute significantly to the sensitization process of the EuIII luminescence. The ancillary ligand increases considerably the luminescence of [Eu2(hfa)6(O(CH2)2NHMe2)2], compared to [Ln(hfa)3(H2O)2], through the formation of intra-ligand states while it is detrimental to TbIII luminescence in both beta-diketonates. Thin films of the most luminescent compound [Eu2(hfa)6(O(CH2)2NHMe2)2] obtained by vacuum sublimation display photophysical properties analogous to those of the solid-state sample, thus opening perspectives for applications in electroluminescent devices.

Hydroxo radicals, C-H activation, and Pt-C bond formation from 77 K photolysis of a platinum(IV) hydroxo complex.

PubMed

Wickramasinghe, Lasantha A; Sharp, Paul R

2014-11-17

Photolysis (380 nm) of trans,cis-Pt(PEt3)2(Cl)2(OH)(4-tft) (4-tft = 4-trifluoromethylphenyl) at 77 K in 2-methyltetrahydrofuran gives triplet emission, platinum(III), and a hydroxo radical. Benzyl radical emission is observed in toluene from the reaction of a portion of the OH radicals with toluene. Warming the photolyzed solutions gives platinacycle trans-Pt(CH2CH2PEt2)(PEt3)(Cl)2(4-tft) by hydrogen-atom abstraction from a PEt3 ligand and trans-Pt(PEt3)2(Cl)(4-tft) from net HOCl photoelimination. The platinacycle undergoes thermal reductive elimination at 298 K or photolytic reductive elimination, even at 77 K.

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

NASA Astrophysics Data System (ADS)

Mencos, Alejandro; Krim, Lahouari

2018-06-01

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

Assessing the exchange coupling in binuclear lanthanide(iii) complexes and the slow relaxation of the magnetization in the antiferromagnetically coupled Dy2 derivative.

PubMed

Chow, Chun Y; Bolvin, Hélène; Campbell, Victoria E; Guillot, Régis; Kampf, Jeff W; Wernsdorfer, Wolfgang; Gendron, Frédéric; Autschbach, Jochen; Pecoraro, Vincent L; Mallah, Talal

2015-07-01

We report here the synthesis and the investigation of the magnetic properties of a series of binuclear lanthanide complexes belonging to the metallacrown family. The isostructural complexes have a core structure with the general formula [Ga 4 Ln 2 (shi 3- ) 4 (Hshi 2- ) 2 (H 2 shi - ) 2 (C 5 H 5 N) 4 (CH 3 OH) x (H 2 O) x ]· x C 5 H 5 N· x CH 3 OH· x H 2 O (where H 3 shi = salicylhydroxamic acid and Ln = Gd III 1 ; Tb III 2 ; Dy III 3 ; Er III 4 ; Y III 5 ; Y III 0.9 Dy III 0.1 6 ). Apart from the Er-containing complex, all complexes exhibit an antiferromagnetic exchange coupling leading to a diamagnetic ground state. Magnetic studies, below 2 K, on a single crystal of 3 using a micro-squid array reveal an opening of the magnetic hysteresis cycle at zero field. The dynamic susceptibility studies of 3 and of the diluted DyY 6 complexes reveal the presence of two relaxation processes for 3 that are due to the excited ferromagnetic state and to the uncoupled Dy III ions. The antiferromagnetic coupling in 3 was shown to be mainly due to an exchange mechanism, which accounts for about 2/3 of the energy gap between the antiferro- and the ferromagnetic states. The overlap integrals between the Natural Spin Orbitals (NSOs) of the mononuclear fragments, which are related to the magnitude of the antiferromagnetic exchange, are one order of magnitude larger for the Dy 2 than for the Er 2 complex.

C-H activations at iridium(I) square-planar complexes promoted by a fifth ligand.

PubMed

Martín, Marta; Torres, Olga; Oñate, Enrique; Sola, Eduardo; Oro, Luis A

2005-12-28

In the presence of ligands such as acetonitrile, ethylene, or propylene, the Ir(I) complex [Ir(1,2,5,6-eta-C8H12)(NCMe)(PMe3)]BF4 (1) transforms into the Ir(III) derivatives [Ir(1-kappa-4,5,6-eta-C8H12)(NCMe)(L)(PMe3)]BF4 (L = NCMe, 2; eta2-C2H4, 3; eta2-C3H6, 4), respectively, through a sequence of C-H oxidative addition and insertion elementary steps. The rate of this transformation depends on the nature of L and, in the case of NCMe, the pseudo-first-order rate constants display a dependence upon ligand concentration suggesting the formation of five-coordinate reaction intermediates. A similar reaction between 1 and vinyl acetate affords the Ir(III) complex [Ir(1-kappa-4,5,6-eta-C8H12){kappa-O-eta2-OC(Me)OC2H3}(PMe3)]BF4 (7) via the isolable five-coordinate Ir(I) compound [Ir(1,2,5,6-eta-C8H12){kappa-O-eta2-OC(Me)OC2H3}(PMe3)]BF4 (6). DFT (B3LYP) calculations in model complexes show that reactions initiated by acetonitrile or ethylene five-coordinate adducts involve C-H oxidative addition transition states of lower energy than that found in the absence of these ligands. Key species in these ligand-assisted transformations are the distorted (nonsquare-planar) intermediates preceding the intramolecular C-H oxidative addition step, which are generated after release of one cyclooctadiene double bond from the five-coordinate species. The feasibility of this mechanism is also investigated for complexes [IrCl(L)(PiPr3)2] (L = eta2-C2H4, 27; eta2-C3H6, 28). In the presence of NCMe, these complexes afford the C-H activation products [IrClH(CH=CHR)(NCMe)(PiPr3)2] (R = H, 29; Me, 30) via the common cyclometalated intermediate [IrClH{kappa-P,C-P(iPr)2CH(CH3)CH2}(NCMe)(PiPr3)] (31). The most effective C-H oxidative addition mechanism seems to involve three-coordinate intermediates generated by photochemical release of the alkene ligand. However, in the absence of light, the reaction rates display dependences upon NCMe concentration again indicating the intermediacy of five-coordinate acetonitrile adducts.

From iron coordination compounds to metal oxide nanoparticles.

PubMed

Iacob, Mihail; Racles, Carmen; Tugui, Codrin; Stiubianu, George; Bele, Adrian; Sacarescu, Liviu; Timpu, Daniel; Cazacu, Maria

2016-01-01

Various types, shapes and sizes of iron oxide nanoparticles were obtained depending on the nature of the precursor, preparation method and reaction conditions. The mixed valence trinuclear iron acetate, [Fe 2 III Fe II O(CH 3 COO) 6 (H 2 O) 3 ]·2H 2 O (FeAc1), μ 3 -oxo trinuclear iron(III) acetate, [Fe 3 O(CH 3 COO) 6 (H 2 O) 3 ]NO 3 ∙4H 2 O (FeAc2), iron furoate, [Fe 3 O(C 4 H 3 OCOO) 6 (CH 3 OH) 3 ]NO 3 ∙2CH 3 OH (FeF), iron chromium furoate, FeCr 2 O(C 4 H 3 OCOO) 6 (CH 3 OH) 3 ]NO 3 ∙2CH 3 OH (FeCrF), and an iron complex with an original macromolecular ligand (FePAZ) were used as precursors for the corresponding oxide nanoparticles. Five series of nanoparticle samples were prepared employing either a classical thermal pathway (i.e., thermal decomposition in solution, solvothermal method, dry thermal decomposition/calcination) or using a nonconventional energy source (i.e., microwave or ultrasonic treatment) to convert precursors into iron oxides. The resulting materials were structurally characterized by wide-angle X-ray diffraction and Fourier transform infrared, Raman, energy-dispersive X-ray, and X-ray fluorescence spectroscopies, as well as thermogravimetric analysis. The morphology was characterized by transmission electron microscopy, atomic force microscopy and dynamic light scattering. The parameters were varied within each route to fine tune the size and shape of the formed nanoparticles.

Alcohol-catalyzed photoreduction of iron-porphyrin complexes revealed by resonance raman and absorption spectroscopies

NASA Astrophysics Data System (ADS)

Ogura, T.; Fidler, V.; Ozaki, Y.; Kitagawa, T.

1990-06-01

Photoreduction of Fe III(OEP) (2-MeIm) (OEP is octaethylporphyrin; 2-MeIm is 2-methylimidazole) was found to be catalyzed by a trace amount of MeOH present in Ch 2Cl 2 as a stabilizer. The absence of either 2-MeIm or MeOH in the CH 2Cl 2 solution of Fe III(OEP) X (X is Cl -, Br - or I -) leads to no photoreduction. The presence of MeOH in the Fe III(OEP) (2-MeIm) solution results in the appearance of a new absorption band at 585 nm, and when Raman scattering was excited at 590 nm, a new Raman band appeared at 524 cm -. This band exhibited an upshift by 4 cm - with 54Fe(OEP) (2-MeIm)(CH 3OH) and a downshift by 12 cm -1 with 56Fe(OEP)(2-MeIm) (CD 3OD) and was therefore assigned to the Fe III-MeOH stretching vibration. The excitation profile of this band gave a peak around 585 nm and accordingly, the new absorption band at 584 nm was assigned to a charge-transfer (CT) band from MeOH to the Fe III ion. It was most unexpected that the photoreduction did not occur upon laser illumination within the CT band.

Theoretical study on the electronic structures and phosphorescent properties of four Ir(III) complexes with different substituents on the ancillary ligand

NASA Astrophysics Data System (ADS)

Han, Deming; Shang, Xiaohong; Zhang, Gang; Zhao, Lihui

2013-12-01

The geometry structures, electronic structures, absorption and phosphorescent properties of four Ir(III) complexes {[(F2-ppy)2Ir(pta-X)], where F2-ppy = (2,4-difluoro)phenylpyridine; pta = pyridine-1,2,4-triazole; X = -CF3; -H; -CH3; -N(CH3)2}, are investigated using the density functional method. The results reveal that the electron-accepting group -CF3 has no obvious effect on absorption and emission properties, while the substitutive group -N(CH3)2 with strong electron-donating ability has obvious effect on the emission properties. The mobility of hole and electron were studied computationally based on the Marcus-Hush theory. Calculations of ionisation potential and electron affinity were used to evaluate the injection abilities of holes and electrons into these complexes. We hope that this theoretical work can provide a suitable guide to the future design and synthesis of novel phosphorescent materials for use in the organic light-emitting diodes.

In situ nanostructure formation of (micro-hydroxo)bis(micro-carboxylato) diruthenium units in nafion membrane and its utilization for selective reduction of nitrosonium ion in aqueous medium.

PubMed

Kumar, Annamalai Senthil; Tanase, Tomoaki; Iida, Masayasu

2007-01-16

Nanostructured molecular film containing the (micro-hydroxo)bis(micro-carboxylato) diruthenium(III) units, [RuIII2(micro-OH)(micro-CH3COO)2(HBpz3)2]+ ({RuIII2(micro-OH)}), was prepared by an in situ conversion of its micro-oxo precursor, [RuIII2(micro-O)(micro-CH3COO)2(HBpz3)2] ({RuIII2(micro-O)}), in a Nafion membrane matrix, where HBpz3 is hydrotris(1-pyrazolyl)borate. The conversion procedure results in fine nanoparticle aggregates of the {RuIII2(micro-OH)} units in the Nafion membrane (Nf-{RuIII2(micro-OH)}), where an average particle size (4.1 +/- 2.3 nm) is close to the Nafion's cluster dimension of approximately 4 nm. Chemically modified electrodes by using the Nafion molecular membrane films (Nf-{RuIII2(micro-OH)}-MMFEs) were further developed on ITO/glass and glassy carbon electrode (GCE) surfaces, and a selective reduction of nitrosonium ion (NO+), presumably through reaction of a {RuIIRuIII(micro-OH)} mixed-valence state with HNO2, was demonstrated without interference by molecular oxygen in an acidic aqueous solution. The Nf-{RuIII2(micro-OH)}-MMFEs are stable even in a physiological condition (pH 7), where the naked {RuIII2(-OH)} complex is readily transformed into its deprotonated {RuIII2(micro-O)} form, demonstrating an unusual stabilizing effects for the {RuIII2(micro-OH)} unit by the Nafion cluster environment.

DFT Virtual Screening Identifies Rhodium–Amidinate Complexes As Potential Homogeneous Catalysts for Methane-to-Methanol Oxidation

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

Fu, Ross; Nielsen, Robert J.; Goddard, William A.

2014-11-11

In the search for new organometallic catalysts for low-temperature selective conversion of CH4 to CH3OH, we apply quantum mechanical virtual screening to select the optimum combination of ligand and solvent on rhodium to achieve low barriers for CH4 activation and functionalization to recommend for experimental validation. Here, we considered Rh because its lower electronegativity compared with Pt and Pd may allow it to avoid poisoning by coordinating media. We report quantum mechanical predictions (including implicit and explicit solvation) of the mechanisms for RhIII(NN) and RhIII(NNF) complexes [where (NN) = bis(N-phenyl)benzylamidinate and (NNF) = bis(N-pentafluorophenyl)pentafluorobenzylamidinate] to catalytically activate and functionalize methanemore » using trifluoroacetic acid (TFAH) or water as a solvent. In particular, we designed the (NNF) ligand as a more electrophilic analogue to the (NN) ligand, and our results predict the lowest transition state barrier (ΔG‡ = 27.6 kcal/mol) for methane activation in TFAH from a pool of four different classes of ligands. To close the catalytic cycle, the functionalization of methylrhodium intermediates was also investigated, involving carbon–oxygen bond formation via SN2 attack by solvent, or SR2 attack by a vanadium oxo. Activation barriers for the functionalization of methylrhodium intermediates via nucleophilic attack are lower when the solvent is water, but CH4 activation barriers are higher. In addition, we have found a correlation between CH4 activation barriers and rhodium–methyl bond energies that allow us to predict the activation transition state energies for future ligands, as well.« less

Syntheses, crystal structures and supramolecular topologies of copper(II)-main group metal complexes derived from N,N‧-o-phenylenebis(3-ethoxysalicylaldimine)

NASA Astrophysics Data System (ADS)

Mondal, Suraj; Hazra, Susanta; Sarkar, Sohini; Sasmal, Sujit; Mohanta, Sasankasekhar

2011-10-01

The work in the present investigation reports the syntheses, crystal structures and supramolecular topologies of 11 copper(II)-main group metal ion complexes [Cu IILNa I(NO 3)(H 2O)]·2CH 3CN ( 1), [Cu IILNa I(N 3)(CH 3OH)]·CH 3OH ( 2), [Cu IILNa I(ClO 4)(CH 3CN)]·0.5CH 3CN ( 3), [Cu IILNa I(BF 4)(CH 3OH)]·H 2O ( 4), [{Cu IILNa I(H 2O)} 2(Cu IIL)](BPh 4) 2 ( 5), [Cu IILK I(ClO 4)(CH 3COCH 3)] ( 6), [Cu IILCa II(ClO 4) 2(H 2O)] ( 7), [{Cu IILCa II(NO 3)(μ-NO 3)(H 2O)}(Cu IIL)]·H 2O·CH 3COCH 3 ( 8), [(Cu IIL) 2Ba II(NO 3) 2]·CH 3OH ( 9), [Cu IILPb II(NO 3) 2]·CH 3OH ( 10) and [Cu IILBi III(NO 3) 3]·CH 3COCH 3 ( 11), where H 2L = N, N'- o-phenylenebis(3-ethoxysalicylaldimine). Among these, eight ( 1-4, 6, 7, 10 and 11) are dinuclear compounds, one ( 9) is trinuclear double-decker sandwich compound, one ( 8) is a [2 × 1 + 1 × 1] trimetallic cocrystal of a dinuclear and a mononuclear units and the remaining ( 5) is a [2 × 2 + 1 × 1] pentametallic cocrystal of two dinuclear and one mononuclear units. All the 11 compounds 1-11 contain one or more deprotonated ligand, L 2-, the salen type N 2O 2 compartment of each of which is occupied by a Cu II ion to result in the formation of a [Cu IIL] moiety. On the other hand, the larger and open O(phenoxo) 2O(ethoxy) 2 compartment of the ligand in one or more [Cu IIL] moieties interact (s) with the metal ions Na I ( 1-5)/K I ( 6)/Ca II ( 7 and 8)/Ba II ( 9)/Pb II ( 10)/Bi III ( 11) to produce the title compounds. It has been observed that the neighbouring di/trinuclear units in 1/ 3/ 4/ 6/ 9/ 10/ 11 are self-assembled to one-/two-dimensional topologies as a result of one or more C sbnd H⋯O/O sbnd H⋯O hydrogen bonding interaction (s). Following self-assemblies are observed: one-dimensional in 4, one-dimensional helical in 1, one-dimensional double-chain (ladder) in 3, 6 and 10, two-dimensional in 9 and 11.

The effect of nitrogen deposition rather than warming on CH4 flux in alpine meadows depends on precipitation variations

NASA Astrophysics Data System (ADS)

Chen, X.; Genxu, W.

2017-12-01

Uncertainties remain regarding the effects of climate warming and increasing nitrogen (N) deposition on GHG flux in alpine grasslands due to a lack of knowledge about how hydrological characteristics control GHGs fluxes. Therefore, a simulated warming and N fertilization experiment was conducted in a non-wetland (alpine meadow, AM) and a wetland (alpine swamp meadow, SM) of a permafrost region. We measured and analysed the CH4 and N2O fluxes of each treatment during two contrasting hydrological growing seasons. The results showed that: (i) warming increased the CH4 uptake in the AM but had no effect in the SM, and warming increased the N2O emissions from the AM and resulted in a change of the SM from a N2O sink into a source; (ii) N fertilization increased the CH4 uptake of the AM during the dry growing season, and had no effect on the CH4 and N2O fluxes of the SM; and (iii) the interaction between warming and N fertilization increased the CH4 uptake of the AM over the two growing seasons while increasing the CH4 uptake and N2O emissions of the SM during the dry growing season. Our results suggest that (i) the GHG flux of wetland ecosystems is more sensitive to precipitation variations than that of non-wetlands and (ii) precipitation controls the CH4 flux response to increasing N deposition of these alpine meadows.

40 CFR 1065.695 - Data requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... restriction. (v) Charge air cooler volume. (vi) Charge air cooler outlet temperature, specified engine.... (iii) “Dry-to-wet” correction. (iv) NMHC, CH4, and contamination correction. (v) NOX humidity...

40 CFR 1066.15 - Overview of test procedures.

Code of Federal Regulations, 2012 CFR

2012-07-01

... ways: (i) Total hydrocarbons, THC. (ii) Nonmethane hydrocarbons, NMHC, which results from subtracting methane (CH4) from THC. (iii) Total hydrocarbon-equivalent, THCE, which results from adjusting THC...

40 CFR 1066.15 - Overview of test procedures.

Code of Federal Regulations, 2013 CFR

2013-07-01

... ways: (i) Total hydrocarbons, THC. (ii) Nonmethane hydrocarbons, NMHC, which results from subtracting methane (CH4) from THC. (iii) Total hydrocarbon-equivalent, THCE, which results from adjusting THC...

Methanotrophy within the water column of a large meromictic tropical lake (Lake Kivu, East Africa)

NASA Astrophysics Data System (ADS)

Morana, C.; Borges, A. V.; Roland, F. A. E.; Darchambeau, F.; Descy, J.-P.; Bouillon, S.

2015-04-01

The permanently stratified Lake Kivu is one of the largest freshwater reservoirs of dissolved methane (CH4) on Earth. Yet CH4 emissions from its surface to the atmosphere have been estimated to be 2 orders of magnitude lower than the CH4 upward flux to the mixed layer, suggesting that microbial CH4 oxidation is an important process within the water column. A combination of natural abundance stable carbon isotope analysis (δ13C) of several carbon pools and 13CH4-labelling experiments was carried out during the rainy and dry season to quantify (i) the contribution of CH4-derived carbon to the biomass, (ii) methanotrophic bacterial production (MBP), and (iii) methanotrophic bacterial growth efficiency (MBGE), defined as the ratio between MBP and gross CH4 oxidation. We also investigated the distribution and the δ13C of specific phospholipid fatty acids (PLFAs), used as biomarkers for aerobic methanotrophs. Maximal MBP rates were measured in the oxycline, suggesting that CH4 oxidation was mainly driven by oxic processes. Moreover, our data revealed that methanotrophic organisms in the water column oxidized most of the upward flux of CH4, and that a significant amount of CH4-derived carbon was incorporated into the microbial biomass in the oxycline. The MBGE was variable (2-50%) and negatively related to CH4 : O2 molar ratios. Thus, a comparatively smaller fraction of CH4-derived carbon was incorporated into the cellular biomass in deeper waters, at the bottom of the oxycline where oxygen was scarce. The aerobic methanotrophic community was clearly dominated by type I methanotrophs and no evidence was found for an active involvement of type II methanotrophs in CH4 oxidation in Lake Kivu, based on fatty acids analyses. Vertically integrated over the water column, the MBP was equivalent to 16-60% of the average phytoplankton particulate primary production. This relatively high magnitude of MBP, and the substantial contribution of CH4-derived carbon to the overall biomass in the oxycline, suggest that methanotrophic bacteria could potentially sustain a significant fraction of the pelagic food web in the deep, meromictic Lake Kivu.

Poly[[tetra-μ3-acetato-hexa-μ2-acetato­diaqua-μ2-oxalato-tetra­lanthanum(III)] dihydrate

PubMed Central

Di, Wen-Jing; Lan, Shao-Min; Zhang, Qun; Liang, Yun-Xiao

2011-01-01

The title compound, {[La4(CH3CO2)10(C2O4)(H2O)2]·2H2O}n, exhibits a two-dimensional layered structure with the oxalate and acetate ligands acting as bridges. The asymmetric unit contains two crystallographically independent lanthanum(III) ions, half of an oxalate ligand, five acetate ligands, one coordinated water mol­ecule and one uncoordinated water mol­ecule. The coordination numbers of the two La ions are 9 and 10. Adjacent layers of the structure, which extend parallel to (100), are linked by O–H⋯O hydrogen bonds and are also held together by van der Waals inter­actions between the CH3 groups of the acetate anions. PMID:22064832

Further studies on lead compounds containing the opioid pharmacophore Dmt-Tic.

PubMed

Balboni, Gianfranco; Fiorini, Stella; Baldisserotto, Anna; Trapella, Claudio; Sasaki, Yusuke; Ambo, Akihiro; Marczak, Ewa D; Lazarus, Lawrence H; Salvadori, Severo

2008-08-28

Some reference opioids containing the Dmt-Tic pharmacophore, especially the delta agonists H-Dmt-Tic-Gly-NH-Ph (1) and H-Dmt-Tic-NH-(S)CH(CH2-COOH)-Bid (4) (UFP-512) were evaluated for the influence of the substitution of Gly with aspartic acid, its chirality, and the importance of the -NH-Ph and N(1)H-Bid hydrogens in the inductions of delta agonism. The results provide the following conclusions: (i) Asp increases delta selectivity by lowering the mu affinity; (ii) -NH-Ph and N(1)H-Bid nitrogens methylation transforms the delta agonists into delta antagonists; (iii) the substitution of Gly with L-Asp/D-Asp in the delta agonist H-Dmt-Tic-Gly-NH-Ph gave delta antagonists; the same substitution in the delta agonist H-Dmt-Tic-NH-CH2-Bid yielded more selective agonists, H-Dmt-Tic-NH-(S)CH(CH2-COOH)-Bid and H-Dmt-Tic-NH-(R)CH(CH2-COOH)-Bid; (iv) L-Asp seems important only in functional bioactivity, not in receptor affinity; (v) H-Dmt-Tic-NH-(S)CH(CH2-COOH)-Bid(N(1)-Me) (10) evidenced analgesia similar to 4, which was reversed by naltrindole only in the tail flick. 4 and 10 had opposite behaviours in mice; 4 caused agitation, 10 gave sedation and convulsions.

Electronically Strongly Coupled Divinylheterocyclic-Bridged Diruthenium Complexes.

PubMed

Pfaff, Ulrike; Hildebrandt, Alexander; Korb, Marcus; Oßwald, Steffen; Linseis, Michael; Schreiter, Katja; Spange, Stefan; Winter, Rainer F; Lang, Heinrich

2016-01-11

Complexes [{Ru(CO)Cl(PiPr3 )2 }2 (μ-2,5-(CH-CH)2 -(c) C4 H2 E] (E=NR; R=C6 H4 -4-NMe2 (10 a), C6 H4 -4-OMe (10 b), C6 H4 -4-Me (10 c), C6 H5 (10 d), C6 H4 -4-CO2 Et (10 e), C6 H4 -4-NO2 (10 f), C6 H3 -3,5-(CF3 )2 (10 g), CH3 (11); E=O (12), S (13)) are discussed. The solid state structures of four alkynes and two complexes are reported. (Spectro)electrochemical studies show a moderate influence of the nature of the heteroatom and the electron-donating or -withdrawing substituents R in 10 a-g on the electrochemical and spectroscopic properties. The CVs display two consecutive one-electron redox events with ΔE°'=350-495 mV. A linear relationship between ΔE°' and the σp Hammett constant for 10 a-f was found. IR, UV/Vis/NIR and EPR studies for 10(+) -13(+) confirm full charge delocalization over the {Ru}CH-CH-heterocycle-CH-CH{Ru} backbone, classifying them as Class III systems according to the Robin and Day classification. DFT-optimized structures of the neutral complexes agree well with the experimental ones and provide insight into the structural consequences of stepwise oxidations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redox Potential and C-H Bond Cleaving Properties of a Nonheme FeIV=O Complex in Aqueous Solution

PubMed Central

Wang, Dong; Zhang, Mo; Bühlmann, Philippe; Que, Lawrence

2010-01-01

High-valent iron-oxo intermediates have been identified as the key oxidants in the catalytic cycles of many nonheme enzymes. Among the large number of synthetic FeIV=O complexes characterized to date, [FeIV(O)(N4Py)]2+ (1) exhibits the unique combination of thermodynamic stability, allowing its structural characterization by X-ray crystallography, and oxidative reactivity sufficient to cleave C-H bonds as strong as those in cyclohexane (DC-H = 99.3 kcal mol-1). However, its redox properties are not yet well understood. In this work, the effect of protons on the redox properties of 1 has been investigated electrochemically in nonaqueous and aqueous solutions. While the cyclic voltammetry of 1 in CH3CN is complicated by coupling of several chemical and redox processes, the FeIV/III couple is reversible in aqueous solution with E1/2 = +0.41 V vs. SCE at pH 4 and involves the transfer of one electron and one proton to give the FeIII-OH species. This is in fact the first example of reversible electrochemistry to be observed for this family of nonheme oxoiron(IV) complexes. C-H bond oxidations by 1 have been studied in H2O and found to have reactions rates that depend on the C-H bond strength but not on the solvent. Furthermore, our electrochemical results have allowed a DO-H value of 78(2) kcal mol-1 to be calculated for the FeIII-OH unit derived from 1. Interestingly, although this DO-H value is 6-11 kcal mol-1 lower than those corresponding to oxidants such as [FeIV(O)(TMP)] (TMP = tetramesitylporphinate), [RuIV(O)(bpy)2(py)]2+ (bpy = bipyridine, py = pyridine) and the tert-butylperoxyl radical, the oxidation of dihydroanthracene by 1 occurs at a rate comparable to those for these other oxidants. This comparison suggests that the nonheme N4Py ligand environment confers a kinetic advantage over the others that enhances the C-H bond cleavage ability of 1. PMID:20476758

Synthesis and Structural Characterization of Tris(dimethyldithiocarbamate)Indium(III), In[S2CN(CH3)2]3

NASA Technical Reports Server (NTRS)

Clark, Eric B.; Breen, Marc L.; Fanwick, Phillip E.; Hepp, Aloysius F.; Duraj, Stan A.

1998-01-01

The synthesis and structure of the indium dithiocarbamate, In[SCN(CH3)2]3*1/2 4-mepy (4-mepy = 4-methylpyridine), is described. Indium metal was oxidized by tetramethylthiuramdisulfide in 4-methylpyridine at 25C to form a new, homoleptic indium(HI) dithiocarbamate in yields exceeding 60%. In[S2CN(CH3)213 exists as a discrete molecule with a distorted-octahedral geometry. The compound crystallizes in the P 1-bar (No. 2) space group with a = 9.282(l)A, b = 10.081(1)A, c = 12.502 A, alpha= 73.91 (1) degrees, beta = 70.21(1) degrees, gamma = 85.84(1) degrees, Z = 2,v(A(exp 3)) =1057.3(3), R = 0.046, and R(sub w) = 0.061.

New Y and T Dwarfs from WISE Identified by Methane Imaging

NASA Astrophysics Data System (ADS)

Tinney, C. G.; Kirkpatrick, J. Davy; Faherty, Jacqueline K.; Mace, Gregory N.; Cushing, Mike; Gelino, Christopher R.; Burgasser, Adam J.; Sheppard, Scott S.; Wright, Edward L.

2018-06-01

We identify new Y- and T-type brown dwarfs from the WISE All Sky data release using images obtained in filters that divide the traditional near-infrared H and J bands into two halves—specifically {CH}}4{{s}} and CH4l in the H and J2, and J3 in the J. This proves to be very effective at identifying cool brown dwarfs via the detection of their methane absorption, as well as providing preliminary classification using methane colors and WISE -to-near-infrared colors. New and updated calibrations between T/Y spectral types and {CH}}4{{s}}–CH4l J3–W2, and {CH}}4{{s}}–W2 colors are derived, producing classification estimates good to a few spectral sub-types. We present photometry for a large sample of T and Y dwarfs in these filters, together with spectroscopy for 23 new ultra-cool dwarfs—2 Y dwarfs and 21 T dwarfs. We identify a further 8 new cool brown dwarfs, which we have high confidence are T dwarfs based on their methane photometry. We find that, for objects observed on a 4 m class telescope at J-band magnitudes of ∼20 or brighter, {CH}}4{{s}}–CH4l is the more powerful color for detecting objects and then estimating spectral types. Due to the lower sky background in the J-band, the J3 and J2 bands are more useful for identifying fainter cool dwarfs at J ≳ 22. The J3–J2 color is poor at estimating spectral types. But fortunately, once J3–J2 confirms that an object is a cool dwarf, the J3–W2 color is very effective at estimating approximate spectral types.

40 CFR 1065.695 - Data requirements.

Code of Federal Regulations, 2010 CFR

2010-07-01

... restriction. (v) Charge air cooler volume. (vi) Charge air cooler outlet temperature, specified engine... following: (i) Drift correction. (ii) Noise correction. (iii) “Dry-to-wet” correction. (iv) NMHC, CH4, and...

40 CFR 1065.695 - Data requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... restriction. (v) Charge air cooler volume. (vi) Charge air cooler outlet temperature, specified engine... following: (i) Drift correction. (ii) Noise correction. (iii) “Dry-to-wet” correction. (iv) NMHC, CH4, and...

40 CFR 1065.695 - Data requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... restriction. (v) Charge air cooler volume. (vi) Charge air cooler outlet temperature, specified engine... following: (i) Drift correction. (ii) Noise correction. (iii) “Dry-to-wet” correction. (iv) NMHC, CH4, and...

Hourly methane production in finishing steers fed at different levels of dry matter intake

USDA-ARS?s Scientific Manuscript database

Methane (CH4) loss from finishing cattle is important as it represents an energy loss that could be used for maintenance and growth, and CH4 is a greenhouse gas with a global warming potential 21 to 25 times that of CO2. Our objectives were to determine hourly CH4 production from growing cattle fed...

Distinct Anaerobic Bacterial Consumers of Cellobiose-Derived Carbon in Boreal Fens with Different CO2/CH4 Production Ratios

PubMed Central

Eiler, Alexander; Biasi, Christina; Tuittila, Eeva-Stiina; Yrjälä, Kim; Fritze, Hannu

2016-01-01

ABSTRACT Northern peatlands in general have high methane (CH4) emissions, but individual peatlands show considerable variation as CH4 sources. Particularly in nutrient-poor peatlands, CH4 production can be low and exceeded by carbon dioxide (CO2) production from unresolved anaerobic processes. To clarify the role anaerobic bacterial degraders play in this variation, we compared consumers of cellobiose-derived carbon in two fens differing in nutrient status and the ratio of CO2 to CH4 produced. After [13C]cellobiose amendment, the mesotrophic fen produced equal amounts of CH4 and CO2. The oligotrophic fen had lower CH4 production but produced 3 to 59 times more CO2 than CH4. RNA stable-isotope probing revealed that in the mesotrophic fen with higher CH4 production, cellobiose-derived carbon was mainly assimilated by various recognized fermenters of Firmicutes and by Proteobacteria. The oligotrophic peat with excess CO2 production revealed a wider variety of cellobiose-C consumers, including Firmicutes and Proteobacteria, but also more unconventional degraders, such as Telmatobacter-related Acidobacteria and subphylum 3 of Verrucomicrobia. Prominent and potentially fermentative Planctomycetes and Chloroflexi did not appear to process cellobiose-C. Our results show that anaerobic degradation resulting in different levels of CH4 production can involve distinct sets of bacterial degraders. By distinguishing cellobiose degraders from the total community, this study contributes to defining anaerobic bacteria that process cellulose-derived carbon in peat. Several of the identified degraders, particularly fermenters and potential Fe(III) or humic substance reducers in the oligotrophic peat, represent promising candidates for resolving the origin of excess CO2 production in peatlands. IMPORTANCE Peatlands are major sources of the greenhouse gas methane (CH4), yet in many peatlands, CO2 production from unresolved anaerobic processes exceeds CH4 production. Anaerobic degradation produces the precursors of CH4 production but also represents competing processes. We show that anaerobic degradation leading to high or low CH4 production involved distinct sets of bacteria. Well-known fermenters dominated in a peatland with high CH4 production, while novel and unconventional degraders could be identified in a site where CO2 production greatly exceeds CH4 production. Our results help identify and assign functions to uncharacterized bacteria that promote or inhibit CH4 production and reveal bacteria potentially producing the excess CO2 in acidic peat. This study contributes to understanding the microbiological basis for different levels of CH4 emission from peatlands. PMID:27913414

Distinct Anaerobic Bacterial Consumers of Cellobiose-Derived Carbon in Boreal Fens with Different CO2/CH4 Production Ratios.

PubMed

Juottonen, Heli; Eiler, Alexander; Biasi, Christina; Tuittila, Eeva-Stiina; Yrjälä, Kim; Fritze, Hannu

2017-02-15

Northern peatlands in general have high methane (CH 4 ) emissions, but individual peatlands show considerable variation as CH 4 sources. Particularly in nutrient-poor peatlands, CH 4 production can be low and exceeded by carbon dioxide (CO 2 ) production from unresolved anaerobic processes. To clarify the role anaerobic bacterial degraders play in this variation, we compared consumers of cellobiose-derived carbon in two fens differing in nutrient status and the ratio of CO 2 to CH 4 produced. After [ 13 C]cellobiose amendment, the mesotrophic fen produced equal amounts of CH 4 and CO 2 The oligotrophic fen had lower CH 4 production but produced 3 to 59 times more CO 2 than CH 4 RNA stable-isotope probing revealed that in the mesotrophic fen with higher CH 4 production, cellobiose-derived carbon was mainly assimilated by various recognized fermenters of Firmicutes and by Proteobacteria The oligotrophic peat with excess CO 2 production revealed a wider variety of cellobiose-C consumers, including Firmicutes and Proteobacteria, but also more unconventional degraders, such as Telmatobacter-related Acidobacteria and subphylum 3 of Verrucomicrobia Prominent and potentially fermentative Planctomycetes and Chloroflexi did not appear to process cellobiose-C. Our results show that anaerobic degradation resulting in different levels of CH 4 production can involve distinct sets of bacterial degraders. By distinguishing cellobiose degraders from the total community, this study contributes to defining anaerobic bacteria that process cellulose-derived carbon in peat. Several of the identified degraders, particularly fermenters and potential Fe(III) or humic substance reducers in the oligotrophic peat, represent promising candidates for resolving the origin of excess CO 2 production in peatlands. Peatlands are major sources of the greenhouse gas methane (CH 4 ), yet in many peatlands, CO 2 production from unresolved anaerobic processes exceeds CH 4 production. Anaerobic degradation produces the precursors of CH 4 production but also represents competing processes. We show that anaerobic degradation leading to high or low CH 4 production involved distinct sets of bacteria. Well-known fermenters dominated in a peatland with high CH 4 production, while novel and unconventional degraders could be identified in a site where CO 2 production greatly exceeds CH 4 production. Our results help identify and assign functions to uncharacterized bacteria that promote or inhibit CH 4 production and reveal bacteria potentially producing the excess CO 2 in acidic peat. This study contributes to understanding the microbiological basis for different levels of CH 4 emission from peatlands. Copyright © 2017 American Society for Microbiology.

Selective methane chlorination to methyl chloride by zeolite Y-based catalysts

NASA Astrophysics Data System (ADS)

Joo, Hyeonho; Kim, Daeho; Lim, Kwang Soo; Choi, Yong Nam; Na, Kyungsu

2018-03-01

The CH4 chlorination over Y zeolites was investigated to produce CH3Cl in a high yield. Three different catalytic systems based on Y zeolite were tested for enhancement of CH4 conversion and CH3Cl selectivity: (i) HY zeolites in H+-form having various Si/Al ratios, (ii) Pt/HY zeolites supporting Pt metal nanoparticles, (iii) Pt/NaY zeolites in Na+-form supporting Pt metal nanoparticles. The reaction was carried out using the gas mixture of CH4 and Cl2 with the respective flow rates of 15 and 10 mL min-1 at 300-350 °C using a fixed-bed reactor under a continuous gas flow condition (gas hourly space velocity = 3000 mL g-1 h-1). Above the reaction temperature of 300 °C, the CH4 chlorination is spontaneous even in the absence of catalyst, achieving 23.6% of CH4 conversion with 73.4% of CH3Cl selectivity. Under sufficient supplement of thermal energy, Cl2 molecules can be dissociated to two chlorine radicals, which triggered the C-H bond activation of CH4 molecule and thereby various chlorinated methane products (i.e., CH3Cl, CH2Cl2, CHCl3, CCl4) could be produced. When the catalysts were used under the same reaction condition, enhancement in the CH4 conversion was observed. The Pt-free HY zeolite series with varied Si/Al ratios gave around 27% of CH4 conversion, but there was a slight decrease in CH3Cl selectivity with about 64%. Despite the difference in acidity of HY zeolites having different Si/Al ratios, no prominent effect of the Si/Al ratios on the catalytic performance was observed. This suggests that the catalytic contribution of HY zeolites under the present reaction condition is not strong enough to overcome the spontaneous CH4 chlorination. When the Pt/HY zeolite catalysts were used, the CH4 conversion reached further up to 30% but the CH3Cl selectivity decreased to 60%. Such an enhancement of CH4 conversion could be attributed to the strong catalytic activity of HY and Pt/HY zeolite catalysts. However, both catalysts induced the radical cleavage of Cl2 more favorably, which ultimately decreased the CH3Cl selectivity. Such trade-off relationship between CH4 conversion and CH3Cl selectivity can be slightly broken by using Pt/NaY zeolite catalyst that is known to possess Frustrated Lewis Pairs (FLP) that are very useful for ionic cleavage of H2 to H+ and H-. Similarly, in the present work, Pt/NaY(FLP) catalysts enhanced the CH4 conversion while keeping the CH3Cl selectivity as compared to the Pt/HY zeolite catalysts.

Limits to Dihydrogen Incorporation into Electron Sinks Alternative to Methanogenesis in Ruminal Fermentation

PubMed Central

Ungerfeld, Emilio M.

2015-01-01

Research is being conducted with the objective of decreasing methane (CH4) production in the rumen, as methane emissions from ruminants are environmentally damaging and a loss of digestible energy to ruminants. Inhibiting ruminal methanogenesis generally results in accumulation of dihydrogen (H2), which is energetically inefficient and can inhibit fermentation. It would be nutritionally beneficial to incorporate accumulated H2 into propionate or butyrate production, or reductive acetogenesis. The objective of this analysis was to examine three possible physicochemical limitations to the incorporation of accumulated H2 into propionate and butyrate production, and reductive acetogenesis, in methanogenesis-inhibited ruminal batch and continuous cultures: (i) Thermodynamics; (ii) Enzyme kinetics; (iii) Substrate kinetics. Batch (N = 109) and continuous (N = 43) culture databases of experiments with at least 50% inhibition in CH4 production were used in this meta-analysis. Incorporation of accumulated H2 into propionate production and reductive acetogenesis seemed to be thermodynamically feasible but quite close to equilibrium, whereas this was less clear for butyrate. With regard to enzyme kinetics, it was speculated that hydrogenases of ruminal microorganisms may have evolved toward high-affinity and low maximal velocity to compete for traces of H2, rather than for high pressure accumulated H2. Responses so far obtained to the addition of propionate production intermediates do not allow distinguishing between thermodynamic and substrate kinetics control. PMID:26635743

Abundant Methanol Ice toward a Massive Young Stellar Object in the Central Molecular Zone

NASA Astrophysics Data System (ADS)

An, Deokkeun; Sellgren, Kris; Boogert, A. C. Adwin; Ramírez, Solange V.; Pyo, Tae-Soo

2017-07-01

Previous radio observations revealed widespread gas-phase methanol (CH3OH) in the Central Molecular Zone (CMZ) at the Galactic center (GC), but its origin remains unclear. Here, we report the discovery of CH3OH ice toward a star in the CMZ, based on a Subaru 3.4-4.0 μm spectrum, aided by NASA/IRTF L\\prime imaging and 2-4 μm spectra. The star lies ˜8000 au away in projection from a massive young stellar object (MYSO). Its observed high CH3OH ice abundance (17 % +/- 3 % relative to H2O ice) suggests that the 3.535 μm CH3OH ice absorption likely arises in the MYSO’s extended envelope. However, it is also possible that CH3OH ice forms with a higher abundance in dense clouds within the CMZ, compared to within the disk. Either way, our result implies that gas-phase CH3OH in the CMZ can be largely produced by desorption from icy grains. The high solid CH3OH abundance confirms the prominent 15.4 μm shoulder absorption observed toward GC MYSOs arises from CO2 ice mixed with CH3OH. Based in part on data collected at Subaru Telescope, which is operated by the National Astronomical Observatory of Japan.

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

PubMed

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

2017-07-26

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

Divalent and trivalent gas-phase coordination complexes of californium: evaluating the stability of Cf(II)

DOE PAGES

Dau, Phuong D.; Shuh, David K.; Sturzbecher-Hoehne, Manuel; ...

2016-07-07

The divalent oxidation state is increasingly stable relative to the trivalent state for the later actinide elements, with californium the first actinide to exhibit divalent chemistry under moderate conditions. Although there is evidence for divalent Cf in solution and solid compounds, there are no reports of discrete complexes in which Cf II is coordinated by anionic ligands. Described here is the divalent Cf methanesulfinate coordination complex, Cf II(CH 3SO 2) 3-, prepared in the gas phase by reductive elimination of CH 3SO 2 from Cf III(CH 3SO 2) 4-. Comparison with synthesis of the corresponding Sm and Cm complexes revealsmore » reduction of CfIII and SmIII, and no evidence for reduction of Cm III. This reflects the comparative 3+/2+ reduction potentials: Cf 3+ (-1.60 V) ≈ Sm 3+ (-1.55 V) >> Cm 3+ (-3.7 V). Association of O 2 to the divalent complexes is attributed to formation of superoxides, with recovery of the trivalent oxidation state. Lastly, the new gas-phase chemistry of californium, now the heaviest element to have been studied in this manner, provides evidence for Cf II coordination complexes and similar chemistry of Cf and Sm.« less

Divalent and trivalent gas-phase coordination complexes of californium: evaluating the stability of Cf(II)

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

Dau, Phuong D.; Shuh, David K.; Sturzbecher-Hoehne, Manuel

The divalent oxidation state is increasingly stable relative to the trivalent state for the later actinide elements, with californium the first actinide to exhibit divalent chemistry under moderate conditions. Although there is evidence for divalent Cf in solution and solid compounds, there are no reports of discrete complexes in which Cf II is coordinated by anionic ligands. Described here is the divalent Cf methanesulfinate coordination complex, Cf II(CH 3SO 2) 3-, prepared in the gas phase by reductive elimination of CH 3SO 2 from Cf III(CH 3SO 2) 4-. Comparison with synthesis of the corresponding Sm and Cm complexes revealsmore » reduction of CfIII and SmIII, and no evidence for reduction of Cm III. This reflects the comparative 3+/2+ reduction potentials: Cf 3+ (-1.60 V) ≈ Sm 3+ (-1.55 V) >> Cm 3+ (-3.7 V). Association of O 2 to the divalent complexes is attributed to formation of superoxides, with recovery of the trivalent oxidation state. Lastly, the new gas-phase chemistry of californium, now the heaviest element to have been studied in this manner, provides evidence for Cf II coordination complexes and similar chemistry of Cf and Sm.« less

Ligand-Promoted Rh(III)-Catalyzed Coupling of Aryl C-H Bonds with Arylboron Reagents.

PubMed

Wang, Huai-Wei; Cui, Pei-Pei; Lu, Yi; Sun, Wei-Yin; Yu, Jin-Quan

2016-04-15

Rhodium(III)-catalyzed C-H arylation of arenes with phenylboronic acid pinacol esters has been achieved using a readily removable N-pentafluorophenylbenzamide directing group for the first time. The use of a bidentate phosphine ligand (Binap) significantly increased the yield of the cross-coupling of C-H bonds with organoboron reagents.

Crystal structures of three lead(II) acetate-bridged di-amino-benzene coordination polymers.

PubMed

Geiger, David K; Parsons, Dylan E; Zick, Patricia L

2014-12-01

Poly[tris-(acetato-κ(2) O,O')(μ2-acetato-κ(3) O,O':O)tetra-kis-(μ3-acetato-κ(4) O,O':O:O')bis-(benzene-1,2-di-amine-κN)tetra-lead(II)], [Pb4(CH3COO)8(C6H8N2)2] n , (I), poly[(acetato-κ(2) O,O')(μ3-acetato-κ(4) O,O':O:O')(4-chloro-benzene-1,2-diamine-κN)lead(II)], [Pb(CH3COO)2(C6H7ClN2)] n , (II), and poly[(κ(2) O,O')(μ3-acetato-κ(4) O,O':O:O')(3,4-di-amino-benzo-nitrile-κN)lead(II)], [Pb(CH3COO)2(C7H7N3)] n , (III), have polymeric structures in which monomeric units are joined by bridging acetate ligands. All of the Pb(II) ions exhibit hemidirected coordination. The repeating unit in (I) is composed of four Pb(II) ions having O6, O6N, O7 and O6N coordination spheres, respectively, where N represents a monodentate benzene-1,2-di-amine ligand and O acetate O atoms. Chains along [010] are joined by bridging acetate ligands to form planes parallel to (10-1). (II) and (III) are isotypic and have one Pb(II) ion in the asymmetric unit that has an O6N coordination sphere. Pb2O2 units result from a symmetry-imposed inversion center. Polymeric chains parallel to [100] exhibit hydrogen bonding between the amine and acetate ligands. In (III), additional hydrogen bonds between cyano groups and non-coordinating amines join the chains by forming R 2 (2)(14) rings.

Reaction of a (Salen)ruthenium(VI) nitrido complex with thiols. C-H bond activation by (Salen)ruthenium(IV) sulfilamido species.

PubMed

Man, Wai-Lun; Lam, William W Y; Kwong, Hoi-Ki; Peng, Shie-Ming; Wong, Wing-Tak; Lau, Tai-Chu

2010-01-04

The reaction of [Ru(VI)(N)(L)(MeOH)](PF(6)) [1; L = N,N'-bis(salicylidene)-o-cyclohexyldiamine dianion] with a stoichiometric amount of RSH in CH(3)CN gives the corresponding (salen)ruthenium(IV) sulfilamido species [Ru(IV){N(H)SR}(L)(NCCH(3))](PF(6)) (2a, R = (t)Bu; 2b, R = Ph). Metathesis of 2a with NaN(3) in methanol affords [Ru(IV){N(H)S(t)Bu}(L)(N(3))] (2c). 2a undergoes further reaction with 1 equiv of RSH to afford a (salen)ruthenium(III) sulfilamine species, [Ru(III){N(H)(2)S(t)Bu}(L)(NCCH(3))](PF(6)) (3). On the other hand, 2b reacts with 2 equiv of PhSH to give a (salen)ruthenium(III) ammine species [Ru(III)(NH(3))(L)(NCCH(3))](PF(6)) (4); this species can also be prepared by treatment of 1 with 3 equiv of PhSH. The X-ray structures of 2c and 4 have been determined. Kinetic studies of the reaction of 1 with excess RSH indicate the following schemes: 1 --> 2a --> 3 (R = (t)Bu), 1 --> 2b --> 4 (R = Ph). The conversion of 1 to 2 probably involves nucleophilic attack of RSH at the nitrido ligand, followed by a proton shift. The conversions of 2a to 3 and 2b to 4 are proposed to involve rate-limiting H-atom abstraction from RSH by 2a or 2b. 2a and 2b are also able to abstract H atoms from hydrocarbons with weak C-H bonds. These reactions occur with large deuterium isotope effects; the kinetic isotope effect values for the oxidation of 9,10-dihydroanthracene, 1,4-cyclohexadiene, and fluorene by 2a are 51, 56, and 11, respectively.

New mixed valence defect dicubane cobalt(II)/cobalt(III) complex: Synthesis, crystal structure, photoluminescence and magnetic properties

NASA Astrophysics Data System (ADS)

Coban, Mustafa Burak; Gungor, Elif; Kara, Hulya; Baisch, Ulrich; Acar, Yasemin

2018-02-01

A new defect dicubane cobalt(II)/cobalt(III), [(CoII2CoIII2L42(H2O)(CH3COO)(CH3COOH]. 4H2O complex (1) where H2L = [1-(3-hydroxypropyliminomethyl)naphthalene-2-ol], has been synthesized and characterized by element analysis, FT-IR, solid UV-Vis spectroscopy and single crystal X-ray diffraction. The crystal structure determination shows a cationic tetrameric arrangement consisting of a defect dicubane core with two missing vertexes. Each cobalt ion has a distorted octahedral geometry with six coordinate ordered CoII and CoIII ions. The solid state photoluminescence properties of complex (1) and its ligand H2L have been investigated under UV light at 349 nm in the visible region. H2L exhibits blue emission while complex (1) shows red emission at room temperature. Variable-temperature magnetic susceptibility measurements on the complex (1) in the range 2-300 K indicate an antiferromagnetic interaction.

Coordination-organometallic hybrid materials based on the trinuclear M(II)-Ru(II) (M=Ni and Zn) complexes: Synthesis, structural characterization, luminescence and electrochemical properties

NASA Astrophysics Data System (ADS)

Pawal, S. B.; Lolage, S. R.; Chavan, S. S.

2018-02-01

A new series of trinuclear complexes of the type Ni[R-C6H4Ndbnd CH(O)C6H3Ctbnd CRu(dppe)2Cl]2 (1a-c) and Zn[Rsbnd C6H4Ndbnd CH(O)C6H3Ctbnd CRu(dppe)2Cl]2 (2a-c) have been prepared from the reaction of trans-[RuCl(dppe)2Ctbnd Csbnd C6H3(OH)(CHO)] (1) with aniline, 4-nitroaniline and 4-methoxyaniline (R1-3) in presence of nickel acetate and zinc acetate in CH2Cl2/MeOH (1:1) mixture. The structural properties of the complexes have been characterized by elemental analyses and spectroscopic techniques viz. FTIR, UV-Visible, 1H NMR and 31P NMR spectral studies. The crystal structure and morphology of the hybrid complexes was investigated with the help of X-ray powder diffraction (XRPD), Scanning electron microscopy (SEM) and Transmission electron microscopy (TEM). The thermal properties of 1a-c and 2a-c were studied by thermogravimetric (TG) analysis. The electrochemical behaviour of the complexes reveals that all complexes displayed a quasireversible redox behaviour corresponding to Ru(II)/Ru(III) and Ni(II)/Ni(III) couples for 1a-c and only Ru(II)/Ru(III) couple for 2a-c. All complexes are emissive in solution at room temperature revealing the influence of substituents and solvent polarity on emission properties of the complexes.

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.

Electroremovable Traceless Hydrazides for Cobalt-Catalyzed Electro-Oxidative C-H/N-H Activation with Internal Alkynes.

PubMed

Mei, Ruhuai; Sauermann, Nicolas; Oliveira, João C A; Ackermann, Lutz

2018-06-27

Electrochemical oxidative C-H/N-H activations have been accomplished with a versatile cobalt catalyst in terms of [4 + 2] annulations of internal alkynes. The electro-oxidative C-H activation manifold proved viable with an undivided cell setup under exceedingly mild reaction conditions at room temperature using earth-abundant cobalt catalysts. The electrochemical cobalt catalysis prevents the use of transition metal oxidants in C-H activation catalysis, generating H 2 as the sole byproduct. Detailed mechanistic studies provided strong support for a facile C-H cobaltation by an initially formed cobalt(III) catalyst. The subsequent alkyne migratory insertion was interrogated by mass spectrometry and DFT calculations, providing strong support for a facile C-H activation and the formation of a key seven-membered cobalta(III) cycle in a regioselective fashion. Key to success for the unprecedented use of internal alkynes in electrochemical C-H/N-H activations was represented by the use of N-2-pyridylhydrazides, for which we developed a traceless electrocleavage strategy by electroreductive samarium catalysis at room temperature.

Halide addition/abstraction in phosphido derivatives: isolation of the thallium and silver intermediates.

PubMed

Forniés, Juan; Fortuño, Consuelo; Ibáñez, Susana; Martín, Antonio

2008-07-07

Reaction of unsaturated (44e (-) skeleton) [PdPt 2(mu-PPh 2) 2(mu-P 2Ph 4)(R F) 4] 4 with Br (-) produces the saturated (48e (-) skeleton) complex [NBu 4][(R F) 2Pt(mu-PPh 2)(mu-Br)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 5 without any M-M' bond. Attempts to eliminate Br (-) of 5 with Ag (+) in CH 2Cl 2 as a solvent gives a mixture of [(R F) 2Pt (III)(mu-PPh 2) 2Pt (III)(R F) 2] and some other unidentified products as a consequence of oxidation and partial fragmentation. However, when the reaction of 5 with Ag (+) is carried out in CH 3CN, no oxidation is observed but the elimination of Br (-) and the formation of [(R F) 2(CH 3CN)Pt(mu-PPh 2)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 6 (46e (-) skeleton), a complex with a Pt-Pd bond, takes place. It is noteworthy that the reaction of 5 with TlPF 6 in CH 2Cl 2 does not precipitate TlBr but forms the adduct [(R F) 2PtTl(mu-PPh 2)(mu-Br)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 7 with a Pt-Tl bond. Likewise, 5 reacts with [AgOClO 3(PPh 3)] in CH 2Cl 2 forming the adduct [AgPdPt 2(mu-Br)(mu-PPh 2) 2(mu-Ph 2P-PPh 2)(R F) 4(PPh 3)] 8, which contains a Pt-Ag bond. Both adducts are unstable in a CH 3CN solution, precipitating TlBr or AgBr and yielding the unsaturated 6. The treatment of [NBu 4] 2[(R F) 2Pt(mu-PPh 2) 2Pd(mu-PPh 2) 2Pt(R F) 2] in CH 3CN with I 2 (1:1 molar ratio) at 233 K yields a mixture of 4 and 6, which after recrystallization from CH 2Cl 2 is totally converted in 4. If the reaction with I 2 is carried out at room temperature, a mixture of the isomers [NBu 4][(R F) 2Pt(mu-PPh 2)(mu-I)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 9 and [NBu 4][(R F)(PPh 2R F)Pt(mu-PPh 2)(mu-I)Pd(mu-PPh 2) 2Pt(R F) 2] 10 are obtained. The structures of the complexes have been established on the bases of NMR data, and the X-ray structures of 5- 8 have been studied. The relationship between the different complexes has been studied.

Univariate and multivariate molecular spectral analyses of lipid related molecular structural components in relation to nutrient profile in feed and food mixtures

NASA Astrophysics Data System (ADS)

Abeysekara, Saman; Damiran, Daalkhaijav; Yu, Peiqiang

2013-02-01

The objectives of this study were (i) to determine lipid related molecular structures components (functional groups) in feed combination of cereal grain (barley, Hordeum vulgare) and wheat (Triticum aestivum) based dried distillers grain solubles (wheat DDGSs) from bioethanol processing at five different combination ratios using univariate and multivariate molecular spectral analyses with infrared Fourier transform molecular spectroscopy, and (ii) to correlate lipid-related molecular-functional structure spectral profile to nutrient profiles. The spectral intensity of (i) CH3 asymmetric, CH2 asymmetric, CH3 symmetric and CH2 symmetric groups, (ii) unsaturation (Cdbnd C) group, and (iii) carbonyl ester (Cdbnd O) group were determined. Spectral differences of functional groups were detected by hierarchical cluster analysis (HCA) and principal components analysis (PCA). The results showed that the combination treatments significantly inflicted modifications (P < 0.05) in nutrient profile and lipid related molecular spectral intensity (CH2 asymmetric stretching peak height, CH2 symmetric stretching peak height, ratio of CH2 to CH3 symmetric stretching peak intensity, and carbonyl peak area). Ratio of CH2 to CH3 symmetric stretching peak intensity, and carbonyl peak significantly correlated with nutrient profiles. Both PCA and HCA differentiated lipid-related spectrum. In conclusion, the changes of lipid molecular structure spectral profiles through feed combination could be detected using molecular spectroscopy. These changes were associated with nutrient profiles and functionality.

Emission of greenhouse gases from controlled incineration of cattle manure.

PubMed

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

2012-01-01

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

Synthesis of Antidotes and Prophylactics for Organophosphorus Acetylcholinesterase Inhibitors

DTIC Science & Technology

1996-01-01

Choline A nalogs .............................................. 13 D . M iscellaneous Com pounds...27b 27c (PN-III-28) CH(CH3 )2 TsO 28a 28b 28c (PN-II-258) Ph I C. Carbamoyl enolates of Choline Analogs The enolates of 1-methyl-3-piperidone and 1...sodium bicarbonate solution. The crystalline solid obtained was filtered and dried to give 4.5 g (77%) of the amine. 6-Benzoyloxyimidazo[1,2-a]pyridine

Water-Stable In(III)-Based Metal-Organic Frameworks with Rod-Shaped Secondary Building Units: Single-Crystal to Single-Crystal Transformation and Selective Sorption of C2H2 over CO2 and CH4.

PubMed

Guo, Zhen-Ji; Yu, Jiamei; Zhang, Yong-Zheng; Zhang, Jian; Chen, Ya; Wu, Yufeng; Xie, Lin-Hua; Li, Jian-Rong

2017-02-20

Three new water-stable In(III)-based metal-organic frameworks, namely, [In 3 (TTTA) 2 (OH) 3 (H 2 O)]·(DMA) 3 (BUT-70, DMA = N,N-dimethylacetamide), [In 3 (TTTA) 2 (CH 3 O) 3 ] (BUT-70A), and [In 3 (TTTA) 2 (OH) 3 ] (BUT-70B), with rod-shaped secondary building units (SBUs) and an new acrylate-based ligand, (2E,2'E,2″E)-3,3',3″-(2,4,6-trimethylbenzene-1,3,5-triyl)-triacrylate (TTTA 3- ) were obtained and structurally characterized. BUT-70A and -70B were generated in a single-crystal to single-crystal transformation fashion from BUT-70 through guest exchange followed by their removal. The solvents used for guest exchange were methanol and dichloromethane, respectively. Single-crystal structure analyses show that the guest exchange and removal process is accompanied by the substitution of coordinated water molecules of In(III) centers with uncoordinated carboxylate O atoms of TTTA 3- ligands. Moreover, hydroxyl groups bridging two In(III) centers are also replaced by methoxyl groups in the transformation from BUT-70 to -70A. Overall, three metal-organic frameworks (MOFs) are constructed by infinite chains consisting of corner-sharing InO 4 (OR) 2 (R = H or Me) octahedral entities, which are interconnected by TTTA 3- ligands to form three-dimensional frameworks. Unlike most reported MOFs with infinite chains as SBUs, such as well-known MIL-53 and M-MOF-74, which have one-dimensional channels along the chain direction, the BUT-70 series contain two-dimensional intersecting channels. The Brunauer-Emmett-Teller surface area and pore volume of BUT-70A were estimated to be 460 m 2 g -1 and 0.18 cm 3 g -1 , respectively, which are obviously lower than those of BUT-70B (695 m 2 g -1 and 0.29 cm 3 g -1 ). Gas adsorption experiments demonstrated that BUT-70A and -70B are able to selectively adsorb C 2 H 2 over CO 2 and CH 4 . At 1 atm and 298 K, BUT-70A uptakes 3.1 mmol g -1 C 2 H 2 , which is 3.6 times that of the CO 2 uptake and 7.2 times that of the CH 4 uptake. Compared with BUT-70A, BUT-70B presents an even higher C 2 H 2 uptake of 3.9 mmol g -1 at the same conditions, but slightly lower Ideal Adsorbed Solution Theory C 2 H 2 /CO 2 and C 2 H 2 /CH 4 selectivities.

[Ni III(OMe)]-mediated reductive activation of CO 2 affording a Ni(κ 1-OCO) complex

DOE PAGES

Chiou, Tzung -Wen; Tseng, Yen -Ming; Lu, Tsai -Te; ...

2016-02-24

Here, carbon dioxide is expected to be employed as an inexpensive and potential feedstock of C 1 sources for the mass production of valuable chemicals and fuel. Versatile chemical transformations of CO 2, i.e. insertion of CO 2 producing bicarbonate/acetate/formate, cleavage of CO 2 yielding μ-CO/μ-oxo transition-metal complexes, and electrocatalytic reduction of CO 2 affording CO/HCOOH/CH 3OH/CH 4/C 2H 4/oxalate were well documented. Herein, we report a novel pathway for the reductive activation of CO 2 by the [Ni III(OMe)(P(C 6H 3-3-SiMe 3-2-S) 3)] – complex, yielding the [Ni III(κ 1-OCO˙ –)(P(C 6H 3-3-SiMe 3-2-S) 3)] – complex. The formationmore » of this unusual Ni III(κ 1-OCO ˙–) complex was characterized by single-crystal X-ray diffraction, EPR, IR, SQUID, Ni/S K-edge X-ray absorption spectroscopy, and Ni valence-to-core X-ray emission spectroscopy. The inertness of the analogous complexes [Ni III(SPh)], [Ni II(CO)], and [Ni II(N 2H 4)] toward CO 2, in contrast, demonstrates that the ionic [Ni III(OMe)] core attracts the binding of weak σ-donor CO 2 and triggers the subsequent reduction of CO 2 by the nucleophilic [OMe] – in the immediate vicinity. This metal–ligand cooperative activation of CO 2 may open a novel pathway promoting the subsequent incorporation of CO 2 in the buildup of functionalized products.« less

Kinetics of the reduction of cobalt(III) amine complexes by 1-hydroxy-1-methylethyl radicals

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

Kusaba, K.; Ogino, Hiroshi; Bakac, A.

1989-03-08

In order to better understand the rate constants for the reduction of several cobalt complexes by 1-hydroxy-1-methylene radicals ({sup {sm bullet}}C(CH{sub 3}){sub 2}OH), the reactions of {sup {sm bullet}}(CH{sub 3}){sub 2}OH with several cobalt(III) complexes of bidentate amines have been studied. The Marcus-Hush theory was deemed the most appropriate for analysis of the kinetic data. The correlation between the kinetics of the reduction of the Co(III) amines by C(CH{sub 3}){sub 2}OH and the reduction of the first d-d band for Co(III) complexes is discussed. 21 refs., 2 figs., 1 tab.

Oxidation of Half-Lantern Pt2(II,II) Compounds by Halocarbons. Evidence of Dioxygen Insertion into a Pt(III)-CH3 Bond.

PubMed

Sicilia, V; Baya, M; Borja, P; Martín, A

2015-08-03

The half-lantern compound [{Pt(bzq)(μ-N^S)}2] (1) [bzq = benzo[h]quinoline, HN^S = 2-mercaptopyrimidine (C4H3N2HS)] reacts with CH3I and haloforms CHX3 (X = Cl, Br, I) to give the corresponding oxidized diplatinum(III) derivatives [{Pt(bzq)(μ-N^S)X}2] (X = Cl 2a, Br 2b, I 2c). These compounds exhibit half-lantern structures with short intermetallic distances (∼2.6 Å) due to Pt-Pt bond formation. The halogen abstraction mechanisms from the halocarbon molecules by the Pt2(II,II) compound 1 were investigated. NMR spectroscopic evidence using labeled reagents support that in the case of (13)CH3I the reaction initiates with an oxidative addition through an SN2 mechanism giving rise to the intermediate species [I(bzq)Pt(μ-N^S)2Pt(bzq)((13)CH3)}]. However, with haloforms the reactions proceed through a radical-like mechanism, thermally (CHBr3, CHI3) or photochemically (CHCl3) activated, giving rise to mixtures of species [X(bzq)Pt(μ-N^S)2Pt(bzq)R] (3a-c) and [X(bzq)Pt(μ-N^S)2Pt(bzq)X] (2a-c). In these cases the presence of O2 favors the formation of species 2 over 3. Transformation of 3 into 2 was possible upon irradiation with UV light. In the case of [I(bzq)Pt(μ-N^S)2Pt(bzq)((13)CH3)}] (3d), in the presence of O2 the formation of the unusual methylperoxo derivative [I(bzq)Pt(μ-N^S)2Pt(bzq)(O-O(13)CH3)}] (4d) was detected, which in the presence of (13)CH3I rendered the final product [{Pt(bzq)(μ-N^S)I}2] (2c) and (13)CH3OH.

Synthesis, structural characterisation and magnetic studies of polymetallic iron phosphonate cages.

PubMed

Khanra, Sumit; Helliwell, Madeleine; Tuna, Floriana; McInnes, Eric J L; Winpenny, Richard E P

2009-08-21

Four new polymetallic iron(III) phosphonate cages have been made and structurally characterised. These are an octanuclear cage [Fe(8)O(3)(OH)(2)(O(2)C(t)Bu)(11)(PhCH(2)PO(3))(3)(py)(3)], a decanuclear cage [Fe(10)O(2)(OH)(8)(O(2)C(t)Bu)(10)(PhCH(2)PO(3))(4)(pip)(2)], a heterometallic cage [Fe(6)Li(5)(mu(3)-O)(2)((t)BuPO(3))(6)(O(2)C(t)Bu)(8)(MeOH)(2)(Py)(4)] and a tridecanuclear cage [Et(3)NH](2)[Fe(13)(mu(3)-O)(3)(mu(2)-OH)(7)((t)BuPO(3))(7)(Me(3)CCO(2))(14)(H(2)O)] (pip = piperidine, py = pyridine). Magnetic studies of the first three compounds show anti-ferromagnetic exchange between the iron(III) centers leading to diamagnetic ground states for the homometallic cages. For the heterometallic cage, the six Fe(III) centers are arranged in two triangles, and each triangle has an S = 1/2 spin ground state.

Silica-Supported, Single-Site Sc and Y Alkyls for Catalytic Hydrogenation of Propylene

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

Getsoian, Andrew G. Bean; Hu, Bo; Miller, Jeffrey T.

Single site Sc and Y on silica catalysts have been prepared by aqueous and organometallic grafting methods. The former yields Y(III) ions with 5 bonds at an average bond distance of 2.31 Å by X-ray absorption spectroscopy. Although the aqueous synthesis gave single site Y with low coordination number, these were not catalytic for alkane dehydrogenation or olefin hydrogenation. Single site Sc(III) and Y(III) species were also prepared by grafting Sc(CH 2Si(CH 3) 3) 3(THF) 2 and Y(CH 2Si(CH 3) 3) 3(THF) 2, respectively and these are catalysts for olefin hydrogenation at temperatures from about 60 to 100°C; however, theymore » were thermally unstable at higher temperatures necessary for alkane dehydrogenation. The structure of the grafted Y complex was determined by X-ray absorption spectroscopy, IR, and NMR. Grafting lead to protonolysis of 2 of the 3 CH 2Si(CH 3) 3 ligands. Additionally, there was loss of one THF ligand. The EXAFS indicated that there were 4 Y-ligand bonds in the surface species, 2 at 2.16 Å and 2 at 2.39 Å. The metal-alkyl ligand was thought to be necessary for catalytic activity and likely proceeds through a sigma bond metathesis mechanism. In the single site centers without alkyl bonds, Sc and Y ions cannot generate metal-alkyl, or metal-hydride, moieties in situ. We conclude that this is likely due to the very high M-O-Si bond strengths, which must be broken through heterolytic dissociation of C-H bonds during alkane activation for either alkane dehydrogenation or olefin hydrogenation reactions. Lastly, this study demonstrates the importance of pre-catalyst choice versus in situ formation of reactive intermediates to produce active catalysts for alkane bond activation.« less

Silica-Supported, Single-Site Sc and Y Alkyls for Catalytic Hydrogenation of Propylene

DOE PAGES

Getsoian, Andrew G. Bean; Hu, Bo; Miller, Jeffrey T.; ...

2017-09-27

Single site Sc and Y on silica catalysts have been prepared by aqueous and organometallic grafting methods. The former yields Y(III) ions with 5 bonds at an average bond distance of 2.31 Å by X-ray absorption spectroscopy. Although the aqueous synthesis gave single site Y with low coordination number, these were not catalytic for alkane dehydrogenation or olefin hydrogenation. Single site Sc(III) and Y(III) species were also prepared by grafting Sc(CH 2Si(CH 3) 3) 3(THF) 2 and Y(CH 2Si(CH 3) 3) 3(THF) 2, respectively and these are catalysts for olefin hydrogenation at temperatures from about 60 to 100°C; however, theymore » were thermally unstable at higher temperatures necessary for alkane dehydrogenation. The structure of the grafted Y complex was determined by X-ray absorption spectroscopy, IR, and NMR. Grafting lead to protonolysis of 2 of the 3 CH 2Si(CH 3) 3 ligands. Additionally, there was loss of one THF ligand. The EXAFS indicated that there were 4 Y-ligand bonds in the surface species, 2 at 2.16 Å and 2 at 2.39 Å. The metal-alkyl ligand was thought to be necessary for catalytic activity and likely proceeds through a sigma bond metathesis mechanism. In the single site centers without alkyl bonds, Sc and Y ions cannot generate metal-alkyl, or metal-hydride, moieties in situ. We conclude that this is likely due to the very high M-O-Si bond strengths, which must be broken through heterolytic dissociation of C-H bonds during alkane activation for either alkane dehydrogenation or olefin hydrogenation reactions. Lastly, this study demonstrates the importance of pre-catalyst choice versus in situ formation of reactive intermediates to produce active catalysts for alkane bond activation.« less

Naringin Mitigates Cardiac Hypertrophy by Reducing Oxidative Stress and Inactivating c-Jun Nuclear Kinase-1 Protein in Type I Diabetes.

PubMed

Adebiyi, A Olubunmi; Adebiyi, Oluwafeysetan O; Owira, Peter M O

2016-02-01

Cardiac hypertrophy (CH) in type 1 diabetes mellitus is attributed to increased oxidative stress-associated activation of c-Jun Nuclear Kinase (JNK). We investigated the effects of naringin on hyperglycemia-associated oxidative stress, activation of JNK-1, and CH. Male Sprague-Dawley rats (225-250 g) (n = 7) were divided into 6 groups. Groups I and II were orally treated with distilled water [3.0 mL/kg body weight/day (BW)] and naringin (50 mg/kg BW), respectively. Groups III-VI were rendered diabetic by a single intraperitoneal injection of 65 mg/kg BW of streptozotocin. Groups III, IV, and V were further treated with insulin (4.0 I.U, s.c, twice daily), naringin (50 mg/kg BW), and ramipril (3.0 mg/kg BW), respectively. After 56 days, the animals were sacrificed and then plasma and cardiac tissues obtained for further analysis. Naringin treatment of diabetic rats significantly reversed oxidative stress, lipid peroxidation, proteins oxidation, CH indices, and JNK protein activation compared with untreated diabetic animals. Our results do suggest that naringin mitigates CH by inhibiting oxidative stress leading to inactivation of JNK-1. Naringin supplements could therefore ameliorate CH in diabetic patients.

Ring opening of azetidine cycle: First examples of 1-azetidinepropanamine molecules as a template in hybrid organic-inorganic compounds

NASA Astrophysics Data System (ADS)

Gurzhiy, Vladislav V.; Tyumentseva, Olga S.; Britvin, Sergey N.; Krivovichev, Sergey V.; Tananaev, Ivan G.

2018-01-01

Three novel uranyl selenate and sulfate oxysalts templated by protonated azetidine molecules, [AzH]+, and its ring-opened counterpart 1-azetidinepropanamine, [AzH(CH2)3NH3]2+, have been prepared and studied by X-ray structural analysis. Conformations of azetidinium cations were analysed by means of infrared vibrational assignments supported by the DFT calculations. Crystallization of [AzH]2 [(UO2)2(SeO4)3(H2O)] (I) from highly acidic solutions suggests that low pH does not necessarily result in the opening of azetidine ring. [AzH(CH2)3NH3][(UO2)2(SeO4)3(H2O)](H2O) (II) and [AzH(CH2)3NH3](H5O2)[(UO2)2(SO4)3(HSO4)] (III) are the first structurally characterized crystalline compounds bearing isolated ring-opened azetidine moiety.

Te(II)/Te(IV) Mediated C-N Bond Formation on 2,5-Diphenyltellurophene and a Reassignment of the Product from the Reaction of PhI(OAc)2 with 2 TMS-OTf.

PubMed

Aprile, Antonino; Iversen, Kalon J; Wilson, David J D; Dutton, Jason L

2015-05-18

We report a novel C-H to C-N bond metathesis at the 3-position of 1,2-diphenyltellurophene via oxidation of the Te(II) center to Te(IV) using the I(III) oxidant [PhI(4-DMAP)2](2+). Spontaneous reduction of a transient Te(IV) coordination compound to Te(II) generates an electrophilic equivalent of 4-DMAP that substitutes at a C-H bond at the 3-position of the tellurophene. Theoretical and synthetic reaction pathway studies confirm that a Te(IV) coordination complex with 4-DMAP is an intermediate. In the course of these pathway studies, it was also found that the identity of the I(III) oxidant generated from PhI(OAc)2 and 2 TMS-OTf is PhI(OAc)(OTf) and not PhI(OTf)2, as had been previously thought.

Quenching the Quantum Tunneling of Magnetization in Heterometallic Octanuclear {TMIII4 DyIII4 } (TM=Co and Cr) Single-Molecule Magnets by Modification of the Bridging Ligands and Enhancing the Magnetic Exchange Coupling.

PubMed

Vignesh, Kuduva R; Langley, Stuart K; Murray, Keith S; Rajaraman, Gopalan

2017-01-31

We report the synthesis, structural characterisation, magnetic properties and provide an ab initio analysis of the magnetic behaviour of two new heterometallic octanuclear coordination complexes containing Co III and Dy III ions. Single-crystal X-ray diffraction studies revealed molecular formulae of [Co III 4 Dy III 4 (μ-OH) 4 (μ 3 -OMe) 4 {O 2 CC(CH 3 ) 3 } 4 (tea) 4 (H 2 O) 4 ]⋅4 H 2 O (1) and [Co III 4 Dy III 4 (μ-F) 4 (μ 3 -OH) 4 (o-tol) 8 (mdea) 4 ]⋅ 3 H 2 O⋅EtOH⋅MeOH (2; tea 3- =triply deprotonated triethanolamine; mdea 2- =doubly deprotonated N-methyldiethanolamine; o-tol=o-toluate), and both complexes display an identical metallic core topology. Furthermore, the theoretical, magnetic and SMM properties of the isostructural complex, [Cr III 4 Dy III 4 (μ-F 4 )(μ 3 -OMe) 1.25 (μ 3 -OH) 2.75 (O 2 CPh) 8 (mdea) 4 ] (3), are discussed and compared with a structurally similar complex, [Cr III 4 Dy III 4 (μ 3 -OH) 4 (μ-N 3 ) 4 (mdea) 4 (O 2 CC(CH 3 ) 3 ) 4 ] (4). DC and AC magnetic susceptibility data revealed single-molecule magnet (SMM) behaviour for 1-4. Each complex displays dynamic behaviour, highlighting the effect of ligand and transition metal ion replacement on SMM properties. Complexes 2, 3 and 4 exhibited slow magnetic relaxation with barrier heights (U eff ) of 39.0, 55.0 and 10.4 cm -1 respectively. Complex 1, conversely, did not exhibit slow relaxation of magnetisation above 2 K. To probe the variance in the observed U eff  values, calculations by using CASSCF, RASSI-SO and POLY_ANISO routine were performed on these complexes to estimate the nature of the magnetic coupling and elucidate the mechanism of magnetic relaxation. Calculations gave values of J Dy-Dy as -1.6, 1.6 and 2.8 cm -1 for complexes 1, 2 and 3, respectively, whereas the J Dy-Cr interaction was estimated to be -1.8 cm -1 for complex 3. The developed mechanism for magnetic relaxation revealed that replacement of the hydroxide ion by fluoride quenched the quantum tunnelling of magnetisation (QTM) significantly, and led to improved SMM properties for complex 2 compared with 1. However, the tunnelling of magnetisation at low-lying excited states was still operational for 2, which led to low-temperature QTM relaxation. Replacement of the diamagnetic Co III ions with paramagnetic Cr III led to Cr III ⋅⋅⋅Dy III coupling, which resulted in quenching of QTM at low temperatures for complexes 3 and 4. The best example was found if both Cr III and fluoride were present, as seen for complex 3, for which both factors additively quenched QTM and led to the observation of highly coercive magnetic hysteresis loops above 2 K. Herein, we propose a synthetic strategy to quench the QTM effects in lanthanide-based SMMs. Our strategy differs from existing methods, in which parameters such as magnetic coupling are difficult to control, and it is likely to have implications beyond the Dy III SMMs studied herein. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

METHANE EMISSIONS FROM THE NATURAL GAS INDUSTRY VOLUME 4: STATISTICAL METHODOLOGY

EPA Science Inventory

The 15-volume report summarizes the results of a comprehensive program to quantify methane (CH4) emissions from the U.S. natural gas industry for the base year. The objective was to determine CH4 emissions from the wellhead and ending downstream at the customer's meter. The accur...

Intramolecular Dynamics: A Study of Molecules at High Levels of Vibrational Excitation.

DTIC Science & Technology

1988-05-27

aareemlent stith the photoa.couxueC rexults.,I4 % obintied t r iii pfii ioaCOI it tic tveaxu retntsx." Si ne thle xhoxs xthat Iii the I ott fi nence...t 0 200 400 ns 6000 between pump and probe pulse for CH3 CHF2 at 660 Pa. Infrared excitation: 10.6 pim P(20) line, 0.5 ns pulse with average fluence

Insertion of a single-molecule magnet inside a ferromagnetic lattice based on a 3D bimetallic oxalate network: towards molecular analogues of permanent magnets.

PubMed

Clemente-León, Miguel; Coronado, Eugenio; Gómez-García, Carlos J; López-Jordà, Maurici; Camón, Agustín; Repollés, Ana; Luis, Fernando

2014-02-03

The insertion of the single-molecule magnet (SMM) [Mn(III)(salen)(H2O)]2(2+) (salen(2-) = N,N'-ethylenebis-(salicylideneiminate)) into a ferromagnetic bimetallic oxalate network affords the hybrid compound [Mn(III)(salen)(H2O)]2[Mn(II)Cr(III)(ox)3]2⋅(CH3OH)⋅(CH3CN)2 (1). This cationic Mn2 cluster templates the growth of crystals formed by an unusual achiral 3D oxalate network. The magnetic properties of this hybrid magnet are compared with those of the analogous compounds [Mn(III)(salen)(H2O)]2[Zn(II)Cr(III)(ox)3]2⋅(CH3OH)⋅(CH3CN)2 (2) and [In(III)(sal2-trien)][Mn(II)Cr(III)(ox)3]⋅(H2O)0.25⋅(CH3OH)0.25⋅(CH3CN)0.25 (3), which are used as reference compounds. In 2 it has been shown that the magnetic isolation of the Mn2 clusters provided by their insertion into a paramagnetic oxalate network of Cr(III) affords a SMM behavior, albeit with blocking temperatures well below 500 mK even for frequencies as high as 160 kHz. In 3 the onset of ferromagnetism in the bimetallic Mn(II) Cr(III) network is observed at Tc = 5 K. Finally, in the hybrid compound 1 the interaction between the two magnetic networks leads to the antiparallel arrangement of their respective magnetizations, that is, to a ferrimagnetic phase. This coupling induces also important changes on the magnetic properties of 1 with respect to those of the reference compounds 2 and 3. In particular, compound 1 shows a large magnetization hysteresis below 1 K, which is in sharp contrast with the near-reversible magnetizations that the SMMs and the oxalate ferromagnetic lattice show under the same conditions. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Univariate and multivariate molecular spectral analyses of lipid related molecular structural components in relation to nutrient profile in feed and food mixtures.

PubMed

Abeysekara, Saman; Damiran, Daalkhaijav; Yu, Peiqiang

2013-02-01

The objectives of this study were (i) to determine lipid related molecular structures components (functional groups) in feed combination of cereal grain (barley, Hordeum vulgare) and wheat (Triticum aestivum) based dried distillers grain solubles (wheat DDGSs) from bioethanol processing at five different combination ratios using univariate and multivariate molecular spectral analyses with infrared Fourier transform molecular spectroscopy, and (ii) to correlate lipid-related molecular-functional structure spectral profile to nutrient profiles. The spectral intensity of (i) CH(3) asymmetric, CH(2) asymmetric, CH(3) symmetric and CH(2) symmetric groups, (ii) unsaturation (CC) group, and (iii) carbonyl ester (CO) group were determined. Spectral differences of functional groups were detected by hierarchical cluster analysis (HCA) and principal components analysis (PCA). The results showed that the combination treatments significantly inflicted modifications (P<0.05) in nutrient profile and lipid related molecular spectral intensity (CH(2) asymmetric stretching peak height, CH(2) symmetric stretching peak height, ratio of CH(2) to CH(3) symmetric stretching peak intensity, and carbonyl peak area). Ratio of CH(2) to CH(3) symmetric stretching peak intensity, and carbonyl peak significantly correlated with nutrient profiles. Both PCA and HCA differentiated lipid-related spectrum. In conclusion, the changes of lipid molecular structure spectral profiles through feed combination could be detected using molecular spectroscopy. These changes were associated with nutrient profiles and functionality. Copyright © 2012 Elsevier B.V. All rights reserved.

A multiplicity of factors contributes to selective RNA polymerase III occupancy of a subset of RNA polymerase III genes in mouse liver

PubMed Central

Canella, Donatella; Bernasconi, David; Gilardi, Federica; LeMartelot, Gwendal; Migliavacca, Eugenia; Praz, Viviane; Cousin, Pascal; Delorenzi, Mauro; Hernandez, Nouria; Hernandez, Nouria; Delorenzi, Mauro; Deplancke, Bart; Desvergne, Béatrice; Guex, Nicolas; Herr, Winship; Naef, Felix; Rougemont, Jacques; Schibler, Ueli; Deplancke, Bart; Guex, Nicolas; Herr, Winship; Guex, Nicolas; Andersin, Teemu; Cousin, Pascal; Gilardi, Federica; Gos, Pascal; Le Martelot, Gwendal; Lammers, Fabienne; Canella, Donatella; Gilardi, Federica; Raghav, Sunil; Fabbretti, Roberto; Fortier, Arnaud; Long, Li; Vlegel, Volker; Xenarios, Ioannis; Migliavacca, Eugenia; Praz, Viviane; Guex, Nicolas; Naef, Felix; Rougemont, Jacques; David, Fabrice; Jarosz, Yohan; Kuznetsov, Dmitry; Liechti, Robin; Martin, Olivier; Ross, Frederick; Sinclair, Lucas; Cajan, Julia; Krier, Irina; Leleu, Marion; Migliavacca, Eugenia; Molina, Nacho; Naldi, Aurélien; Rey, Guillaume; Symul, Laura; Guex, Nicolas; Naef, Felix; Rougemont, Jacques; Bernasconi, David; Delorenzi, Mauro; Andersin, Teemu; Canella, Donatella; Gilardi, Federica; Le Martelot, Gwendal; Lammers, Fabienne; Raghav, Sunil

2012-01-01

The genomic loci occupied by RNA polymerase (RNAP) III have been characterized in human culture cells by genome-wide chromatin immunoprecipitations, followed by deep sequencing (ChIP-seq). These studies have shown that only ∼40% of the annotated 622 human tRNA genes and pseudogenes are occupied by RNAP-III, and that these genes are often in open chromatin regions rich in active RNAP-II transcription units. We have used ChIP-seq to characterize RNAP-III-occupied loci in a differentiated tissue, the mouse liver. Our studies define the mouse liver RNAP-III-occupied loci including a conserved mammalian interspersed repeat (MIR) as a potential regulator of an RNAP-III subunit-encoding gene. They reveal that synteny relationships can be established between a number of human and mouse RNAP-III genes, and that the expression levels of these genes are significantly linked. They establish that variations within the A and B promoter boxes, as well as the strength of the terminator sequence, can strongly affect RNAP-III occupancy of tRNA genes. They reveal correlations with various genomic features that explain the observed variation of 81% of tRNA scores. In mouse liver, loci represented in the NCBI37/mm9 genome assembly that are clearly occupied by RNAP-III comprise 50 Rn5s (5S RNA) genes, 14 known non-tRNA RNAP-III genes, nine Rn4.5s (4.5S RNA) genes, and 29 SINEs. Moreover, out of the 433 annotated tRNA genes, half are occupied by RNAP-III. Transfer RNA gene expression levels reflect both an underlying genomic organization conserved in dividing human culture cells and resting mouse liver cells, and the particular promoter and terminator strengths of individual genes. PMID:22287103

Overexpression of 3-Ketoacyl-Acyl-Carrier Protein Synthase IIIs in Plants Reduces the Rate of Lipid Synthesis1

PubMed Central

Dehesh, Katayoon; Tai, Heeyoung; Edwards, Patricia; Byrne, James; Jaworski, Jan G.

2001-01-01

A cDNA coding for 3-ketoacyl-acyl-carrier protein (ACP) synthase III (KAS III) from spinach (Spinacia oleracea; So KAS III) was used to isolate two closely related KAS III clones (Ch KAS III-1 and Ch KAS III-2) from Cuphea hookeriana. Both Ch KAS IIIs are expressed constitutively in all tissues examined. An increase in the levels of 16:0 was observed in tobacco (Nicotiana tabacum, WT-SR) leaves overexpressing So KAS III when under the control of the cauliflower mosaic virus-35S promoter and in Arabidopsis and rapeseed (Brassica napus) seeds overexpressing either of the Ch KAS IIIs driven by napin. These data indicate that this enzyme has a universal role in fatty acid biosynthesis, irrespective of the plant species from which it is derived or the tissue in which it is expressed. The transgenic rapeseed seeds also contained lower levels of oil as compared with the wild-type levels. In addition, the rate of lipid synthesis in transgenic rapeseed seeds was notably slower than that of the wild-type seeds. The results of the measurements of the levels of the acyl-ACP intermediates as well as any changes in levels of other fatty acid synthase enzymes suggest that malonyl-ACP, the carbon donor utilized by all the 3- ketoacyl-ACP synthases, is limiting in the transgenic plants. This further suggests that malonyl-coenzyme A is a potential limiting factor impacting the final oil content as well as further extension of 16:0. PMID:11161065

Overexpression of 3-ketoacyl-acyl-carrier protein synthase IIIs in plants reduces the rate of lipid synthesis.

PubMed

Dehesh, K; Tai, H; Edwards, P; Byrne, J; Jaworski, J G

2001-02-01

A cDNA coding for 3-ketoacyl-acyl-carrier protein (ACP) synthase III (KAS III) from spinach (Spinacia oleracea; So KAS III) was used to isolate two closely related KAS III clones (Ch KAS III-1 and Ch KAS III-2) from Cuphea hookeriana. Both Ch KAS IIIs are expressed constitutively in all tissues examined. An increase in the levels of 16:0 was observed in tobacco (Nicotiana tabacum, WT-SR) leaves overexpressing So KAS III when under the control of the cauliflower mosaic virus-35S promoter and in Arabidopsis and rapeseed (Brassica napus) seeds overexpressing either of the Ch KAS IIIs driven by napin. These data indicate that this enzyme has a universal role in fatty acid biosynthesis, irrespective of the plant species from which it is derived or the tissue in which it is expressed. The transgenic rapeseed seeds also contained lower levels of oil as compared with the wild-type levels. In addition, the rate of lipid synthesis in transgenic rapeseed seeds was notably slower than that of the wild-type seeds. The results of the measurements of the levels of the acyl-ACP intermediates as well as any changes in levels of other fatty acid synthase enzymes suggest that malonyl-ACP, the carbon donor utilized by all the 3- ketoacyl-ACP synthases, is limiting in the transgenic plants. This further suggests that malonyl-coenzyme A is a potential limiting factor impacting the final oil content as well as further extension of 16:0.

Effect of iron(III) ion on moso bamboo pyrolysis under microwave irradiation.

PubMed

Dong, Qing; Li, Xiangqian; Wang, Zhaoyu; Bi, Yanhong; Yang, Rongling; Zhang, Jinfeng; Luo, Hongzhen; Niu, Miaomiao; Qi, Bo; Lu, Chen

2017-11-01

The effect of iron(III) ion on microwave pyrolysis of moso bamboo was investigated. Hydrofluoric acid washing was used as a pilot process to demineralize moso bamboo in order to eliminate the influences of the other inorganics contained in moso bamboo itself. The results indicated that the addition of iron(III) ion increased the maximal reaction temperatures under microwave condition dependent on the amount of the added iron(III) ion. The production of the non-condensable gases was promoted by the addition of iron(III) ion mainly at the expense of liquid products. Iron(III) ion exhibited the positive effect for syngas production and inhibited the formation of CO 2 and CH 4 . The formation of Fe 2 O 3 and Fe 3 O 4 was found during microwave pyrolysis and the mechanism of the two metallic oxides formation was described in this work. Copyright © 2017 Elsevier Ltd. All rights reserved.

Assessing the exchange coupling in binuclear lanthanide(iii) complexes and the slow relaxation of the magnetization in the antiferromagnetically coupled Dy2 derivative† †Electronic supplementary information (ESI) available: Additional magnetic data, additional figures and computational details. CCDC 1020818–1020822. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc01029b

PubMed Central

Chow, Chun Y.; Bolvin, Hélène; Campbell, Victoria E.; Guillot, Régis; Kampf, Jeff W.; Wernsdorfer, Wolfgang; Gendron, Frédéric; Autschbach, Jochen

2015-01-01

We report here the synthesis and the investigation of the magnetic properties of a series of binuclear lanthanide complexes belonging to the metallacrown family. The isostructural complexes have a core structure with the general formula [Ga4Ln2(shi3–)4(Hshi2–)2(H2shi–)2(C5H5N)4(CH3OH)x(H2O)x]·xC5H5N·xCH3OH·xH2O (where H3shi = salicylhydroxamic acid and Ln = GdIII1; TbIII2; DyIII3; ErIII4; YIII5; YIII0.9DyIII0.16). Apart from the Er-containing complex, all complexes exhibit an antiferromagnetic exchange coupling leading to a diamagnetic ground state. Magnetic studies, below 2 K, on a single crystal of 3 using a micro-squid array reveal an opening of the magnetic hysteresis cycle at zero field. The dynamic susceptibility studies of 3 and of the diluted DyY 6 complexes reveal the presence of two relaxation processes for 3 that are due to the excited ferromagnetic state and to the uncoupled DyIII ions. The antiferromagnetic coupling in 3 was shown to be mainly due to an exchange mechanism, which accounts for about 2/3 of the energy gap between the antiferro- and the ferromagnetic states. The overlap integrals between the Natural Spin Orbitals (NSOs) of the mononuclear fragments, which are related to the magnitude of the antiferromagnetic exchange, are one order of magnitude larger for the Dy2 than for the Er2 complex. PMID:29218180

Cobalt-Catalyzed C(sp(2))-H Borylation: Mechanistic Insights Inspire Catalyst Design.

PubMed

Obligacion, Jennifer V; Semproni, Scott P; Pappas, Iraklis; Chirik, Paul J

2016-08-24

A comprehensive study into the mechanism of bis(phosphino)pyridine (PNP) cobalt-catalyzed C-H borylation of 2,6-lutidine using B2Pin2 (Pin = pinacolate) has been conducted. The experimentally observed rate law, deuterium kinetic isotope effects, and identification of the catalyst resting state support turnover limiting C-H activation from a fully characterized cobalt(I) boryl intermediate. Monitoring the catalytic reaction as a function of time revealed that borylation of the 4-position of the pincer in the cobalt catalyst was faster than arene borylation. Cyclic voltammetry established the electron withdrawing influence of 4-BPin, which slows the rate of C-H oxidative addition and hence overall catalytic turnover. This mechanistic insight inspired the next generation of 4-substituted PNP cobalt catalysts with electron donating and sterically blocking methyl and pyrrolidinyl substituents that exhibited increased activity for the C-H borylation of unactivated arenes. The rationally designed catalysts promote effective turnover with stoichiometric quantities of arene substrate and B2Pin2. Kinetic studies on the improved catalyst, 4-(H)2BPin, established a change in turnover limiting step from C-H oxidative addition to C-B reductive elimination. The iridium congener of the optimized cobalt catalyst, 6-(H)2BPin, was prepared and crystallographically characterized and proved inactive for C-H borylation, a result of the high kinetic barrier for reductive elimination from octahedral Ir(III) complexes.

Syntheses, structures, and magnetic properties of three new MnII-[MoIII(CN)7]4- molecular magnets.

PubMed

Wei, Xiao-Qin; Pi, Qian; Shen, Fu-Xing; Shao, Dong; Wei, Hai-Yan; Wang, Xin-Yi

2018-05-22

By reaction of K4[MoIII(CN)7]·2H2O, Mn(ClO4)2·6H2O and bidentate chelating ligands, three new cyano-bridged compounds, namely Mn2(3-pypz)(H2O)(CH3CN)[Mo(CN)7] (1), Mn2(1-pypz)(H2O)(CH3CN)[Mo(CN)7] (2) and Mn2(pyim)(H2O)(CH3CN)[Mo(CN)7] (3) (3-pypz = 2-(1H-pyrazol-3-yl)pyridine, 1-pypz = 2-(1H-pyrazol-1-yl)pyridine, pyim = 2-(1H-imidazol-2-yl)pyridine), have been synthesized and characterized structurally and magnetically. Single crystal X-ray analyses revealed that although the chelating ligands are different, compounds 1 to 3 are isomorphous and crystallize in the same monoclinic space group C2/m. Connected by the bridging cyano groups, one crystallographically unique [Mo(CN)7]4- unit and three crystallographically unique MnII ions of different coordination environments form similar three-dimensional frameworks, which have a four-nodal 3,4,4,7-connecting topological net with a vertex symbol of {43}{44·62}2{410·611}. Magnetic measurements revealed that compounds 1-3 display long-range magnetic ordering with critical temperatures of 64, 66 and 62 K, respectively. These compounds are rare examples of a small number of chelating co-ligand coordinated [Mo(CN)7]4--based magnetic materials. Specifically, the bidentate chelating ligands were successfully introduced into the heptacyanomolybdate system for the first time.

Coder’s Manual: A Guide to TEPIAC Documentation.

DTIC Science & Technology

1977-07-01

Po Polonium Am Americium Hg Mercury Pr Praseodymium *Ar Argon (Hydrargyrum) Pt Platinum (also A) Ho Holmium Pu Plutonium *As Arsenic *1 Iodine Ra...Er 20 3 208 D ChD2 110 F F 2 Fe (FeF 21 209 E C 6H1 5ErO1 2S 3[Er(C 2 HSO 4)3] III G GaO4P [GaPO4] 210 F CH3 F 112 H 1iNO 212 G C8 H20Ge [Ge(C 2 H 5...Fluidity, 69 Heat conductance (contact), 62 Fluidized bed, 27 Heat conduction, 57 Fluorescence, 125 Heat conductivity, 57 Food products, 31 Heat content

Thermodynamics of axial substitution and kinetics of reactions with amino acids for the paddlewheel complex tetrakis(acetato)chloridodiruthenium(II,III).

PubMed

Santos, Rodrigo L S R; van Eldik, Rudi; de Oliveira Silva, Denise

2012-06-18

The known paddlewheel, tetrakis(acetato)chloridodiruthenium(II,III), offers a versatile synthetic route to a novel class of antitumor diruthenium(II,III) metallo drugs, where the equatorial ligands are nonsteroidal anti-inflammatory carboxylates. This complex was studied here as a soluble starting prototype model for antitumor analogues to elucidate the reactivity of the [Ru(2)(CH(3)COO)(4)](+) framework. Thermodynamic studies on equilibration reactions for axial substitution of water by chloride and kinetic studies on reactions of the diaqua complexes with the amino acids glycine, cysteine, histidine, and tryptophan were performed. The standard thermodynamic reaction parameters ΔH°, ΔS°, and ΔV° were determined and showed that both of the sequential axial substitution reactions are enthalpy driven. Kinetic rate laws and rate constants were determined for the axial substitution reactions of coordinated water by the amino acids that gave the corresponding aqua(amino acid)-Ru(2) substituted species. The results revealed that the [Ru(2)(CH(3)COO)(4)](+) paddlewheel framework remained stable during the axial ligand substitution reactions and was also mostly preserved in the presence of the amino acids.

METHANE EMISSIONS FROM THE NATURAL GAS INDUSTRY VOLUME 9: UNDERGROUND PIPELINES

EPA Science Inventory

The 15-volume report summarizes the results of a comprehensive program to quantify methane (CH4) emissions from the U.S. natural gas industry for the base year. The objective was to determine CH4 emissions from the wellhead and ending downstream at the customer's meter. The accur...

METHANE EMISSIONS FROM THE NATURAL GAS INDUSTRY VOLUME 14: GLYCOL DEHYDRATORS

EPA Science Inventory

The 15-volume report summarizes the results of a comprehensive program to quantify methane (CH4) emissions from the U.S. natural gas industry for the base year. The objective was to determine CH4 emissions from the wellhead and ending downstream at the customer's meter. The accur...

METHANE EMISSIONS FROM THE NATURAL GAS INDUSTRY VOLUME 8: EQUIPMENT LEAKS

EPA Science Inventory

The 15-volume report summarizes the results of a comprehensive program to quantify methane (CH4) emissions from the U.S. natural gas industry for the base year. The objective was to determine CH4 emissions from the wellhead and ending downstream at the customer's meter. The accur...

METHANE EMISSIONS FROM THE NATURAL GAS INDUSTRY VOLUME 5: ACTIVITY FACTORS

EPA Science Inventory

The 15-volume report summarizes the results of a comprehensive program to quantify methane (CH4) emissions from the U.S. natural gas industry for the base year. The objective was to determine CH4 emissions from the wellhead and ending downstream at the customer's meter. The accur...

METHANE EMISSIONS FROM THE NATURAL GAS INDUSTRY VOLUME 2: TECHNICAL REPORT

EPA Science Inventory

The 15-volume report summarizes the results of a comprehensive program to quantify methane (CH4) emissions from the U.S. natural gas industry for the base year. The objective was to determine CH4 emissions from the wellhead and ending downstream at the customer's meter. The accur...

METHANE EMISSIONS FROM THE NATURAL GAS INDUSTRY VOLUME 3: GENERAL METHODOLOGY

EPA Science Inventory

The 15-volume report summarizes the results of a comprehensive program to quantify methane (CH4) emissions from the U.S. natural gas industry for the base year. The objective was to determine CH4 emissions from the wellhead and ending downstream at the customer's meter. The accur...

METHANE EMISSIONS FROM THE NATURAL GAS INDUSTRY VOLUME 12: PNEUMATIC DEVICES

EPA Science Inventory

The 15-volume report summarizes the results of a comprehensive program to quantify methane (CH4) emissions from the U.S. natural gas industry for the base year. The objective was to determine CH4 emissions from the wellhead and ending downstream at the customer's meter. The accur...

METHANE EMISSIONS FROM THE NATURAL GAS INDUSTRY VOLUME 1: EXECUTIVE SUMMARY

EPA Science Inventory

The 15-volume report summarizes the results of a comprehensive program to quantify methane (CH4) emissions from the U.S. natural gas industry for the base year. The objective was to determine CH4 emissions from the wellhead and ending downstream at the customer's meter. The accur...

Solubility of lead and copper in biochar-amended small arms range soils: influence of soil organic carbon and pH.

PubMed

Uchimiya, Minori; Bannon, Desmond I

2013-08-14

Biochar is often considered a strong heavy metal stabilizing agent. However, biochar in some cases had no effects on, or increased the soluble concentrations of, heavy metals in soil. The objective of this study was to determine the factors causing some biochars to stabilize and others to dissolve heavy metals in soil. Seven small arms range soils with known total organic carbon (TOC), cation exchange capacity, pH, and total Pb and Cu contents were first screened for soluble Pb and Cu concentrations. Over 2 weeks successive equilibrations using weak acid (pH 4.5 sulfuric acid) and acetate buffer (0.1 M at pH 4.9), Alaska soil containing disproportionately high (31.6%) TOC had nearly 100% residual (insoluble) Pb and Cu. This soil was then compared with sandy soils from Maryland containing significantly lower (0.5-2.0%) TOC in the presence of 10 wt % (i) plant biochar activated to increase the surface-bound carboxyl and phosphate ligands (PS450A), (ii) manure biochar enriched with soluble P (BL700), and (iii) unactivated plant biochars produced at 350 °C (CH350) and 700 °C (CH500) and by flash carbonization (corn). In weak acid, the pH was set by soil and biochar, and the biochars increasingly stabilized Pb with repeated extractions. In pH 4.9 acetate buffer, PS450A and BL700 stabilized Pb, and only PS450A stabilized Cu. Surface ligands of PS450A likely complexed and stabilized Pb and Cu even under acidic pH in the presence of competing acetate ligand. Oppositely, unactivated plant biochars (CH350, CH500, and corn) mobilized Pb and Cu in sandy soils; the putative mechanism is the formation of soluble complexes with biochar-borne dissolved organic carbon. In summary, unactivated plant biochars can inadvertently increase dissolved Pb and Cu concentrations of sandy, low TOC soils when used to stabilize other contaminants.

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

NASA Astrophysics Data System (ADS)

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

2000-03-01

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

Spectroscopy, electrochemistry and antiproliferative properties of Au(iii), Pt(ii) and Cu(ii) complexes bearing modified 2,2':6',2''-terpyridine ligands.

PubMed

Maroń, Anna; Czerwińska, Katarzyna; Machura, Barbara; Raposo, Luis; Roma-Rodrigues, Catarina; Fernandes, Alexandra R; Małecki, Jan G; Szlapa-Kula, Agata; Kula, Slawomir; Krompiec, Stanisław

2018-05-08

Structural, spectroscopic and electrochemical properties of six complexes [AuCl(L1)](PF6)2·CH3CN (1), [AuCl(L2)](PF6)2 (2), [PtCl(L1)](BPh4)·CH3CN (3), [PtCl(L2)](SO3CF3) (4), [CuCl2(L1)] (5) and [CuCl2(L2)]·CH3CN (6) with modified 2,2':6',2''-terpyridine ligands, 4'-(4-methoxyphenyl)-2,2':6',2''-terpyridine (L1) and 4'-(4-methoxynaphthalen-1-yl)-2,2':6',2''-terpyridine (L2) were thoroughly investigated and a significant role of the substituent (4-methoxyphenyl or 4-methoxynaphthalen-1-yl) and the metal center was demonstrated. The naphthyl-based substituent was found to increase the emission quantum yield of the luminescent Au(iii) and Pt(ii) complexes. Furthermore, the antiproliferative potential of the reported complexes was examined towards human colorectal (HCT116) and ovarian (A2780) carcinoma cell lines as well as towards normal human fibroblasts. The Au(iii) complex 2 and Cu(ii) complex 5 were found to have a higher antiproliferative effect on HCT116 colorectal and A2780 ovarian carcinoma cells when compared with the Pt(ii) complex with the same ligand (4). The order of cytotoxicity in both cell lines is 2 > 6 > 1 > 3 > 4. Complex 2 seems to be more cytotoxic towards HCT116 and A2780 cancer cell lines with IC50 values 300× and 130× higher in normal human fibroblasts compared to the respective cancer cells. The viability loss induced by the complexes agrees with Hoechst 33258 staining and the typical morphological apoptotic characteristics like chromatin condensation and nuclear fragmentation and flow cytometry assay. The induction of apoptosis correlates with the induction of reactive oxygen species (ROS). Fluorescence microscopy analysis indicates that after 3 h of incubation, complexes 1-4 are localized inside HCT116 cells and the high levels of internalization correlate with their cytotoxicity.

Thermodynamic considerations of the vapor phase reactions in III-nitride metal organic vapor phase epitaxy

NASA Astrophysics Data System (ADS)

Sekiguchi, Kazuki; Shirakawa, Hiroki; Chokawa, Kenta; Araidai, Masaaki; Kangawa, Yoshihiro; Kakimoto, Koichi; Shiraishi, Kenji

2017-04-01

We analyzed the metal organic vapor phase epitaxial growth mechanism of the III-nitride semiconductors GaN, AlN, and InN by first-principles calculations and thermodynamic analyses. In these analyses, we investigated the decomposition processes of the group III source gases X(CH3)3 (X = Ga, Al, In) at finite temperatures and determined whether the (CH3)2GaNH2 adduct can be formed or not. The results of our calculations show that the (CH3)2GaNH2 adduct cannot be formed in the gas phase in GaN metal organic vapor phase epitaxy (MOVPE), whereas, in AlN MOVPE, the formation of the (CH3)2AlNH2 adduct in the gas phase is exclusive. In the case of GaN MOVPE, trimethylgallium (TMG, [Ga(CH3)3]) decomposition into Ga gas on the growth surface with the assistance of H2 carrier gas, instead of the formation of the (CH3)2GaNH2 adduct, occurs almost exclusively. Moreover, in the case of InN MOVPE, the formation of the (CH3)2InNH2 adduct does not occur and it is relatively easy to produce In gas even without H2 in the carrier gas.

Factors affecting methane production and mitigation in ruminants.

PubMed

Shibata, Masaki; Terada, Fuminori

2010-02-01

Methane (CH(4)) is the second most important greenhouse gas (GHG) and that emitted from enteric fermentation in livestock is the single largest source of emissions in Japan. Many factors influence ruminant CH(4) production, including level of intake, type and quality of feeds and environmental temperature. The objectives of this review are to identify the factors affecting CH(4) production in ruminants, to examine technologies for the mitigation of CH(4) emissions from ruminants, and to identify areas requiring further research. The following equation for CH(4) prediction was formulated using only dry matter intake (DMI) and has been adopted in Japan to estimate emissions from ruminant livestock for the National GHG Inventory Report: Y = -17.766 + 42.793X - 0.849X(2), where Y is CH(4) production (L/day) and X is DMI (kg/day). Technologies for the mitigation of CH(4) emissions from ruminants include increasing productivity by improving nutritional management, the manipulation of ruminal fermentation by changing feed composition, the addition of CH(4) inhibitors, and defaunation. Considering the importance of ruminant livestock, it is essential to establish economically feasible ways of reducing ruminant CH(4) production while improving productivity; it is therefore critical to conduct a full system analysis to select the best combination of approaches or new technologies to be applied under long-term field conditions.

Aerial Photography Estimation of CH4 and N2O Emissions from Adelie Penguins During 1983-2012 in Victoria Land, Antarctic

NASA Astrophysics Data System (ADS)

He, H.; Li, X.; Cheng, X.

2016-12-01

Sea animals are the "bio-indicators" of the climate change in the Antarctic. The abundant nutrient components in their excreta such as carbon (C) and nitrogen (N) promote the emissions of greenhouse gases (GHGs) including methane (CH4) and nitrous oxide (N2O). Adélie Penguins are important sea animals, their colonies therefore become the potential "hotspots" of the GHGs emissions. Some field observations have been carried out to study the penguin excreta on CH4 and N2O emissions in the Antarctic peninsula. However, due to the lacking of the penguin population data, the total emissions of GHGs have not been estimated at regional scale. This study aimed to extract penguin information from two period aerial photographs respectively in 1983 and 2012 using object-oriented method in Victoria Land, Antarctic, and then estimate the Adélie penguin populations on Inexpressible Island combined with the shadow analysis. Meanwhile, a GHGs model was developed to estimate CH4 and N2O emissions from Adelie penguins based on the CH4 and N2O fluxes of penguin guanos, the number of penguins, and the fresh weight of penguin guanos and so on. The results indicated that object-oriented method was effective in penguin information extraction from high-resolution images, and there were 17120 and 21183 Adélie penguins respectively in 1983 and 2012, respectively. The main reasons for the increase in penguin populations from 1983 to 2012 might be explained from physical environment and biological environment, such as the rising temperatures and reduced Antarctic toothfishes. And the total CH4 and N2O emissions from penguins on Inexpressible Island during breeding season were 246 kg CH4 and 2.67 kg N2O in 1983, and 304 kg CH4 and 3.31 kg N2O in 2012. Our study aimed to provide important reference value for the estimation of GHG budget in Antarctic.

40 CFR 1065.650 - Emission calculations.

Code of Federal Regulations, 2011 CFR

2011-07-01

... following sequence of preliminary calculations on recorded concentrations: (i) Correct all THC and CH4.... (iii) Calculate all THC and NMHC concentrations, including dilution air background concentrations, as... NMHC to background corrected mass of THC. If the background corrected mass of NMHC is greater than 0.98...

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.

Preparation, spectroscopic and high field NMR relaxometry studies of gadolinium(III) complexes with the asymmetric tetraamine 1,4,7,11-tetraazaundecane

NASA Astrophysics Data System (ADS)

Hatzipanayioti, Despina; Veneris, Antonis

2009-10-01

The reaction of Gd(III) with asymmetric tetramine 1,4,7,11-tetraazaundecane (2,2,3-tet, L1) ligand has been studied via NMR spectroscopy. The ligand proton longitudinal relaxation rates ( R1) have been used to estimate the distances of these protons from the Gd(III) center, in Gd(III)- L1 reaction solutions, in H 2O/D 2O 5/1 mixtures. Two Gd(III) complexes [Gd(III)( L1)(NH 3)(H 2O) 4](CH 3COO) 3·2H 2O ( 1) and [Gd(III)( L1)(NH 3)(H 2O) 2]Cl 3·EtOH ( 2) have been isolated and characterized by elemental analyses, TGA, IR, NMR and relaxometry measurements. The NMR relaxation measurements of 2 in aqueous solutions have been performed, under various temperature or concentration conditions, and compared with those of the commercial contrast agents Gd(III)-DTPA and Gd(III)-DTPA-BMA. It has also been studied the influence of (i) the Gd(III) inner-sphere water molecule number ( q) alteration and (ii) the steric constraint enhancement on the metal site, over the relaxation rate values of the parent aqueous solution of Gd(III)-2,2,3-tet, and of the aqueous solutions of 2.

Gas-phase nitrosation of ethylene and related events in the C2H4NO+ landscape.

PubMed

Gerbaux, Pascal; Dechamps, Noemie; Flammang, Robert; Nam, Pham Cam; Nguyen, Minh Tho; Djazi, Fayçal; Berruyer, Florence; Bouchoux, Guy

2008-06-19

The C2H4NO(+) system has been examined by means of quantum chemical calculations using the G2 and G3B3 approaches and tandem mass spectrometry experiments. Theoretical investigation of the C2H4NO(+) potential-energy surface includes 19 stable C2H4NO(+) structures and a large set of their possible interconnections. These computations provide insights for the understanding of the (i) addition of the nitrosonium cation NO(+) to the ethylene molecule, (ii) skeletal rearrangements evidenced in previous experimental studies on comparable systems, and (iii) experimental identification of new C2H4NO(+) structures. It is predicted from computation that gas-phase nitrosation of ethylene may produce C2H4(*)NO(+) adducts, the most stable structure of which is a pi-complex, 1, stabilized by ca. 65 kJ/mol with respect to its separated components. This complex was produced in the gas phase by a transnitrosation process involving as reactant a complex between water and NO(+) (H2O.NO(+)) and the ethylene molecule and fully characterized by collisional experiments. Among the other C 2H 4NO (+) structures predicted by theory to be protected against dissociation or isomerization by significant energy barriers, five were also experimentally identified. These finding include structures CH3CHNO(+) (5), CH 3CNOH (+) ( 8), CH3NHCO(+) (18), CH3NCOH(+) (19), and an ion/neutral complex CH2O...HCNH(+) (12).

METHANE EMISSIONS FROM THE NATURAL GAS INDUSTRY VOLUME 13: CHEMICAL INJECTION PUMPS

EPA Science Inventory

The 15-volume report summarizes the results of a comprehensive program to quantify methane (CH4) emissions from the U.S. natural gas industry for the base year. The objective was to determine CH4 emissions from the wellhead and ending downstream at the customer's meter. The accur...

METHANE EMISSIONS FROM THE NATURAL GAS INDUSTRY VOLUME 15: GAS-ASSISTED GLYCOL PUMPS

EPA Science Inventory

The 15-volume report summarizes the results of a comprehensive program to quantify methane (CH4) emissions from the U.S. natural gas industry for the base year. The objective was to determine CH4 emissions from the wellhead and ending downstream at the customer's meter. The accur...

METHANE EMISSIONS FROM THE NATURAL GAS INDUSTRY VOLUME 6: VENTED & COMBUSTION SOURCE SUMMARY

EPA Science Inventory

The 15-volume report summarizes the results of a comprehensive program to quantify methane (CH4) emissions from the U.S. natural gas industry for the base year. The objective was to determine CH4 emissions from the wellhead and ending downstream at the customer's meter. The accur...

METHANE EMISSIONS FROM THE NATURAL GAS INDUSTRY VOLUME 11: COMPRESSOR DRIVER EXHAUST

EPA Science Inventory

The 15-volume report summarizes the results of a comprehensive program to quantify methane (CH4) emissions from the U.S. natural gas industry for the base year. The objective was to determine CH4 emissions from the wellhead and ending downstream at the customer's meter. The accur...

METHANE EMISSIONS FROM THE NATURAL GAS INDUSTRY VOLUME 7: BLOW AND PURGE ACTIVITIES

EPA Science Inventory

The 15-volume report summarizes the results of a comprehensive program to quantify methane (CH4) emissions from the U.S. natural gas industry for the base year. The objective was to determine CH4 emissions from the wellhead and ending downstream at the customer's meter. The accur...

A DFT-Elucidated Comparison of the Solution-Phase and SAM Electrochemical Properties of Short-Chain Mercaptoalkylferrocenes: Synthetic and Spectroscopic Aspects, and the Structure of Fc-CH2CH2-S-S-CH2CH2-Fc.

PubMed

Lewtak, Jan P; Landman, Marilé; Fernández, Israel; Swarts, Jannie C

2016-03-07

Facile synthetic procedures to synthesize a series of difficult-to-obtain mercaptoalkylferrocenes, namely, Fc(CH2)nSH, where n = 1 (1), 2 (2), 3 (3), or 4 (4) and Fc = Fe(η(5)-C5H5)(η(5)-C5H4), are reported. Dimerization of 1-4 to the corresponding disulfides 19-22 was observed in air. Dimer 20 (Z = 2) crystallized in the triclinic space group P1̅. Dimers 20-22 could be reduced back to the original Fc(CH2)nSH derivatives with LiAlH4 in refluxing tetrahydrofuran. Density functional theory (DFT) calculations showed that the highest occupied molecular orbital of 1-4 lies exclusively on the ferrocenyl group implying that the electrochemical oxidation observed at ca. -15 < Epa < 76 mV versus FcH/FcH(+) involves exclusively an Fe(II) to Fe(III) process. Further DFT calculations showed this one-electron oxidation is followed by proton loss on the thiol group to generate a radical, Fc(CH2)nS(•), with spin density mainly located on the sulfur. Rapid exothermic dimerization leads to the observed dimers, Fc(CH2)n-S-S-(CH 2)nFc. Reduction of the ferrocenium groups on the dimer occurs at potentials that still showed the ferrocenyl group ΔE = Epa,monomer - Epc,dimer ≤ 78 mV, indicating that the redox properties of the ferrocenyl group on the mercaptans are very similar to those of the dimer. (1)H NMR measurements showed that, like ferrocenyl oxidation, the resonance position of the sulfhydryl proton, SH, and others, are dependent on -(CH2)n- chain length. Self-assembled monolayers (SAMs) on gold were generated to investigate the electrochemical behavior of 1-4 in the absence of diffusion. Under these conditions, ΔE approached 0 mV for the longer chain derivatives at slow scan rates. The surface-bound ferrocenyl group of the metal-thioether, Fc(CH2)n -S-Au, is oxidized at approximately equal potentials as the equivalent CH2Cl2-dissolved ferrocenyl species 1-4. Surface coverage by the SAMs is dependent on alkyl chain length with the largest coverage obtained for 4, while the rate of heterogeneous electron transfer between SAM substrate and electrode was the fastest for the shortest chain derivative, Fc-CH2-S-Au.

Global Inventory of Gas Geochemistry Data from Fossil Fuel, Microbial and Burning Sources, version 2017

NASA Astrophysics Data System (ADS)

Sherwood, Owen A.; Schwietzke, Stefan; Arling, Victoria A.; Etiope, Giuseppe

2017-08-01

The concentration of atmospheric methane (CH4) has more than doubled over the industrial era. To help constrain global and regional CH4 budgets, inverse (top-down) models incorporate data on the concentration and stable carbon (δ13C) and hydrogen (δ2H) isotopic ratios of atmospheric CH4. These models depend on accurate δ13C and δ2H end-member source signatures for each of the main emissions categories. Compared with meticulous measurement and calibration of isotopic CH4 in the atmosphere, there has been relatively less effort to characterize globally representative isotopic source signatures, particularly for fossil fuel sources. Most global CH4 budget models have so far relied on outdated source signature values derived from globally nonrepresentative data. To correct this deficiency, we present a comprehensive, globally representative end-member database of the δ13C and δ2H of CH4 from fossil fuel (conventional natural gas, shale gas, and coal), modern microbial (wetlands, rice paddies, ruminants, termites, and landfills and/or waste) and biomass burning sources. Gas molecular compositional data for fossil fuel categories are also included with the database. The database comprises 10 706 samples (8734 fossil fuel, 1972 non-fossil) from 190 published references. Mean (unweighted) δ13C signatures for fossil fuel CH4 are significantly lighter than values commonly used in CH4 budget models, thus highlighting potential underestimation of fossil fuel CH4 emissions in previous CH4 budget models. This living database will be updated every 2-3 years to provide the atmospheric modeling community with the most complete CH4 source signature data possible. Database digital object identifier (DOI): https://doi.org/10.15138/G3201T.

40 CFR 1066.15 - Overview of test procedures.

Code of Federal Regulations, 2014 CFR

2014-07-01

...) Hydrocarbons, HC, which may be expressed in the following ways: (i) Total hydrocarbons, THC. (ii) Nonmethane hydrocarbons, NMHC, which results from subtracting methane, CH4, from THC. (iii) Total hydrocarbon-equivalent, THCE, which results from adjusting THC mathematically to be equivalent on a carbon-mass basis. (iv...

Gd-DTPA L-cystine bisamide copolymers as novel biodegradable macromolecular contrast agents for MR blood pool imaging.

PubMed

Kaneshiro, Todd L; Ke, Tianyi; Jeong, Eun-Kee; Parker, Dennis L; Lu, Zheng-Rong

2006-06-01

The purpose of this study was to synthesize biodegradable Gd-DTPA L-cystine bisamide copolymers (GCAC) as safe and effective, macromolecular contrast agents for magnetic resonance imaging (MRI) and to evaluate their biodegradability and efficacy in MR blood pool imaging in an animal model. Three new biodegradable GCAC with different substituents at the cystine bisamide [R = H (GCAC), CH2CH2CH3 (Gd-DTPA L-cystine bispropyl amide copolymers, GCPC), and CH(CH3)2 (Gd-DTPA cystine bisisopropyl copolymers, GCIC)] were prepared by the condensation copolymerization of diethylenetriamine pentaacetic acid (DTPA) dianhydride with cystine bisamide or bisalkyl amides, followed by complexation with gadolinium triacetate. The degradability of the agents was studied in vitro by incubation in 15 microM cysteine and in vivo with Sprague-Dawley rats. The kinetics of in vivo contrast enhancement was investigated in Sprague-Dawley rats on a Siemens Trio 3 T scanner. The apparent molecular weight of the polydisulfide Gd(III) chelates ranged from 22 to 25 kDa. The longitudinal (T1) relaxivities of GCAC, GCPC, and GCIC were 4.37, 5.28, and 5.56 mM(-1) s(-1) at 3 T, respectively. The polymeric ligands and polymeric Gd(III) chelates readily degraded into smaller molecules in incubation with 15 microM cysteine via disulfide-thiol exchange reactions. The in vitro degradation rates of both the polymeric ligands and macromolecular Gd(III) chelates decreased as the steric effect around the disulfide bonds increased. The agents readily degraded in vivo, and the catabolic degradation products were detected in rat urine samples collected after intravenous injection. The agents showed strong contrast enhancement in the blood pool, major organs, and tissues at a dose of 0.1 mmol Gd/kg. The difference of their in vitro degradability did not significantly alter the kinetics of in vivo contrast enhancement of the agents. These novel GCAC are promising contrast agents for cardiovascular and tumor MRI, which are later cleaved into low molecular weight Gd(III) chelates and rapidly cleared from the body.

Synthesis of oxindole from acetanilide via Ir(iii)-catalyzed C-H carbenoid functionalization.

PubMed

Patel, Pitambar; Borah, Gongutri

2016-12-22

Herein we disclose the first report on the synthesis of oxindole derivatives from acetanilide via Ir(iii)-catalyzed intermolecular C-H functionalization with diazotized Meldrum's acid. A broad range of substituted anilides were found to react smoothly under the Ir(iii)-catalytic system to afford the corresponding N-protected oxindoles. The N-protecting groups, such as Ac, Bz or Piv, can be easily removed to furnish the oxindole. Various synthetic applications of the synthesized oxindole were also demonstrated.

An unusual stable mononuclear Mn(III) bis-terpyridine complex exhibiting Jahn-Teller compression: electrochemical synthesis, physical characterisation and theoretical study.

PubMed

Romain, Sophie; Duboc, Carole; Neese, Frank; Rivière, Eric; Hanton, Lyall R; Blackman, Allan G; Philouze, Christian; Leprêtre, Jean-Claude; Deronzier, Alain; Collomb, Marie-Noëlle

2009-01-01

The mononuclear manganese bis-terpyridine complex [Mn(tolyl-terpy)(2)](X)(3) (1(X)(3); X=BF(4), ClO(4), PF(6); tolyl-terpy=4'-(4-methylphenyl)-2,2':6',2"-terpyridine), containing Mn in the unusual +III oxidation state, has been isolated and characterised. The 1(3+) ion is a rare example of a mononuclear Mn(III) complex stabilised solely by neutral N ligands. Complex 1(3+) is obtained by electrochemical oxidation of the corresponding Mn(II) compound 1(2+) in anhydrous acetonitrile. Under these conditions the cyclic voltammogram of 1(2+) exhibits not only the well-known Mn(II)/Mn(III) oxidation at E(1/2)=+0.91 V versus Ag/Ag(+) (+1.21 V vs. SCE) but also a second metal-based oxidation process corresponding to Mn(III)/Mn(IV) at E(1/2)=+1.63 V (+1.93 V vs. SCE). Single crystals of 1(PF(6))(3)2 CH(3)CN were obtained by an electrocrystallisation procedure. X-ray analysis unambiguously revealed its tetragonally compressed octahedral geometry and high-spin character. The electronic properties of 1(3+) were investigated in detail by magnetic measurements and theoretical calculations, from which a D value of +4.82 cm(-1) was precisely determined. Density functional and complete active space self consistent field ab initio calculations both correctly predict a positive sign of D, in agreement with the compressed tetragonal distortion observed in the X-ray structure of 1(PF(6))(3)2 CH(3)CN. The different contributions to D were calculated, and the results show that 1) the spin-orbit coupling part (+2.593 cm(-1)) is predominant compared to the spin-spin interaction (+1.075 cm(-1)) and 2) the excited triplet states make the dominant contribution to the total D value.

Heptanuclear CoII5CoIII2 Cluster as Efficient Water Oxidation Catalyst.

PubMed

Xu, Jia-Heng; Guo, Ling-Yu; Su, Hai-Feng; Gao, Xiang; Wu, Xiao-Fan; Wang, Wen-Guang; Tung, Chen-Ho; Sun, Di

2017-02-06

Inspired by the transition-metal-oxo cubical Mn 4 CaO 5 in photosystem II, we herein report a disc-like heptanuclear mixed-valent cobalt cluster, [Co II 5 Co III 2 (mdea) 4 (N 3 ) 2 (CH 3 CN) 6 (OH) 2 (H 2 O) 2 ·4ClO 4 ] (1, H 2 mdea = N-methyldiethanolamine), for photocatalytic oxygen evolution. The topology of the Co 7 core resembles a small piece of cobaltate protected by terminal H 2 O, N 3 - , CH 3 CN, and multidentate N-methyldiethanolamine at the periphery. Under the optimal photocatalytic conditions, 1 exhibits water oxidation activity with a turnover number (TON) of 210 and a turnover frequency (TOF initial ) of 0.23 s -1 . Importantly, electrospray mass spectrometry (ESI-MS) was used to not only identify the possible main active species in the water oxidation reaction but also monitor the evolutions of oxidation states of cobalt during the photocatalytic reactions. These results shed light on the design concept of new water oxidation catalysts and mechanism-related issues such as the key active intermediate and oxidation state evolution in the oxygen evolution process. The magnetic properties of 1 were also discussed in detail.

Separation of Trivalent Actinides from Lanthanides Using a Capillary Electrophoresis

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

Mori, Tomotaka; Ishii, Yasuo; Hayashi, Kazunori

2007-07-01

A separation of {sup 241}Am(III) from {sup 152,154}Eu(III) was carried out using a capillary electrophoresis technique in a mixed solvent (CH{sub 3}OH/H{sub 2}O) system containing thiocyanate ion. First, the formation constants ({beta}{sub n}) between thiocyanate ion and Eu(III) or Am(III) were investigated in the mixed solvent solutions by a back-extraction technique using bis (2-ethylhexyl) hydrogen phosphate-toluene. The mean charges calculated on the basis of the data of {beta}{sub n} for Eu(III) were comparatively higher than those for Am(III). Based on the differences between the mean charges of Eu(III) and Am(III), separations for Am(III)/Eu(III) by means of capillary electrophoresis technique weremore » tried in the (H{sup +}, Na{sup +})(SCN{sup -}, ClO{sub 4}{sup -}) mixed solvent solutions. It was proved that Am(III) was completely separated from Eu(III). (authors)« less

Manganese-catalysed benzylic C(sp3)-H amination for late-stage functionalization

NASA Astrophysics Data System (ADS)

Clark, Joseph R.; Feng, Kaibo; Sookezian, Anasheh; White, M. Christina

2018-06-01

Reactions that directly install nitrogen into C-H bonds of complex molecules are significant because of their potential to change the chemical and biological properties of a given compound. Although selective intramolecular C-H amination reactions are known, achieving high levels of reactivity while maintaining excellent site selectivity and functional-group tolerance remains a challenge for intermolecular C-H amination. Here, we report a manganese perchlorophthalocyanine catalyst [MnIII(ClPc)] for intermolecular benzylic C-H amination of bioactive molecules and natural products that proceeds with unprecedented levels of reactivity and site selectivity. In the presence of a Brønsted or Lewis acid, the [MnIII(ClPc)]-catalysed C-H amination demonstrates unique tolerance for tertiary amine, pyridine and benzimidazole functionalities. Mechanistic studies suggest that C-H amination likely proceeds through an electrophilic metallonitrene intermediate via a stepwise pathway where C-H cleavage is the rate-determining step of the reaction. Collectively, these mechanistic features contrast with previous base-metal-catalysed C-H aminations and provide new opportunities for tunable selectivities.

Manganese-catalysed benzylic C(sp3)-H amination for late-stage functionalization.

PubMed

Clark, Joseph R; Feng, Kaibo; Sookezian, Anasheh; White, M Christina

2018-06-01

Reactions that directly install nitrogen into C-H bonds of complex molecules are significant because of their potential to change the chemical and biological properties of a given compound. Although selective intramolecular C-H amination reactions are known, achieving high levels of reactivity while maintaining excellent site selectivity and functional-group tolerance remains a challenge for intermolecular C-H amination. Here, we report a manganese perchlorophthalocyanine catalyst [MnIII(ClPc)] for intermolecular benzylic C-H amination of bioactive molecules and natural products that proceeds with unprecedented levels of reactivity and site selectivity. In the presence of a Brønsted or Lewis acid, the [MnIII(ClPc)]-catalysed C-H amination demonstrates unique tolerance for tertiary amine, pyridine and benzimidazole functionalities. Mechanistic studies suggest that C-H amination likely proceeds through an electrophilic metallonitrene intermediate via a stepwise pathway where C-H cleavage is the rate-determining step of the reaction. Collectively, these mechanistic features contrast with previous base-metal-catalysed C-H aminations and provide new opportunities for tunable selectivities.

A mass balance model to estimate the rate of composting, methane oxidation and anaerobic digestion in soil covers and shallow waste layers.

PubMed

Rafiee, Reza; Obersky, Lizanne; Xie, Sihuang; Clarke, William P

2017-05-01

Although CH 4 oxidation in landfill soil covers is widely studied, the extent of composting and CH 4 oxidation in underlying waste layers has been speculated but not measured. The objective of this study was to develop and validate a mass balance model to estimate the simultaneous rates of anaerobic digestion (r AD ), CH 4 oxidation (r OX ) and composting (r COM ) in environments where O 2 penetration is variable and zones of aerobic and anaerobic activity are intermingled. The modelled domain could include, as an example, a soil cover and the underlying shallow waste to a nominated depth. The proposed model was demonstrated on a blend of biogas from three separate known sources of gas representing the three reaction processes: (i) a bottle of laboratory grade 50:50% CH 4 :CO 2 gas representing anaerobic digestion biogas; (ii) an aerated 250mL bottle containing food waste that represented composting activity; and (iii) an aerated 250mL bottle containing non-degradable graphite granules inoculated with methanotrophs and incubated with CH 4 and O 2 to represent methanotrophic activity. CO 2 , CH 4 , O 2 and the stable isotope 13 C-CO 2 were chosen as the components for the mass balance model. The three reaction rates, r (=r AD , r OX , r COM ) were calculated as fitting parameters to the overdetermined set of 4mass balance equations with the net flux of these components from the bottles q (= [Formula: see text] , [Formula: see text] , [Formula: see text] and [Formula: see text] ) as inputs to the model. The coefficient of determination (r 2 ) for observed versus modelled values of r were 1.00, 0.97, 0.98 when the stoichiometry of each reaction was based on gas yields measured in the individual bottles and q was calculated by summing yields from the three bottles. r 2 deteriorated to 0.95, 0.96, 0.87 when using an average stoichiometry from 11 incubations of each of the composting and methane oxidation processes. The significant deterioration in the estimation of r COM showed that this output is highly sensitive to the evaluated stoichiometry coefficients for the reactions. r 2 deteriorated further to 0.86, 0.77, 0.74 when using the average stoichiometry and experimental measurement of the composition and volume of the blended biogas to determine q. This was primarily attributed to average errors of 8%, 7%, 11% and 14% in the measurement of [Formula: see text] , [Formula: see text] , [Formula: see text] and [Formula: see text] relative to the measurement of the same quantities from the individual bottles. Copyright © 2016 Elsevier Ltd. All rights reserved.

Only low methane production and emission in degraded peat extraction sites after rewetting

NASA Astrophysics Data System (ADS)

Agethen, Svenja; Waldemer, Carolin; Knorr, Klaus-Holger

2015-04-01

In Central Europe rewetting of bogs after peat extraction is a wide spread technique to halt secondary aerobic decomposition and to reestablish plant species such as Sphagnum spp. and Eriophorum spp. that initialize accumulation of organic carbon in peat. Before extraction, such sites are often used for agriculture causing the aerobic degradation of peat and mobilization of phosphorus, ammonia, and dissolved organic matter (DOM). In nutrient poor ecosystems such as bogs, additional supply of P and N does not only trigger the establishment of uncharacteristic vegetation but also the formation of more labile plant litter and DOM that is readily degradable. Therefore, after rewetting and the development of anoxic conditions especially in initial stages high methane (CH4) emissions are reported for these systems compared to pristine bogs. Regarding the potential of methane production and emissions we investigated three common practices to prepare extraction fields for restoration (years since rewetting): i) Filling of drainage ditches, passive rewetting (1 site, Altendorfer Moor, Stade, NW-Germany, ca. 20 yr.), ii) Removal of upper 30 cm peat layer, removed peat used for construction of polder dikes (2 sites, Königsmoor, Leer, NW-Germany, 2 and 3 yr.), iii) Removal upper peat layer down to 50 cm grown peat, not extracted peat used as polder walls (2 sites, Benthullener Moor, Wardenburg, NW-Germany, 3 and 7 yr.). In each site two vegetated replicate mesocosms (diam. 30 cm, depth 40 cm) were sampled and placed in a greenhouse from May-October 2014 to maintain the water table at surface level. Pore water concentrations of ions, fermentation products and DOM, DOM electron acceptor capacity (EAC), soil gas concentrations of CO2, CH4 and H2, gas fluxes as well as element composition and organic matter quality of DOM and SOM were analyzed. We found out that practice i) with least efforts of nutrient removal in the peat produced the highest CH4 emissions (3.5 mmol m-2 d-1) although still within the range of northern pristine bogs. Also practice ii) showed still inputs of external nutrients and labile DOM, but CH4 production was not yet developed (0.23 and 0.07 mmol m-2 d-1). Practice iii) was most effective in nutrient removal, but only in the 7 yr. site little methane (in the 3 yr. site 0.025 vs. 0.41 mmol m-2 d-1in the 7 yr. site) was emitted. The emissions were well in accord with soil gas concentrations, maximum values for CH4 in practice i) were 115 μmol L-1, 2-5 μmol L-1 in practice ii) and 0.5 vs. 16 μmol L-1 in practice iii). Only small concentrations of inorganic electron acceptors such as sulfate imply the importance of organic matter as electron acceptor. The results show that restored bogs on former strongly degraded extraction fields do not necessarily act as exceptionally high CH4 sources. Contrary to other findings in early stages of rewetting CH4 emissions can also be very low until other electron acceptors are exhausted and methanogens become effective competitors for substrates which happens in the order of years.

Anaerobic degradation of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA).

PubMed

Finneran, K T; Lovley, D R

2001-05-01

The potential for anaerobic degradation of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) was investigated in laboratory incubations of sediments from a petroleum-contaminated aquifer and in aquatic sediments. The addition of humic substances (HS) stimulated the anaerobic degradation of MTBE in aquifer sediments in which Fe(III) was available as an electron acceptor. This is attributed to the fact that HS and other extracellular quinones can stimulate the activity of Fe(III)-reducing microorganisms by acting as an electron shuttle between Fe(III)-reducing microorganisms and insoluble Fe(III) oxides. MTBE was not degraded in aquifer sediments without Fe(III) and HS. [14C]-MTBE added to aquatic sediments adapted for anaerobic MTBE degradation was converted to 14CO2 in the presence or absence of HS or the HS analog, anthraquione-2,6-disulfonate. Unamended aquatic sediments produced 14CH4 as well as 14CO2 from [14C]-MTBE. The aquatic sediments also rapidly consumed TBA under anaerobic conditions and converted [14C]-TBA to 14CH4 and 14CO2. An adaptation period of ca. 250-300 days was required prior to the most rapid anaerobic MTBE degradation in both sediment types, whereas TBA was metabolized in the aquatic sediments without a lag. These results demonstrate that, under the appropriate conditions, MTBE and TBA can be degraded in the absence of oxygen. This suggests that it may be possible to design strategies for the anaerobic remediation of MTBE in petroleum-contaminated subsurface environments.

Fast and accurate predictions of covalent bonds in chemical space.

PubMed

Chang, K Y Samuel; Fias, Stijn; Ramakrishnan, Raghunathan; von Lilienfeld, O Anatole

2016-05-07

We assess the predictive accuracy of perturbation theory based estimates of changes in covalent bonding due to linear alchemical interpolations among molecules. We have investigated σ bonding to hydrogen, as well as σ and π bonding between main-group elements, occurring in small sets of iso-valence-electronic molecules with elements drawn from second to fourth rows in the p-block of the periodic table. Numerical evidence suggests that first order Taylor expansions of covalent bonding potentials can achieve high accuracy if (i) the alchemical interpolation is vertical (fixed geometry), (ii) it involves elements from the third and fourth rows of the periodic table, and (iii) an optimal reference geometry is used. This leads to near linear changes in the bonding potential, resulting in analytical predictions with chemical accuracy (∼1 kcal/mol). Second order estimates deteriorate the prediction. If initial and final molecules differ not only in composition but also in geometry, all estimates become substantially worse, with second order being slightly more accurate than first order. The independent particle approximation based second order perturbation theory performs poorly when compared to the coupled perturbed or finite difference approach. Taylor series expansions up to fourth order of the potential energy curve of highly symmetric systems indicate a finite radius of convergence, as illustrated for the alchemical stretching of H2 (+). Results are presented for (i) covalent bonds to hydrogen in 12 molecules with 8 valence electrons (CH4, NH3, H2O, HF, SiH4, PH3, H2S, HCl, GeH4, AsH3, H2Se, HBr); (ii) main-group single bonds in 9 molecules with 14 valence electrons (CH3F, CH3Cl, CH3Br, SiH3F, SiH3Cl, SiH3Br, GeH3F, GeH3Cl, GeH3Br); (iii) main-group double bonds in 9 molecules with 12 valence electrons (CH2O, CH2S, CH2Se, SiH2O, SiH2S, SiH2Se, GeH2O, GeH2S, GeH2Se); (iv) main-group triple bonds in 9 molecules with 10 valence electrons (HCN, HCP, HCAs, HSiN, HSiP, HSiAs, HGeN, HGeP, HGeAs); and (v) H2 (+) single bond with 1 electron.

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

USGS Publications Warehouse

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

2015-01-01

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

Upland beech trees significantly contribute to forest methane exchange

NASA Astrophysics Data System (ADS)

Machacova, Katerina; Maier, Martin; Svobodova, Katerina; Halaburt, Ellen; Haddad, Sally; Lang, Friederike; Urban, Otmar

2016-04-01

Methane (CH4) can be emitted not only from soil, but also from plants. Fluxes of CH4were predominantly investigated in riparian herbaceous plants, whereas studies on trees, particularly those lacking an aerenchyma, are rare. In soil produced CH4 can be taken up by roots, transported via intercellular spaces and the aerenchyma system, or transpiration stream to aboveground plant tissues and released to the atmosphere via lenticels or stomata. Although CH4 might be also produced by microorganisms living in plant tissues or photochemical processes in plants, these processes are relatively minor. It has been shown that seedlings of European beech (Fagus sylvatica) emit CH4 from its stems despite the lack of an aerenchyma. Our objectives were to determine the CH4 fluxes from mature beech trees and adjacent soil under natural field conditions, and to estimate the role of trees in the CH4exchange within the soil-tree-atmosphere continuum. Measurements were conducted in two mountain beech forests with different geographical and climatic conditions (White Carpathians, Czech Republic; Black Forest, Germany). CH4 fluxes at stems (profile) and root bases level were simultaneously measured together with soil-atmosphere fluxes using static chamber systems followed by chromatographic analysis or continuous laser detection of CH4 concentrations. Our study shows that mature beech trees have the ability to exchange CH4 with the atmosphere. The beech stems emitted CH4 into the atmosphere at the White Carpathians site in the range from 2.00 to 179 μg CH4 m-2 stem area h-1, while CH4 flux rates ranged between -1.34 to 1.73 μg CH4 m-2 h-1 at the Black Forest site. The root bases of beech trees from the White Carpathians released CH4 into the atmosphere (from 0.62 to 49.8 μg CH4 m-2 root area h-1), whereas a prevailing deposition was observed in the Black Forest (from -1.21 to 0.81 μg CH4 m-2 h-1). These fluxes seem to be affected by soil water content and its spatial heterogeneity. Compared to beech trees, forest floor was a sink for CH4 on the both sites. The deposition rates reached -52 and -161 μg CH4 m-2 soil area h-1 at the White Carpathians and Black Forest site, respectively. Concluded, CH4 emissions from upland beech trees significantly contribute to total CH4 flux and have to be counted towards the overall CH4 balance of beech forest. Acknowledgement This research was financially supported by the Czech Academy of Sciences and the German Academic Exchange Service within the project "Methane (CH4) and nitrous oxide (N2O) emissions from Fagus sylvatica trees" (DAAD-15-03), National Programme for Sustainability I (LO1415) and DFG project (MA 5826/2-1). We thank Marek Jakubik for technical support and Sinikka Paulus for help by field measurements.

Methane uptake in urban forests and lawns.

PubMed

Groffman, Peter M; Pouyat, Richard V

2009-07-15

The largest natural biological sink for the radiatively active trace gas methane (CH4) is bacteria in soils that consume CH4 as an energy and carbon source. This sink has been shown to be sensitive to nitrogen (N) inputs and alterations of soil physical conditions. Given this sensitivity, conversion of native ecosystems to urban, suburban, and exurban managed lawns thus has potential to affect regional CH4 budgets. We measured CH4 fluxes monthly from four urban forest, four rural forest and four urban lawn plots in the Baltimore, MD, metropolitan area from 2001 to 2005. Our objectives were to evaluate the effects of urban atmospheric and land use change on CH4 uptake and the importance of these changes relative to other greenhouse forcings in the urban landscape. Rural forests had a high capacity for CH4 uptake (1.68 mg m(-2) day(-1)). This capacity was reduced in urban forests (0.23 mg m(-2) day(-1)) and almost completely eliminated in lawns. Possible mechanisms for these reductions include increases in atmospheric N deposition and CO2 levels, fertilization of lawns, and alteration of soil physical conditions that influence diffusion. Although conversion of native forests to lawns had dramatic effects on CH4 uptake, these effects do not appear to be significant to statewide greenhouse gas forcing.

Effects of organic nitrification inhibitors on methane and nitrous oxide emission from tropical rice paddy

NASA Astrophysics Data System (ADS)

Datta, A.; Adhya, T. K.

2014-08-01

We have studied the effects of application of different nitrification inhibitors on methane (CH4) and nitrous oxide (N2O) emissions from rice paddy and associated soil chemical and biological dynamics during wet and dry seasons of rice crop in a tropical climate of eastern India. The experiment consisted of four treatments viz. (i) Prilled urea amended control (ii) urea + Dicyandiamide (DCD), (iii) urea + Nimin and (iv) urea + Karanjin. CH4 emission was significantly higher from the DCD (372.36 kg ha-1) and Karanjin (153.07 kg ha-1) applied plots during the wet and dry season, respectively. N2O emission was significantly inhibited in the Nimin applied plots during both seasons (69% and 85% over control during wet season and dry season respectively). CH4 and N2O emissions per Mg of rice grain yield were lowest from the Nimin applied plots during both seasons. Global warming potential (GWP) of the plot treated with DCD (13.93) was significantly higher during the experimental period. CH4 production potential was significantly higher from the nitrification inhibitor applied plots compared to control. While, CH4 oxidation potential followed the order; urea + Nimin > urea + Karanjin > urea + DCD > control. Application of Nimin significantly increased the methanotrophic bacterial population in the soil during the maximum tillering to flowering stage and may be attributed to low CH4 emission from the plots. Denitrification enzyme activity (DEA) of the soil was significantly low from the Nimin and Karanjin applied plots. Results suggest that apart from being potent nitrification inhibitors, Nimin and Karanjin also have the potential to reduce the denitrification activity in the soil. This in turn, would reduce N2O emission from flooded paddy where both nitrification and denitrification processes causes N2O emission.

No limits to peat bog growth? Transport and thermodynamic constraints on anaerobic organic matter decomposition

NASA Astrophysics Data System (ADS)

Blodau, C.; Julia, B.; Siems, M.

2009-05-01

In diffusion dominated systems, for which many thick peat deposits provide a model, slowness of transport and lack of free energy may pose a limit to methanogenic decomposition of organic matter and ultimately to closing the carbon cycle. To test this hypothesis we (I) conducted controlled column experiments with homogenized peat over an 18 month period, (II) investigated transport, in situ respiration pathways, rates and thermodynamic conditions in a nothern peatland, and (III) modelled depth profiles of CO2 and CH4 in the deposits. Vertical transport in the peatland was dominated by diffusion leading to the buildup of DIC and CH4 with depth (5500 µmol L 1 DIC, 500 µmol L 1 CH4). Highest DIC and CH4 production rates occurred close to the water table (decomposition constant kd ~10-3 to 10 4 a-1) and decreased to about kd = 10-7 a-1. The accumulation of metabolic end-products diminished in situ energy yields of acetoclastic methanogenesis to the threshold for microbially mediated processes (-20 to -25 kJ mol-1 CH4). The methanogenic precursor acetate also accumulated (150 µmol L 1). In line with these findings, CH4 was formed by hydrogenotrophic methanogenesis at Gibbs free energies of 35 to 40 kJ mol-1 CH4. This was indicated by an isotopic fractionation αCO2-CH4 of 1.069 to 1.079. Fermentative degradation of acetate, propionate and butyrate attained Gibbs free energies close to 0 kJ mol-1 substrate. In peat columns with homogenenous peat-sand mixtures of 50%, 15% and 5% dry weight, steady state CO2 production also decreased from about 10 to 0 nmol cm-3 d-1 and of CH4 from 1 to 0 nmol cm-3 d-1 with depth. Very similar depth profiles of concentrations and volumetric rates developed near endproduct thresholds of 600µmol CH4 and 10 mmol L-1 CO2, despite the differences in organic matter content. The modeling exercise showed that a consistent development of CH4 concentration profiles over time in the columns could only be accomplished with rates of acetoclastic methanogenesis decreasing to 0 near a critical Gibbs free energy of about -27 KJ mol-1. The results thus suggest that, even in absence of inorganic electron acceptors, respiration rates in peat bogs are likely higher near the redox interface to the atmosphere due to lower respiration endproduct concentrations. Similar effects ensue when rates of transport are elevated or pools of CO2 and CH4 are eliminated. With decomposition being constrained, peat bog growth may occur longer than previously thought.

Oxidation of methane in biotrickling filters inoculated with methanotrophic bacteria.

PubMed

Cáceres, Manuel; Dorado, Antonio D; Gentina, Juan C; Aroca, Germán

2017-11-01

The oxidation of methane (CH 4 ) using biofilters has been proposed as an alternative to mitigate anthropogenic greenhouse gas emissions with a low concentration of CH 4 that cannot be used as a source of energy. However, conventional biofilters utilize organic packing materials that have a short lifespan, clogging problems, and are commonly inoculated with non-specific microorganisms leading to unpredictable CH 4 elimination capacities (EC) and removal efficiencies (RE). The main objective of this work was to characterize the oxidation of CH 4 in two biotrickling filters (BTFs) packed with polyethylene rings and inoculated with two methanotrophic bacteria, Methylomicrobium album and Methylocystis sp., in order to determine EC and CO 2 production (pCO 2 ) when using a specific inoculum. The repeatability of the results in both BTFs was determined when they operated at the same inlet load of CH 4 . A dynamic mathematical model that describes the CH 4 abatement in the BTFs was developed and validated using mass transfer and kinetic parameters estimated independently. The results showed that EC and pCO 2 of the BTFs are not identical but very similar for all the conditions tested. The use of specific inoculum has shown a faster startup and higher EC per unit area (0.019 gCH 4  m -2  h -1 ) in comparison to most of the previous studies at the same CH 4 load rate (23.2 gCH 4  m -3  h -1 ). Global mass balance showed that the maximum reduction of CO 2 equivalents was 98.5 gCO 2eq  m -3  h -1 . The developed model satisfactorily described CH 4 abatement in BTFs for a wide range of conditions.

Bis(μ-ferrocene­carboxyl­ato)bis­[aqua­­bis(ferrocene­carboxyl­ato)methano­l­erbium(III)] methanol disolvate

PubMed Central

Liu, Jianmin; Li, Yuanyuan; Li, Dacheng

2012-01-01

In the centrosymmetric title coordination compound, [Er2{Fe(C5H5)(C6H4O2)}6(CH3OH)2(H2O)2]·2CH3OH, the two ErIII ions are bridged by two ferrocene­carboxyl­ate anions as asymmetrically bridging ligands, leading to dimeric cores. The ErIII ion has a distorted dodeca­hedral coordination with six coordinating O atoms derived from the ferrocene­carboxyl­ate ligands and two coordinated O atoms from one water mol­ecule and one methanol mol­ecule. The asymmetric unit comprises a half of the complex mol­ecule and a methanol solvent mol­ecule. Intra­molecular O—H⋯O and C—H⋯O inter­actions occur. In the crystal, mol­ecules are linked by inter­molecular O—H⋯O hydrogen bonds and C—H⋯O as well as C—H⋯π inter­actions. PMID:22259358

Characterization of methane oxidation in a simulated landfill cover system by comparing molecular and stable isotope mass balances.

PubMed

Schulte, Marcel; Jochmann, Maik A; Gehrke, Tobias; Thom, Andrea; Ricken, Tim; Denecke, Martin; Schmidt, Torsten C

2017-11-01

Biological methane oxidation may be regarded as a method of aftercare treatment for landfills to reduce climate relevant methane emissions. It is of social and economic interest to estimate the behavior of bacterial methane oxidation in aged landfill covers due to an adequate long-term treatment of the gas emissions. Different approaches assessing methane oxidation in laboratory column studies have been investigated by other authors recently. However, this work represents the first study in which three independent approaches, ((i) mass balance, (ii) stable isotope analysis, and (iii) stoichiometric balance of product (CO 2 ) and reactant (CH 4 ) by CO 2 /CH 4 -ratio) have been compared for the estimation of the biodegradation by a robust statistical validation on a rectangular, wide soil column. Additionally, an evaluation by thermal imaging as a potential technique for the localization of the active zone of bacterial methane oxidation has been addressed in connection with stable isotope analysis and CO 2 /CH 4 -ratios. Although landfills can be considered as open systems the results for stable isotope analysis based on a closed system correlated better with the mass balance than calculations based on an open system. CO 2 /CH 4 -ratios were also in good agreement with mass balance. In general, highest values for biodegradation were determined from mass balance, followed by CO 2 /CH 4 -ratio, and stable isotope analysis. The investigated topsoil proved to be very suitable as a potential cover layer by removing up to 99% of methane for CH 4 loads of 35-65gm -2 d -1 that are typical in the aftercare phase of landfills. Finally, data from stable isotope analysis and the CO 2 /CH 4 -ratios were used to trace microbial activity within the reactor system. It was shown that methane consumption and temperature increase, as a cause of high microbial activity, correlated very well. Copyright © 2017 Elsevier Ltd. All rights reserved.

Rhodium(III)-Catalyzed Amidation of Unactivated C(sp(3) )-H Bonds.

PubMed

Wang, He; Tang, Guodong; Li, Xingwei

2015-10-26

Nitrogenation by direct functionalization of C-H bonds represents an important strategy for constructing C-N bonds. Rhodium(III)-catalyzed direct amidation of unactivated C(sp(3) )-H bonds is rare, especially under mild reaction conditions. Herein, a broad scope of C(sp(3) )-H bonds are amidated under rhodium catalysis in high efficiency using 3-substituted 1,4,2-dioxazol-5-ones as the amide source. The protocol broadens the scope of rhodium(III)-catalyzed C(sp(3) )-H activation chemistry, and is applicable to the late-stage functionalization of natural products. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

How Do Type Ia Supernova Nebular Spectra Depend on Explosion Properties? Insights from Systematic Non-LTE Modeling

NASA Astrophysics Data System (ADS)

Botyánszki, János; Kasen, Daniel

2017-08-01

We present a radiative transfer code to model the nebular phase spectra of supernovae (SNe) in non-LTE (NLTE). We apply it to a systematic study of SNe Ia using parameterized 1D models and show how nebular spectral features depend on key physical parameters, such as the time since explosion, total ejecta mass, kinetic energy, radial density profile, and the masses of 56Ni, intermediate-mass elements, and stable iron-group elements. We also quantify the impact of uncertainties in atomic data inputs. We find the following. (1) The main features of SN Ia nebular spectra are relatively insensitive to most physical parameters. Degeneracy among parameters precludes a unique determination of the ejecta properties from spectral fitting. In particular, features can be equally well fit with generic Chandrasekhar mass ({M}{ch}), sub-{M}{Ch}, and super-{M}{Ch} models. (2) A sizable (≳0.1 {M}⊙ ) central region of stable iron-group elements, often claimed as evidence for {M}{Ch} models, is not essential to fit the optical spectra and may produce an unusual flat-top [Co III] profile. (3) The strength of [S III] emission near 9500 Å can provide a useful diagnostic of explosion nucleosynthesis. (4) Substantial amounts (≳0.1 {M}⊙ ) of unburned C/O mixed throughout the ejecta produce [O III] emission not seen in observations. (5) Shifts in the wavelength of line peaks can arise from line-blending effects. (6) The steepness of the ejecta density profile affects the line shapes, offering a constraint on explosion models. (7) Uncertainties in atomic data limit the ability to infer physical parameters.

Neptunium and plutonium complexes with a sterically encumbered triamidoamine (TREN) scaffold

DOE PAGES

Brown, Jessie L.; Gaunt, Andrew J.; King, David M.; ...

2016-03-11

Here, the syntheses and characterization of isostructural neptunium(IV) and plutonium(IV) complexes [M IV(TREN TIPS)(Cl)] [An = Np, Pu; TREN TIPS = {N(CH 2CH 2NSiPr i 3) 3} 3] are reported, along with the demonstration that they are likely reduced to the corresponding neptunium(III) and plutonium(III) products [M III(TREN TIPS)]; this chemistry provides new platforms from which to target a plethora of unprecedented molecular functionalities in transuranic chemistry and the neptunium(IV) molecule is the first structurally characterized neptunium(IV)–amide complex.

Assessment of farm soil, biochar, compost and weathered pine mulch to mitigate methane emissions.

PubMed

Syed, Rashad; Saggar, Surinder; Tate, Kevin; Rehm, Bernd H A

2016-11-01

Previous studies have demonstrated the effective utility of volcanic pumice soil to mitigate both high and low levels of methane (CH 4 ) emissions through the activity of both γ-proteobacterial (type I) and α-proteobacterial (type II) aerobic methanotrophs. However, the limited availability of volcanic pumice soil necessitates the assessment of other farm soils and potentially suitable, economical and widely available biofilter materials. The potential biofilter materials, viz. farm soil (isolated from a dairy farm effluent pond bank area), pine biochar, garden waste compost and weathered pine bark mulch, were inoculated with a small amount of volcanic pumice soil. Simultaneously, a similar set-up of potential biofilter materials without inoculum was studied to understand the effect of the inoculum on the ability of these materials to oxidise CH 4 and their effect on methanotroph growth and activity. These materials were incubated at 25 °C with periodic feeding of CH 4 , and flasks were aerated with air (O 2 ) to support methanotroph growth and activity by maintaining aerobic conditions. The efficiency of CH 4 removal was monitored over 6 months. All materials supported the growth and activity of methanotrophs. However, the efficiency of CH 4 removal by all the materials tested fluctuated between no or low removal (0-40 %) and high removal phases (>90 %), indicating biological disturbances rather than physico-chemical changes. Among all the treatments, CH 4 removal was consistently high (>80 %) in the inoculated farm soil and inoculated biochar, and these were more resilient to changes in the methanotroph community. The CH 4 removal from inoculated farm soil and inoculated biochar was further enhanced (up to 99 %) by the addition of a nutrient solution. Our results showed that (i) farm soil and biochar can be used as a biofilter material by inoculating with an active methanotroph community, (ii) an abundant population of α-proteobacterial methanotrophs is essential for effective and stable CH 4 removal and (iii) addition of nutrients enhances the growth and activity of methanotrophs in the biofilter materials. Further studies are underway to assess the feasibility of these materials at small plot and field scales.

Crystal structure of [(1,2,3,4,11,12-η)-anthracene]tris­(tri­methyl­stann­yl)cobalt(III)

PubMed Central

Brennessel, William W.; Ellis, John E.

2014-01-01

The asymmetric unit of the title structure, [Co(η6-C14H10){Sn(CH3)3}3], contains two independent mol­ecules. Each anthracene ligand is η6-coordinating to a CoIII cation and is nearly planar [fold angles of 5.4 (3) and 9.7 (3)°], as would be expected for its behaving almost entirely as a donor to a high-oxidation-state metal center. The slight fold in each anthracene ligand gives rise to slightly longer Co—C bond lengths to the ring junction carbon atoms than to the other four. Each CoIII cation is further coordinated by three Sn(CH3)3 ligands, giving each mol­ecule a three-legged piano-stool geometry. In each of the two independent mol­ecules, the trio of SnMe3 ligands are modeled as disordered over two positions, rotated by approximately 30%, such that the C atoms nearly overlap. In one mol­ecule, the disorder ratio refined to 0.9365 (8):0.0635 (8), while that for the other refined to 0.9686 (8):0.0314 (8). The mol­ecules are well separated, and thus no significant inter­molecular inter­actions are observed. The compound is of inter­est as the first structure report of an η6-anthracene cobalt(III) complex. PMID:25484731

METHANE EMISSIONS FROM THE NATURAL GAS INDUSTRY VOLUME 10: METERING AND PRESSURE REGULATING STATIONS IN NATURAL GAS TRANSMISSIONS AND DISTRIBUTION

EPA Science Inventory

The 15-volume report summarizes the results of a comprehensive program to quantify methane (CH4) emissions from the U.S. natural gas industry for the base year. The objective was to determine CH4 emissions from the wellhead and ending downstream at the customer's meter. The accur...

Metal aminocarboxylate coordination polymers with chain and layered structures.

PubMed

Dan, Meenakshi; Rao, C N R

2005-11-18

The synthesis and structures of metal aminocarboxylates prepared in acidic, neutral, or alkaline media have been explored with the purpose of isolating coordination polymers with linear chain and two-dimensional layered structures. Metal glycinates of the formulae [CoCl2(H2O)2(CO2CH2NH3)] (I), [MnCl2(CO2CH2NH3)2] (II), and [Cd3Cl6(CO2CH2NH3)4] (III) with one-dimensional chain structures have been obtained by the reaction of the metal salts with glycine in an acidic medium under hydro/solvothermal conditions. These chain compounds contain glycine in the zwitterionic form. 4-Aminobutyric acid transforms to a cyclic amide under such reaction conditions, and the amide forms a chain compound of the formula [CdBr2(C4H7NO)2] (IV). Glycine in the zwitterionic form also forms a two-dimensional layered compound of the formula [Mn(H2O)2(CO2CH2NH3)2]Br2 (V). 6-Aminocaproic acid under alkaline conditions forms layered compounds with metals at room temperature, the metal being coordinated both by the amino nitrogen and the carboxyl oxygen atoms. Of the two layered compounds [Cd{CO2(CH2)5NH2}2]2 H2O (VI) and [Cu{CO2(CH2)5NH2}2]2 H2O (VII), the latter has voids in which water molecules reside.

Louisiana SIP: LAC 33:III Ch. 14 Subchap A, 1401 to 1415--Determining Conformity of General Federal Actions to State or Federal Implementation Plans; SIP effective 1996-11-12 (LAc67) and 1998-05-08 (LAc75)

EPA Pesticide Factsheets

Louisiana SIP: LAC 33:III Ch. 14 Subchap A, 1401 to 1415--Determining Conformity of General Federal Actions to State or Federal Implementation Plans; SIP effective 1996-11-12 (LAc67) and 1998-05-08 (LAc75)

Louisiana SIP: LAC 33:III Ch 21 Subchap J, 2147--Limiting Volatile Organic Compound (VOC) Emissions from Reactor Processes and Distillation Operations in Synthetic Organic Chemical manufacturing Industry (SOCMI); SIP effective 1998-02-02 (LAc74) to more..

EPA Pesticide Factsheets

Louisiana SIP: LAC 33:III Ch 21 Subchap J, 2147--Limiting Volatile Organic Compound (VOC) Emissions from Reactor Processes and Distillation Operations in Synthetic Organic Chemical manufacturing Industry (SOCMI); SIP effective 1998-02-02 (LAc74) more...

Louisiana SIP: LAC 33:III Ch 2147. Limiting Volatile Organic Compound (VOC) Emissions from Reactor Processes and Distillation Operations in Synthetic Organic Chemical manufacturing Industry (SOCMI); SIP effective 2011-08-04 (LAd34) to 2017-09-27

EPA Pesticide Factsheets

Louisiana SIP: LAC 33:III Ch 2147. Limiting Volatile Organic Compound (VOC) Emissions from Reactor Processes and Distillation Operations in Synthetic Organic Chemical manufacturing Industry (SOCMI); SIP effective 2011-08-04 (LAd34) to 2017-09-27

Selective dry etching of III-V nitrides in Cl{sub 2}/Ar, CH{sub 4}/H{sub 2}/Ar, ICi/Ar, and IBr/Ar

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

Vartuli, C.B.; Pearton, S.J.; MacKenzie, J.D.

1996-10-01

The selectivity for etching the binary (GaN, AlN, and InN) and ternary nitrides (InGaN and InAlN) relative to each other in Cl{sub 2}/Ar, CH{sub 4}/H{sub 2}/Ar, ICl/Ar, or IBr/Ar electron cyclotron resonance (ECR) plasmas, and Cl{sub 2}/Ar or CH{sub 4}/H{sub 2}/Ar reactive ion (RIE) plasmas was investigated. Cl-based etches appear to be the best choice for maximizing the selectivity of GaN over the other nitrides. GaN/AlN and GaN/InGaN etch rate ratios of {approximately} 10 were achieved at low RF power in Cl{sub 2}/Ar under ECR and RIE conditions, respectively. GaN/InN selectivity of 10 was found in ICl under ECR conditions.more » A relatively high selectivity (> 6) of InN/GaN was achieved in CH{sub 4}/H{sub 2}/Ar under ECR conditions at low RF powers (50 W). Since the high bond strengths of the nitrides require either high ion energies or densities to achieve practical etch rates it is difficult to achieve high selectivities.« less

Facile O-atom insertion into CC and CH bonds by a trinuclear copper complex designed to harness a singlet oxene

PubMed Central

Chen, Peter P.-Y.; Yang, Richard B.-G.; Lee, Jason C.-M.; Chan, Sunney I.

2007-01-01

Two trinuclear copper [CuICuICuI(L)]1+ complexes have been prepared with the multidentate ligands (L) 3,3′-(1,4-diazepane-1,4-diyl)bis(1-((2-(dimethylamino)ethyl)(methyl)amino)propan-2-ol) (7-Me) and (3,3′-(1,4-diazepane-1,4-diyl)bis(1-((2-(diethylamino) ethyl)(ethyl) amino)propan-2-ol) (7-Et) as models for the active site of the particulate methane monooxygenase (pMMO). The ligands were designed to form the proper spatial and electronic geometry to harness a “singlet oxene,” according to the mechanism previously suggested by our laboratory. Consistent with the design strategy, both [CuICuICuI(L)]1+ reacted with dioxygen to form a putative bis(μ3-oxo)CuIICuIICuIII species, capable of facile O-atom insertion across the central CC bond of benzil and 2,3-butanedione at ambient temperature and pressure. These complexes also catalyze facile O-atom transfer to the CH bond of CH3CN to form glycolonitrile. These results, together with our recent biochemical studies on pMMO, provide support for our hypothesis that the hydroxylation site of pMMO contains a trinuclear copper cluster that mediates CH bond activation by a singlet oxene mechanism. PMID:17804786

Biocompatible interpolymer complex matrix tablets - an oral sustained release class-III antidiabetic drug

NASA Astrophysics Data System (ADS)

Ershadul Haque, S. K.; Sheela, A.

2017-11-01

Development of sustained release formulations of Metformin hydrochloride (Met) having low bioavailability and short half-life is one of the frontier areas of research towards achieving novel drug delivery systems. Towards the same, we have prepared interpolymer complexes (IPCs) of chitosan (CH) and two different viscosity grades of hydroxypropyl methylcellulose - HPMC (K4M and K100M) in various ratios, say, 4:6, 2:8, 1:9, respectively. The IPCs are characterized by Fourier transform infrared spectroscopy (FT-IR) and Thermo gravimetric analysis (TGA) techniques. Drug compatibility study is carried out by FT-IR and powder X-ray diffraction (XRD) techniques. The physical properties and drug content of formulated tablets are evaluated and found to be optimum. In addition, in vitro drug release kinetics is carried out at two different pH, say, 1.2 and 6.8. The release pattern from different polymeric matrices is shown in figure below: a) Chitosan, HPMC K4M and HPMC K100M b) IPCs of CH/HPMC K4M in [2:3, 1:4 and 1:9 ratios] c) IPCs of CH/HPMC K100M in [2:3, 1:4 and 1:9 ratios]. From the study, it has been observed that the drug release is sustained for a period of 12h in 1:9 ratio of CH: K100M IPC due to the formation of complex network matrix.

Parenting styles and coping strategies among patients with early detected and treated congenital hypothyroidism.

PubMed

Pardo Campos, María L; Musso, Mariel; Keselman, Ana; Gruñeiro, Laura; Bergadá, Ignacio; Chiesa, Ana

2018-04-01

Congenital hypothyroidism (CH), as any chronic disease, has an impact on the parent-child relationship and on the child's resources to cope with conflicting situations. To describe parenting styles according to the perception of children with CH and their coping strategies. Children aged 9-10 years who had CH detected by newborn screening and had received adequate treatment and a group without CH (control group). The Argentine Coping Questionnaire, the Argentine Scale for the Perception of Parent Relations, and the comprehension subtest of the Wechsler Intelligence Scale for Children III (WISC III) were used. Results were compared using a multivariate analysis of variance (MANOVA). Sixty children with CH were included; they perceived that their mothers exercised a strict control and that their fathers showed more acceptance. They sought more support and became paralyzed more often in conflicting situations than the 60 children without CH. These findings may be associated with a higher level of dependence. They should be taken into consideration in CH care. Sociedad Argentina de Pediatría.

The Missing Link: Early Methane ("T") Dwarfs in the Sloan Digital Sky Survey.

PubMed

Leggett; Geballe; Fan; Schneider; Gunn; Lupton; Knapp; Strauss; McDaniel; Golimowski; Henry; Peng; Tsvetanov; Uomoto; Zheng; Hill; Ramsey; Anderson; Annis; Bahcall; Brinkmann; Chen; Csabai; Fukugita; Hennessy; Hindsley; Ivezic; Lamb; Munn; Pier; Schlegel; Smith; Stoughton; Thakar; York

2000-06-10

We report the discovery of three cool brown dwarfs that fall in the effective temperature gap between the latest L dwarfs currently known, with no methane absorption bands in the 1-2.5 µm range, and the previously known methane (T) dwarfs, whose spectra are dominated by methane and water. The newly discovered objects were detected as very red objects in the Sloan Digital Sky Survey imaging data and have JHK colors between the red L dwarfs and the blue Gl 229B-like T dwarfs. They show both CO and CH(4) absorption in their near-infrared spectra in addition to H(2)O, with weaker CH(4) absorption features in the H and K bands than those in all other methane dwarfs reported to date. Due to the presence of CH(4) in these bands, we propose that these objects are early T dwarfs. The three form part of the brown dwarf spectral sequence and fill in the large gap in the overall spectral sequence from the hottest main-sequence stars to the coolest methane dwarfs currently known.

The interstellar C-H stretching band near 3.4 microns - Constraints on the composition of organic material in the diffuse interstellar medium

NASA Technical Reports Server (NTRS)

Sandford, S. A.; Allamandola, L. J.; Tielens, A. G. G. M.; Pendleton, Y.; Sellgren, K.

1991-01-01

The composition and history of dust in the diffuse ISM was studied using 3600-2700/cm absorption spectra of objects which have widely varying amounts of visual extinctions along different lines of sight. The 3300/cm and 2950/cm features are attributed to O-H and C-H stretching vibrations, respectively. The O-H feature in OH 32.8-0.3 is suggestive of circumstellar water ice and is probably not due to material in the diffuse ISM. The features in the 3100-2700/cm region are attributed either to C-H vibrations or to M stars. The spectra of the latter show a series of narrow features in this region that are identified with photospheric OH. Objects in which these bands are seen include OH 01-477, T629-5, and the Galactic center source IRS 7. The C-H stretch feature of diffuse ISM dust has subpeaks which fall within 5/cm of C-H stretching vibrations in the -CH2- and -CH3 groups of saturated aliphatic hydrocarbons.

MEMO2 - MEthane goes MObile - MEasurements and Modelling - Part 2

NASA Astrophysics Data System (ADS)

Röckmann, Thomas; Walter, Sylvia

2017-04-01

As mitigation of climate change is a key scientific and societal challenge, the 2015 United Nations Climate Change Conference in Paris (COP21) agreed to limit global warming "well below" 2˚ C and, if possible, below 1.5˚ C. Reaching this target requires massive reductions of greenhouse gas emissions, and achieving significant reduction of greenhouse gas emissions is a logical headline targets of the EU climate action and of the H2020 strategy. CH4 emissions are a major contributor to Europe's global warming impact and emissions are not well quantified yet. There are significant discrepancies between official inventories of emissions and estimates derived from direct atmospheric measurement. Effective emission reduction can only be achieved if sources are properly quantified, and mitigation efforts are verified. New advanced combinations of measurement and modelling are needed to archive such quantification. MEMO2 will contribute to the targets of the EU with a focus on methane (CH4). The project will bridge the gap between large-scale scientific estimates from in situ monitoring programs and the 'bottom-up' estimates of emissions from local sources that are used in the national reporting by I) developing new and advanced mobile methane (CH4) measurements tools and networks, II) isotopic source identification, and III) modelling at different scales. Within the project qualified scientists will be educated in the use and implementation of interdisciplinary knowledge and techniques that are essential to meet and verify emission reduction goals. MEMO2 will facilitate intensive collaboration between the largely academic greenhouse gas monitoring community and non-academic partners who are responsible for evaluating and reporting greenhouse gas emissions to policy makers. MEMO2 is a European Training Network with more than 20 collaborators from 7 countries. It is a 4-years project and we will present the project and its objectives to the scientific community to foster collaboration and scientific exchange from the beginning.

Raman and Fourier Transform Infrared (FT-IR) Mineral to Matrix Ratios Correlate with Physical Chemical Properties of Model Compounds and Native Bone Tissue.

PubMed

Taylor, Erik A; Lloyd, Ashley A; Salazar-Lara, Carolina; Donnelly, Eve

2017-10-01

Raman and Fourier transform infrared (FT-IR) spectroscopic imaging techniques can be used to characterize bone composition. In this study, our objective was to validate the Raman mineral:matrix ratios (ν 1 PO 4 :amide III, ν 1 PO 4 :amide I, ν 1 PO 4 :Proline + hydroxyproline, ν 1 PO 4 :Phenylalanine, ν 1 PO 4 :δ CH 2 peak area ratios) by correlating them to ash fraction and the IR mineral:matrix ratio (ν 3 PO 4 :amide I peak area ratio) in chemical standards and native bone tissue. Chemical standards consisting of varying ratios of synthetic hydroxyapatite (HA) and collagen, as well as bone tissue from humans, sheep, and mice, were characterized with confocal Raman spectroscopy and FT-IR spectroscopy and gravimetric analysis. Raman and IR mineral:matrix ratio values from chemical standards increased reciprocally with ash fraction (Raman ν 1 PO 4 /Amide III: P < 0.01, R 2  = 0.966; Raman ν 1 PO 4 /Amide I: P < 0.01, R 2  = 0.919; Raman ν 1 PO 4 /Proline + Hydroxyproline: P < 0.01, R 2  = 0.976; Raman ν 1 PO 4 /Phenylalanine: P < 0.01, R 2  = 0.911; Raman ν 1 PO 4 /δ CH 2 : P < 0.01, R 2  = 0.894; IR P < 0.01, R 2  = 0.91). Fourier transform infrared mineral:matrix ratio values from native bone tissue were also similar to theoretical mineral:matrix ratio values for a given ash fraction. Raman and IR mineral:matrix ratio values were strongly correlated ( P < 0.01, R 2  = 0.82). These results were confirmed by calculating the mineral:matrix ratio for theoretical IR spectra, developed by applying the Beer-Lambert law to calculate the relative extinction coefficients of HA and collagen over the same range of wavenumbers (800-1800 cm -1 ). The results confirm that the Raman mineral:matrix bone composition parameter correlates strongly to ash fraction and to its IR counterpart. Finally, the mineral:matrix ratio values of the native bone tissue are similar to those of both chemical standards and theoretical values, confirming the biological relevance of the chemical standards and the characterization techniques.

Reducing methane emissions and the methanogen population in the rumen of Tibetan sheep by dietary supplementation with coconut oil.

PubMed

Ding, Xuezhi; Long, Ruijun; Zhang, Qian; Huang, Xiaodan; Guo, Xusheng; Mi, Jiandui

2012-10-01

The objective was to evaluate the effect of dietary coconut oil on methane (CH(4)) emissions and the microbial community in Tibetan sheep. Twelve animals were assigned to receive either a control diet (oaten hay) or a mixture diet containing concentrate (maize meal), in which coconut oil was supplemented at 12 g/day or not for a period of 4 weeks. CH(4) emissions were measured by using the 'tunnel' technique, and microbial communities were examined using quantitative real-time PCR. Daily CH(4) production for the control and forage-to-concentrate ratio of 6:4 was 17.8 and 15.3 g, respectively. Coconut oil was particularly effective at reducing CH(4) emissions from Tibetan sheep. The inclusion of coconut oil for the control decreased CH(4) production (in grams per day) by 61.2%. In addition, there was a positive correlation between the number of methanogens and the daily CH(4) production (R = 0.95, P < 0.001). Oaten hay diet containing maize meal (6:4) plus coconut oil supplemented at 12 g/day decreases the number of methanogens by 77% and a decreases in the ruminal fungal population (85-95%) and Fibrobacter succinogenes (50-98%) but an increase in Ruminococcus flavefaciens (25-70%). The results from our experiment suggest that adding coconut oil to the diet can reduce CH(4) emissions in Tibetan sheep and that these reductions persist for at least the 4-week feeding period.

Genetic parameters of methane emissions determined using portable accumulation chambers in lambs and ewes grazing pasture and genetic correlations with emissions determined in respiration chambers.

PubMed

Jonker, A; Hickey, S M; Rowe, S J; Janssen, P H; Shackell, G; Elmes, S; Bain, W E; Wing, J; Greer, G J; Bryson, B; MacLean, S; Dodds, K G; Pinares-Patiño, C S; Young, E A; Knowler, K; Pickering, N K; McEwan, J C

2018-05-07

Methane (CH4) emission traits were previously found to be heritable and repeatable in sheep fed alfalfa pellets in respiration chambers (RC). More rapid screening methods are, however, required to increase genetic progress and to provide a cost effective method to the farming industry for maintaining the generation of breeding values in the future. The objective of the current study was to determine CH4 and carbon dioxide (CO2) emissions using several one-hour portable accumulation chamber (PAC) measurements from lambs and again as ewes, while grazing ryegrass based pasture. Many animals with PAC measurements were also measured in RC while fed alfalfa pellets at 2.0 × maintenance metabolizable energy requirements (MEm). Heritability estimates from mixed models for CH4 and CO2 production (g/d) were 0.19 and 0.16, respectively, when measured using PAC with lambs; 0.20 and 0.27, respectively, when measured using PAC with ewes; and 0.23 and 0.34, respectively, when measured using RC with lambs. For measured gas traits, repeatabilities of measurements collected 14 days apart ranged from 0.33 to 0.55 for PAC (combined lambs and ewes) and were greater at 0.65 to 0.76 for the same traits measured using RC. Genetic correlations (rg) between PAC in lambs and ewes were 0.99 for CH4, 0.93 for CH4+CO2 and 0.85 for CH4/(CH4+CO2), suggesting CH4 emissions in lambs and ewes are the same trait. Genetic correlations between PAC and RC measurements were lower, at 0.62 to 0.67 for CH4 and 0.41 to 0.42 for CH4+CO2, likely reflecting different environmental conditions associated with the protocols used with the two measurement methods. The CH4/(CH4+CO2) ratio was the most similar genetic trait measured using PAC (both lambs and ewes, 63 and 66% selection efficiency, respectively) compared with CH4 yield (g/kg DMI) measured using RC. These results suggest that PAC measurements have considerable value as a rapid low cost method to estimate breeding values for CH4 emissions in sheep.

Synthesis and spectroscopic studies of biologically active compounds derived from oxalyldihydrazide and benzil, and their Cr(III), Fe(III) and Mn(III) complexes.

PubMed

Singh, D P; Kumar, Ramesh; Singh, Jitender

2009-04-01

A new series of complexes have been synthesized by template condensation of oxalyldihydrazide and benzil in methanolic medium in the presence of trivalent chromium, manganese and iron salts forming complexes of the type [M(C(32)H(24)N(8)O(4))X]X(2) where M = Cr(III), Mn(III), Fe(III) and X = Cl(-1), NO(3)(-1), CH(3)COO(-1). The complexes have been characterized with the help of elemental analyses, conductance measurements, magnetic susceptibility measurements, electronic, NMR, infrared and far infrared spectral studies. On the basis of these studies, a five coordinate square pyramidal geometry has been proposed for all these complexes. The biological activities of the metal complexes have been tested in vitro against a number of pathogenic bacteria to assess their inhibiting potential. Some of these complexes have been found to exhibit remarkable antibacterial activities.

Enhancement of farmland greenhouse gas emissions from leakage of stored CO2: simulation of leaked CO2 from CCS.

PubMed

Zhang, Xueyan; Ma, Xin; Wu, Yang; Li, Yue

2015-06-15

The effects of leaked CO2 on plant and soil constitute a key objective of carbon capture and storage (CCS) safety. The effects of leaked CO2 on trace soil gas (e.g., methane (CH4) and nitrous oxide (N2O) emissions in farmlands are not well-understood. This study simulated the effects of elevated soil CO2 on CH4 and N2O through pot experiments. The results revealed that significant increases of CH4 and N2O emissions were induced by the simulated CO2 leakages; the emission rates of CH4 and N2O were substantial, reaching about 222 and 48 times than that of the control, respectively. The absolute global warming potentials (GWPs) of the additional CH4 and N2O are considerable, but the cumulative GWPs of the additional CH4 and N2O only accounted for 0.03% and 0.06%, respectively, of the cumulative amount of leaked CO2 under high leakage conditions. The results demonstrate that leakage from CCS projects may lead to additional greenhouse gas emissions from soil; however, in general, the amount of additional CH4 and N2O emissions is negligible when compared with the amount of leaked CO2. Copyright © 2015 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Nitroethane, 2-nitro-methyl-propionate and dimethyl-2-nitroglutarate markedly reduce ruminal methane production without adversely affecting ruminal fermentation

USDA-ARS?s Scientific Manuscript database

Ruminal methanogenesis is considered a digestive inefficiency that results in the loss of 2-12% of the host’s gross energy intake and accounts for nearly 20% of the United States’ annual CH4 emissions. The objective of the present experiment was to evaluate the effects of the known CH4 inhibitor, n...

Louisiana SIP: LAC 33:III Ch. 7 Section 701. Purpose and Information Regarding Standards for PM10, SO2, CO, Atmospheric Oxidants, NOx and Pb; SIP effective 1989-05-08 (LAc49) to 2011-08-03 (LAd34 - Revised)

EPA Pesticide Factsheets

Louisiana SIP: LAC 33:III Ch. 7 Section 701. Purpose and Information Regarding Standards for PM10, SO2, CO, Atmospheric Oxidants, NOx and Pb; SIP effective 1989-05-08 (LAc49) to 2011-08-03 (LAd34 - Revised)

Louisiana SIP: LAC 33:III Ch 2132. Stage II Vapor Recovery Systems for Control of Vehicle Refuelling Emissions at Gasoline Dispensing Facilities; SIP effective 2011-08-04 (LAd34) and 2016-02-29 (LAd47) to 2017-09-27

EPA Pesticide Factsheets

Louisiana SIP: LAC 33:III Ch 2132. Stage II Vapor Recovery Systems for Control of Vehicle Refuelling Emissions at Gasoline Dispensing Facilities; SIP effective 2011-08-04 (LAd34) and 2016-02-29 (LAd47) to 2017-09-27

U.S. Air Force Environmental Assessment, Add To and Alter Type III Hydrant Fueling System, Tinker Air Force Base, Oklahoma

DTIC Science & Technology

2011-12-01

burning of fossil fuels (e.g., oil , natural gas , coal), solid waste decay, and trees and wood products and also as a result of chemical reactions...to negative GHG effects. Methane. CH4 is a GHG that is emitted during the production and transport of coal, natural gas , and oil . Methane...the pump station (Facility 486); Control Room (Facility 487); and the oil -water separator (Facility 488). • Construction of a new Type III pump house

Tetra­ethyl­ammonium dicyanido(5,10,15,20-tetra­phenyl­porphyrinato)ferrate(III) di­chloro­methane monosolvate

PubMed Central

Kassenova, Nazira; Hietsoi, Oleksandr; Yerkassov, Rakhmetulla; Shatruk, Michael

2013-01-01

The title compound, (C8H20N)[Fe(C44H28N4)(CN)2]·CH2Cl2 or (Et4N)[Fe(TPP)(CN)2], was recrystallized from di­chloro­methane–diethyl ether. The compound crystallizes with the two unique halves of the FeIII porphyrinato complex, one tetra­ethyl­ammonium cation and one inter­stitial di­chloro­methane mol­ecule within the asymmetric unit. Both anionic FeIII complexes exhibit inversion symmetry. Both the cation and the solvent mol­ecules show positional disorder. The cation is disordered over two sets of sites with an occupancy ratio of 0.710 (3):0.290 (3); the solvent mol­ecule is disordered over three positions with a 0.584 (6):0.208 (3):0.202 (5) ratio. The crystal packing features columns of [Fe(TPP)(CN)2]− anions that propagate along [001]. The columns further pack into layers that are parallel to (011) and also include the Et4N+ cations. The inter­stitial CH2Cl2 mol­ecules appear in the inter­layer space. This complex may serve as a useful precursor for the assembly of multinuclear and extended CN-bridged complexes for the design of single-mol­ecule and single-chain magnets, respectively. PMID:24109282

Trapping a Highly Reactive Nonheme Iron Intermediate That Oxygenates Strong C-H Bonds with Stereoretention.

PubMed

Serrano-Plana, Joan; Oloo, Williamson N; Acosta-Rueda, Laura; Meier, Katlyn K; Verdejo, Begoña; García-España, Enrique; Basallote, Manuel G; Münck, Eckard; Que, Lawrence; Company, Anna; Costas, Miquel

2015-12-23

An unprecedentedly reactive iron species (2) has been generated by reaction of excess peracetic acid with a mononuclear iron complex [Fe(II)(CF3SO3)2(PyNMe3)] (1) at cryogenic temperatures, and characterized spectroscopically. Compound 2 is kinetically competent for breaking strong C-H bonds of alkanes (BDE ≈ 100 kcal·mol(-1)) through a hydrogen-atom transfer mechanism, and the transformations proceed with stereoretention and regioselectively, responding to bond strength, as well as to steric and polar effects. Bimolecular reaction rates are at least an order of magnitude faster than those of the most reactive synthetic high-valent nonheme oxoiron species described to date. EPR studies in tandem with kinetic analysis show that the 490 nm chromophore of 2 is associated with two S = 1/2 species in rapid equilibrium. The minor component 2a (∼5% iron) has g-values at 2.20, 2.19, and 1.99 characteristic of a low-spin iron(III) center, and it is assigned as [Fe(III)(OOAc)(PyNMe3)](2+), also by comparison with the EPR parameters of the structurally characterized hydroxamate analogue [Fe(III)(tBuCON(H)O)(PyNMe3)](2+) (4). The major component 2b (∼40% iron, g-values = 2.07, 2.01, 1.95) has unusual EPR parameters, and it is proposed to be [Fe(V)(O)(OAc)(PyNMe3)](2+), where the O-O bond in 2a has been broken. Consistent with this assignment, 2b undergoes exchange of its acetate ligand with CD3CO2D and very rapidly reacts with olefins to produce the corresponding cis-1,2-hydroxoacetate product. Therefore, this work constitutes the first example where a synthetic nonheme iron species responsible for stereospecific and site selective C-H hydroxylation is spectroscopically trapped, and its catalytic reactivity against C-H bonds can be directly interrogated by kinetic methods. The accumulated evidence indicates that 2 consists mainly of an extraordinarily reactive [Fe(V)(O)(OAc)(PyNMe3)](2+) (2b) species capable of hydroxylating unactivated alkyl C-H bonds with stereoretention in a rapid and site-selective manner, and that exists in fast equilibrium with its [Fe(III)(OOAc)(PyNMe3)](2+) precursor.

Coinage metal coordination chemistry of stable primary, secondary and tertiary ferrocenylethyl-based phosphines.

PubMed

Azizpoor Fard, M; Rabiee Kenaree, A; Boyle, P D; Ragogna, P J; Gilroy, J B; Corrigan, J F

2016-02-21

Ferrocene-based phosphines constitute an important auxiliary ligand in inorganic chemistry. Utilizing the (ferrocenylethyl)phosphines (FcCH2CH2)3-nHnP (Fc = ferrocenyl; n = 2, 1; n = 1, 2; n = 0, 3) the synthesis of a series of coordination complexes [(FcCH2CH2)3-nHnPCuCl]4 (n = 2, 1-CuCl; n = 0, 3-CuCl), [(FcCH2CH2)2HPCuCl] (2-CuCl), {[(FcCH2CH2)H2P]2AgCl}2 (1-AgCl), [(FcCH2CH2)2HPAgCl] (2-AgCl), [(FcCH2CH2)3PAgCl]4 (3-AgCl), [(FcCH2CH2)3PM(OAc)]4 (M = Cu, 3-CuOAc M = Ag, 3-AgOAc), [(FcCH2CH2)3-nHnPAuCl] (n = 1, 2-AuCl; n = 0, 3-AuCl), via the reaction between the free phosphine and MX (M = Cu, Ag and Au; X = Cl, OAc), is described. The reaction between the respective phosphine with a suspension of metal-chloride or -acetate in a 1 : 1 ratio in THF at ambient temperature affords coordinated phosphine-coinage metal complexes. Varying structural motifs are observed in the solid state, as determined via single crystal X-ray analysis of 1-CuCl, 3-CuCl, 1-AgCl, 3-AgCl, 3-CuOAc, 3-AgOAc, 2-AuCl and 3-AuCl. Complexes 1-CuCl and 3-CuCl are tetrameric Cu(i) cubane-like structures with a Cu4Cl4 core, whereas silver complexes with primary and tertiary phosphine reveal two different structural types. The structure of 1-AgCl, unlike the rest, displays the coordination of two phosphines to each silver atom and shows a quadrangle defined by two Ag and two Cl atoms. In contrast, 3-AgCl is distorted from a cubane structure via elongation of one of the ClAg distances. 3-CuOAc and 3-AgOAc are isostructural with step-like cores, while complexes 2-AuCl and 3-AuCl reveal a linear geometry of a phosphine gold(i) chloride devoid of any aurophilic interactions. All of the complexes were characterized in solution by multinuclear (1)H, (13)C{(1)H} and (31)P NMR spectroscopic techniques; the redox chemistry of the series of complexes was examined using cyclic voltammetry. This class of complexes has been found to exhibit one reversible Fe(ii)/Fe(iii) oxidation couple, suggesting the absence of electronic communication between the ferrocenyl units on individual phosphine ligands as well as between different phosphines on the polymetallic cores.

Pyrroloindolone synthesis via a Cp*Co(III)-catalyzed redox-neutral directed C-H alkenylation/annulation sequence.

PubMed

Ikemoto, Hideya; Yoshino, Tatsuhiko; Sakata, Ken; Matsunaga, Shigeki; Kanai, Motomu

2014-04-09

A unique synthetic utility of a Cp*Co(III) catalyst in comparison with related Cp*Rh(III) catalysts is described. A C2-selective indole alkenylation/annulation sequence proceeded smoothly with catalytic amount of a [Cp*Co(III)(C6H6)](PF6)2 complex and KOAc. Intramolecular addition of an alkenyl-Cp*Co species to a carbamoyl moiety gave pyrroloindolones in 58-89% yield in one pot. Clear difference was observed between the catalytic activity of the Cp*Co(III) complex and those of Cp*Rh(III) complexes, highlighting the unique nucleophilic activity of the organocobalt species. The Cp*Co(III) catalysis was also suitable for simple alkenylation process of N-carbamoyl indoles, and broad range of alkynes, including terminal alkynes, were applicable to give C2-alkenylated indoles in 50-99% yield. Mechanistic studies on C-H activation step under Cp*Co(III) catalysis with the aid of an acetate unit as well as evaluation of the difference between organo-Co(III) species and organo-Rh(III) species are also described.

Environmental factors influencing landfill gas biofiltration: Lab scale study on methanotrophic bacteria growth.

PubMed

Amodeo, Corrado; Sofo, Adriano; Tito, Maria Teresa; Scopa, Antonio; Masi, Salvatore; Pascale, Raffaella; Mancini, Ignazio M; Caniani, Donatella

2018-03-29

The post-management of landfills represents an important challenge for landfill gas treatment. Traditional systems (energy recovery, flares, etc.) present technical problems in treating flow with low methane (CH 4 ) concentrations. The objective of this study was to isolate methanotrophic bacteria from a field-scale biofilter in order to study the bacteria in laboratories and evaluate the environmental factors that mostly influence Microbial Aerobic Methane Oxidation (MAMO). The soil considered was sampled from the biofilter located in the landfill of Venosa (Basilicata Region, Italy) and it was mainly composed of wood chips and compost. The results showed that methanotrophic microorganisms are mainly characterized by a slow growth and a significant sensitivity to CH 4 levels. Temperature and nitrogen (N) also have a very important role on their development. On the basis of the results, biofilters for biological CH 4 oxidation can be considered a viable alternative to mitigate CH 4 emissions from landfills.

Are closed landfills free of CH_{4} emissions? A case study of Arico's landfill, Tenerife, Canary Islands

NASA Astrophysics Data System (ADS)

Barrancos, José; Cook, Jenny; Phillips, Victoria; Asensio-Ramos, María; Melián, Gladys; Hernández, Pedro A.; Pérez, Nemesio M.

2016-04-01

Landfills are authentic chemical and biological reactors that introduce in the environment a wide amount of gas pollutants (CO2, CH4, volatile organic compounds, etc.) and leachates. Even after years of being closed, a significant amount of landfill gas could be released to the atmosphere through the surface in a diffuse form, also known as non-controlled emission. The study of the spatial-temporal distribution of diffuse emissions provides information of how a landfill degassing takes place. The main objective of this study was to estimate the diffuse uncontrolled emission of CH4 into the atmosphere from the closed Arico's landfill (0.3 km2) in Tenerife Island, Spain. To do so, a non-controlled biogenic gas emission survey of nearly 450 sampling sites was carried out during August 2015. Surface gas sampling and surface landfill CO2 efflux measurements were carried out at each sampling site by means of a portable non-dispersive infrared spectrophotometer (NDIR) model LICOR Li800 following the accumulation chamber method. Landfill gases, CO2 and CH4, were analyzed using a double channel VARIAN 4900 micro-GC. The CH4 efflux was computed combining CO2 efflux and CH4/CO2 ratio in the landfill's surface gas. To quantify the total CH4 emission, CH4 efflux contour map was constructed using sequential Gaussian simulation (sGs) as interpolation method. The total diffuse CH4 emission was estimated in 2.2 t d-1, with CH4 efflux values ranging from 0-922 mg m-2 d-1. This type of studies provides knowledge of how a landfill degasses and serves to public and private entities to establish effective systems for extraction of biogas. This aims not only to achieve higher levels of controlled gas release from landfills resulting in a higher level of energy production but also will contribute to minimize air pollution caused by them.

Louisiana SIP: LAC 33:III Ch. 14 Subchap B, 1431 to 1434--Conformity to State or Federal Implementation Plans of Transportation Plans, Programs, and Projects Developed, Funded, or Approved Under Title 23 U.S.C. or the Federal Transit Laws

EPA Pesticide Factsheets

Louisiana SIP: LAC 33:III Ch. 14 Subchap B, 1431 to 1434--Conformity to State or Federal Implementation Plans of Transportation Plans, Programs, and Projects Developed, Funded, or Approved Under Title 23 U.S.C. or the Federal Transit Laws

Computational study of An-X bonding (An = Th, U; X = p-block-based ligands) in pyrrolic macrocycle-supported complexes from the quantum theory of atoms in molecules and bond energy decomposition analysis.

PubMed

O'Brien, Kieran T P; Kaltsoyannis, Nikolas

2017-01-17

A systematic computational study of organoactinide complexes of the form [LAnX] n+ has been carried out using density functional theory, the quantum theory of atoms in molecules (QTAIM) and Ziegler-Rauk energy decomposition analysis (EDA) methods. The systems studied feature L = trans-calix[2]benzene[2]pyrrolide, An = Th(iv), Th(iii), U(iii) and X = BH 4 , BO 2 C 2 H 4 , Me, N(SiH 3 ) 2 , OPh, CH 3 , NH 2 , OH, F, SiH 3 , PH 2 , SH, Cl, CH 2 Ph, NHPh, OPh, SiH 2 Ph, PHPh 2 , SPh, CPh 3 , NPh 2 , OPh, SiPh 3 PPh 2 , SPh. The PBE0 hybrid functional proved most suitable for geometry optimisations based on comparisons with available experimental data. An-X bond critical point electron densities, energy densities and An-X delocalisation indices, calculated with the PBE functional at the PBE0 geometries, are correlated with An-X bond energies, enthalpies and with the terms in the EDA. Good correlations are found between energies and QTAIM metrics, particularly for the orbital interaction term, provided the X ligand is part of an isoelectronic series and the number of open shell electrons is low (i.e. for the present Th(iv) and Th(iii) systems).

Molecular assembly and magnetic dynamics of two novel Dy6 and Dy8 aggregates.

PubMed

Guo, Yun-Nan; Chen, Xiao-Hua; Xue, Shufang; Tang, Jinkui

2012-04-02

Complexation of dysprosium(III) with the heterodonor chelating ligand o-vanillin picolinoylhydrazone (H(2)ovph) in the presence of a carbonato ligand affords two novel Dy(6) and Dy(8) clusters, namely, [Dy(6)(ovph)(4)(Hpvph)(2)Cl(4)(H(2)O)(2)(CO(3))(2)]·CH(3)OH·H(2)O·CH(3)CN (2) and [Dy(8)(ovph)(8)(CO(3))(4)(H(2)O)(8)]·12CH(3)CN·6H(2)O (3). Compound 2 is composed of three petals of the Dy(2) units linked by two carbonato ligands, forming a triangular prism arrangement, while compound 3 possesses an octanuclear core with an unprecedented tub conformation, in which Dy(ovph) fragments are attached to the sides of the carbonato core. The static and dynamic magnetic properties are reported and discussed. In the Dy(6) aggregate, three Dy(2) "skeletons", having been well preserved (see the scheme), contribute to the single-molecule-magnet behavior with a relatively slow tunneling rate, while the Dy(8) cluster only exhibits a rather small relaxation barrier.

From iron coordination compounds to metal oxide nanoparticles

PubMed Central

Iacob, Mihail; Racles, Carmen; Tugui, Codrin; Stiubianu, George; Bele, Adrian; Sacarescu, Liviu; Timpu, Daniel

2016-01-01

Various types, shapes and sizes of iron oxide nanoparticles were obtained depending on the nature of the precursor, preparation method and reaction conditions. The mixed valence trinuclear iron acetate, [Fe2 IIIFeIIO(CH3COO)6(H2O)3]·2H2O (FeAc1), μ3-oxo trinuclear iron(III) acetate, [Fe3O(CH3COO)6(H2O)3]NO3∙4H2O (FeAc2), iron furoate, [Fe3O(C4H3OCOO)6(CH3OH)3]NO3∙2CH3OH (FeF), iron chromium furoate, FeCr2O(C4H3OCOO)6(CH3OH)3]NO3∙2CH3OH (FeCrF), and an iron complex with an original macromolecular ligand (FePAZ) were used as precursors for the corresponding oxide nanoparticles. Five series of nanoparticle samples were prepared employing either a classical thermal pathway (i.e., thermal decomposition in solution, solvothermal method, dry thermal decomposition/calcination) or using a nonconventional energy source (i.e., microwave or ultrasonic treatment) to convert precursors into iron oxides. The resulting materials were structurally characterized by wide-angle X-ray diffraction and Fourier transform infrared, Raman, energy-dispersive X-ray, and X-ray fluorescence spectroscopies, as well as thermogravimetric analysis. The morphology was characterized by transmission electron microscopy, atomic force microscopy and dynamic light scattering. The parameters were varied within each route to fine tune the size and shape of the formed nanoparticles. PMID:28144555

Anaerobic methane oxidation may be more prevalent in surface soils than was originally thought

NASA Astrophysics Data System (ADS)

Gauthier, Mathieu; Bradley, Robert L.; Šimek, Miloslav

2013-04-01

Anaerobic oxidation of methane (CH4) (AOM) is a process that was first reported to occur in deep anoxic marine sediments. In this environment, CH4 is oxidized with sulphate (SO42-) as the terminal electron acceptor. It is mediated by a syntrophic consortium formed by SO42- reducing bacteria and anaerobic CH4 oxidizing Archaea, or by the latter alone. Since this landmark discovery, AOM was found to occur in other environments including freshwater lake sediments and water columns, mud volcanoes, landfill leachate, deep buried Holocene sediments and hydrocarbon contaminated aquifers. All of these situations are very specific and point to AOM as being primarily occurring in highly reducing conditions. Thus, observations of AOM in surface soils with fluctuating REDOX conditions are relatively scarce, although a few independent studies have reported AOM in surface peatlands as well as in a forest soil. Furthermore, AOM may follow different pathways, such as via the coupled oxidation of CH4 and reduction of manganese (Mn(IV)) or iron (Fe(III)), or by a lone denitrifying species that converts nitrite to nitric oxide in order to generate O2 that is then used internally to oxidize CH4. Thus, the goal of our study was to determine whether AOM is more prevalent than was thought in hydromorphic surface soils across different environments, and whether the addition of NO3- or SO4= as alternative electron acceptors may stimulate the process. We collected samples from 3 peatland soils in Scotland, 2 acid-sulphate soils in Finland, and shore sediments of 15 drained fish ponds in the Czech Republic. Subsamples were incubated in the absence of O2 and amended with either NO3-, SO42-, or left unamended (control). The net flux of CH4 and CO2 were assessed by gas chromatography after 2, 20, 40 and 60 days. We also used a 13C-CH4 isotope dilution technique to determine gross production and consumption rates of CH4. We detected AOM in all of our soils, with oxidation rates ranging between 0.001 and 37.28 nmol g-1 day-1, suggesting that AOM may be more ubiquitous than was originally thought. On the other hand, no clear patterns emerged as to the effects of NO3- or SO42- amendments on this process.

Effect of Fodder Tree Species with Condensed Tannin Contents on In vitro Methane Production

PubMed Central

Vázquez, Ernestina Gutiérrez; Medina, Leonardo Hernández; Benavides, Liliana Márquez; Caratachea, Aureliano Juárez; Razo, Guillermo Salas; Burgos, Armin Javier Ayala; Rodríguez, Ruy Ortiz

2016-01-01

The objective was to evaluate the effect of fodder tree species (FTS) with condensed tannin contents: Cordia elaeagnoides, Platymiscium lasiocarpum, Vitex mollis, and Haematoxylon brasiletto, on in vitro methane (CH4) production at 24 h post incubation. The analysis was performed using the in vitro gas production technique, with three levels of inclusion/species: 600, 800, and 1,000 mg and with 4 replicates/species/level of inclusion. The substrate was incubated at 39°C, and the gas and CH4 production were recorded at 4, 8, 12, and 24 h post incubation. The data collected was analyzed through Pearson correlation, polinomial regression and fixed effects models. There were negative correlations between FTS-total gas volume (r = −0.40; p<0.001); FTS-volume of CH4 produced (r = −0.40; p<0.001) and between the inclusion level-volume of CH4 produced (r = −0.20; p<0.001). As well as a positive correlation between hours post incubation-total gas volume (r = 0.42; p<0.001) and between hours post incubation-volume of CH4 produced (r = 0.48; p<0.001). The FTS: C. elaeagnoides, V. mollis, and H. brasiletto have potential, in the three inclusion levels analyzed, to reduce CH4 emission on in vitro trials (>32.7%), taking into account the total CH4 production at 24 h of the forage used as reference (Avena sativa). It’s suggested that C. elaeagnoides-according to its crude protein, neutral detergent fiber, and condensed tannins content- is the best alternative within the FTS analyzed, for feeding ruminants and for the control of CH4 emissions during the dry season. PMID:26732330

Synthesis, Electrochemistry, and Excited-State Properties of Three Ru(II) Quaterpyridine Complexes

DOE PAGES

Rudd, Jennifer A.; Brennaman, M. Kyle; Michaux, Katherine E.; ...

2016-03-09

The complexes [Ru(qpy)LL']2+ (qpy = 2,2':6',2'':6'',2''-quaterpyridine), with 1: L = acetonitrile, L'= chloride; 2: L = L'= acetonitrile; and 3: L = L'= vinylpyridine, have been prepared from [Ru(qpy) (Cl)2]. Their absorption spectra in CH3CN exhibit broad metal-to-ligand charge transfer (MLCT) absorptions arising from overlapping 1A1 → 1MLCT transitions. Photoluminescence is not observed at room temperature, but all three are weakly emissive in 4:1 ethanol/methanol glasses at 77 K with broad, featureless emissions observed between 600 and 1000 nm consistent with MLCT phosphorescence. Cyclic voltammograms in CH3CN reveal the expected RuIII/II redox couples. In 0.1 M trifluoroacetic acid (TFA), 1more » and 2 undergo aquation to give [RuII(qpy)(OH2)2]2+, as evidenced by the appearance of waves for the couples [RuIII(qpy)(OH2)2]3+/[RuII(qpy)(OH2)2]2+, [RuIV(qpy)(O)(OH2)]2+/[RuIII(qpy)(OH2)2]3+, and [RuVI(qpy)(O)2]2+/[RuIV(qpy)(O)(OH2)]2+ in cyclic voltammograms.« less

Screening for diets that reduce urinary nitrogen excretion and methane emissions while maintaining or increasing production by dairy cows.

PubMed

Gregorini, Pablo; Beukes, Pierre C; Dalley, Dawn; Romera, Alvaro J

2016-05-01

Farmers face complex decisions at the time to feed animals, trying to achieve production goals while contemplating social and environmental constraints. Our purpose was to facilitate such decision making for pastoral dairy farmers, aiming to reduce urinary N (UN) and methane emissions (CH4), while maintaining or increasing milk production (MP). There is a number of feeds the farmers can choose from and combine. We used 50 feeds (forages and grains) combined systematically in different proportions producing 11,526 binary diets. Diets were screened, using an a posteriori approach and a Pareto front (PF) analysis of model (Molly) outputs. The objective was to identify combinations with the best possible compromise (i.e. frontier) between UN, CH4, and MP. Using high MP and low UN as objective functions, PF included 10, 14, 12 and 50 diets, for non-lactating, early-, mid- and late-lactation periods, with cereals and beets featuring strongly. Using the same objective functions, but including ryegrass as dietary base PF included 2, 4, 8 and 4 diets for those periods. Therefore, from a wide range of diets, farmers could choose from few feeds combined into binary diets to reduce UN while maintaining or increasing MP. If the intention is maintaining pasture-based systems, there are fewer suitable options. Reducing UN will simply require dilution of N supplied by pasture by supplementing low N conserved forages. The results also evidence the risk of pollution swapping, reaching the frontier means arriving at a point where trade-off decisions need to be made. Any further reduction in UN implies an increment in CH4, or reduction in CH4 emissions increases UN. There is no perfect diet to optimize all objectives simultaneously; but if the current diet is not in the frontier some options can offset pollution swapping. The choice is with the farmers and conditioned by their context. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis and structure determination of new open-framework chromium carboxylate MIL-105 or Cr{sup III}(OH).{l_brace}O{sub 2}C-C{sub 6}(CH{sub 3}){sub 4}-CO{sub 2}{r_brace}.nH{sub 2}O

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

Serre, Christian; Millange, Franck; Devic, Thomas

2006-08-10

Two new three-dimensional chromium(III) dicarboxylate, MIL-105 or Cr{sup III}(OH).{l_brace}O{sub 2}C-C{sub 6}(CH{sub 3}){sub 4}-CO{sub 2}{r_brace}.nH{sub 2}O, have been obtained under hydrothermal conditions, and their structures solved using X-ray powder diffraction data. Both solids are structural analogs of the known Cr benzenedicarboxylate compound (MIL-53). Both contain trans corner-sharing CrO{sub 4}(OH){sub 2} octahedral chains connected by tetramethylterephthalate di-anions. Each chain is linked by the ligands to four other chains to form a three-dimensional framework with an array of 1D pores channels. The pores of the high temperature form of the solid, MIL-105ht, are empty. However, MIL-105ht re-hydrates at room temperature to finally givemore » MIL-105lt with pores channels filled with free water molecules (lt: low temperature form; ht: high temperature form). The thermal behaviour of the two solids has been investigated using TGA. Crystal data for MIL-105ht: monoclinic space group C2/c with a = 19.653(1) A, b = 9.984(1) A, c = 6.970(1) A, {beta} = 110.67(1){sup o} and Z = 4. Crystal data for MIL-105lt: orthorhombic space group Pnam with a = 17.892(1) A, b = 11.165(1) A, c = 6.916(1) A and Z = 4.« less

Linseed oil supplementation to dairy cows fed diets based on red clover silage or corn silage: Effects on methane production, rumen fermentation, nutrient digestibility, N balance, and milk production.

PubMed

Benchaar, C; Hassanat, F; Martineau, R; Gervais, R

2015-11-01

The objective of this study was to examine the effect of linseed oil (LO) supplementation to red clover silage (RCS)- or corn silage (CS)-based diets on enteric CH4 emissions, ruminal fermentation characteristics, nutrient digestibility, N balance, and milk production. Twelve rumen-cannulated lactating cows were used in a replicated 4×4 Latin square design (35-d periods) with a 2×2 factorial arrangement of treatments. Cows were fed (ad libitum) RCS- or CS-based diets [forage:concentrate ratio 60:40; dry matter (DM) basis] without or with LO (4% of DM). Supplementation of LO to the RCS-based diet reduced enteric CH4 production (-9%) and CH4 energy losses (-11%) with no adverse effects on DM intake, digestion, ruminal fermentation characteristics, protozoa numbers, or milk production. The addition of LO to the CS-based diet caused a greater decrease in CH4 production (-26%) and CH4 energy losses (-23%) but was associated with a reduction in DM intake, total-tract fiber digestibility, protozoa numbers, acetate:propionate ratio, and energy-corrected milk yield. Urinary N excretion (g/d) decreased with LO supplementation to RCS- and CS-based diets, suggesting reduced potential of N2O emissions. Results from this study show that the depressive effect of LO supplementation on enteric CH4 production is more pronounced with the CS- than with the RCS-based diet. However, because of reduced digestibility with the CS-based diet, the reduction in enteric CH4 production may be offset by higher CH4 emissions from manure storage. Thus, the type of forage of the basal diet should be taken into consideration when using fat supplementation as a dietary strategy to reduce enteric CH4 production from dairy cows. Copyright © 2015 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Photoinduced Cobalt(III)-Trifluoromethyl Bond Activation Enables Arene C-H Trifluoromethylation.

PubMed

Harris, Caleb F; Kuehner, Christopher S; Bacsa, John; Soper, Jake D

2018-01-26

Visible-light capture activates a thermodynamically inert Co III -CF 3 bond for direct C-H trifluoromethylation of arenes and heteroarenes. New trifluoromethylcobalt(III) complexes supported by a redox-active [OCO] pincer ligand were prepared. Coordinating solvents, such as MeCN, afford green, quasi-octahedral [( S OCO)Co III (CF 3 )(MeCN) 2 ] (2), but in non-coordinating solvents the complex is red, square pyramidal [( S OCO)Co III (CF 3 )(MeCN)] (3). Both are thermally stable, and 2 is stable in light. But exposure of 3 to low-energy light results in facile homolysis of the Co III -CF 3 bond, releasing . CF 3 radical, which is efficiently trapped by TEMPO . or (hetero)arenes. The homolytic aromatic substitution reactions do not require a sacrificial or substrate-derived oxidant because the Co II by-product of Co III -CF 3 homolysis produces H 2 . The photophysical properties of 2 and 3 provide a rationale for the disparate light stability. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Seven 3d-4f coordination polymers of macrocyclic oxamide with polycarboxylates: Syntheses, crystal structures and magnetic properties

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

Xin, Na; Key Laboratory of Inorganic-Organic Hybrid Functional Material Chemistry, Ministry of Education; Tianjin Key Laboratory of Structure and Performance for Functional Molecules

2016-11-15

Seven new 3d–4f heterometallic coordination polymers, [Ln(CuL){sub 2}(Hbtca)(btca)(H{sub 2}O)]·2H{sub 2}O (Ln = Tb{sup III}1, Pr{sup III}2, Sm{sup III}3, Eu{sup III}4, Yb{sup III}5), [Nd(NiL)(nip)(Rnip)]·0·25H{sub 2}O·0.25CH{sub 3}OH (R= 0.6CH{sub 3}, 0.4H) 6 and [Nd{sub 2}(NiL)(nip){sub 3}(H{sub 2}O)]·2H{sub 2}O 7(CuL or NiL, H{sub 2}L = 2, 3-dioxo-5, 6, 14, 15-dibenzo-1, 4, 8, 12-tetraazacyclo-pentadeca-7, 13-dien; H{sub 2}btca = benzotriazole-5-carboxylic acid; H{sub 2}nip = 5-nitroisophthalic acid) have been synthesized by a solvothermal method and characterized by single-crystal X-ray diffraction. Complexes 1–5 exhibit a double-strand meso-helical chain structures formed by [Ln{sup III}Cu{sup II}{sub 2}] units via the oxamide and benzotriazole-5-carboxylate bridges, while complex 6 exhibits amore » four-strand meso-helical chain formed by NdNi unit via the oxamide and 5-nitroisophthalate bridges. Complex 7 consists of a 2D layer framework formed by four-strand meso-helical chain via the nip{sup 2−} bridges. Moreover, the magnetic properties of them were investigated, and the best-fit analysis of χ{sub M}T versus T show that the anisotropic contribution of Ln(III) ions (arising from the spin-orbit coupling or the crystal field perturbation) dominates (weak exchange limit) in these complexes(for 3, λ = 214.6 cm{sup −1}, zj’ = −0.33 cm{sup −1}, g{sub av} = 1.94; for 5, Δ = 6.98 cm{sup −1}, zj’ = 1.53 cm{sup −1}, g{sub av} = 1.85). - Graphical-abstract: Seven novel oxamido-bridged 3d-4f heterometallic coordination polymers with benzotriazole-5-carboxylate or 5-nitroisophthalate co-ligands under solvothermal reaction conditions. Polymers 1–7 hold 1D or 2D framework structure, viz., double-strand meso-helical chain of 1–5, four-strand meso-helical chain of 6, and 2D net of 7 consisting of four-strand meso-helical chain. Moreover, the temperature dependences of magnetic susceptibilities of compounds 1–7 were also studied.« less

Catalyst-Dependent Chemoselective Formal Insertion of Diazo Compounds into C-C or C-H Bonds of 1,3-Dicarbonyl Compounds.

PubMed

Liu, Zhaohong; Sivaguru, Paramasivam; Zanoni, Giuseppe; Anderson, Edward A; Bi, Xihe

2018-05-08

A catalyst-dependent chemoselective one-carbon insertion of diazo compounds into the C-C or C-H bonds of 1,3-dicarbonyl species is reported. In the presence of silver(I) triflate, diazo insertion into the C(=O)-C bond of the 1,3-dicarbonyl substrate leads to a 1,4-dicarbonyl product containing an all-carbon α-quaternary center. This reaction constitutes the first example of an insertion of diazo-derived carbenoids into acyclic C-C bonds. When instead scandium(III) triflate was applied as the catalyst, the reaction pathway switched to formal C-H insertion, affording 2-alkylated 1,3-dicarbonyl products. Different reaction pathways are proposed to account for this powerful catalyst-dependent chemoselectivity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Speciation analysis of arsenic compounds in seafood by ion chromatography-atomic fluorescence spectrometry

NASA Astrophysics Data System (ADS)

Han, Tingting; Ji, Hongwei; Li, Huixin; Cui, He; Song, Tian; Duan, Xiaojuan; Zhu, Qianlin; Cai, Feng; Zhang, Li

2017-06-01

Ion chromatography-ultra violet-hydride generation-Atomic Florescence Spectrometry was applied to detect 5 arsenic species in seafoods. The arsenic species studied include arsenobetaine (AsB), arsenite (As(III)), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), and arsenate (As(V)), which were extracted from samples using 2% formic acid. Gradient elution using 33 mmol L-1 CH3COONH4 and 15 mmol L-1 Na2CO3 with 10 mL CH3CH2OH at pH 8.4 allowed the chromatographic separation of all the species on a Hamilton PRP-X100 anion-exchange column in less than 8 min. In this study, an ultrasound extraction method was used to extract arsenic species from seafood. The extraction efficiency was good and the recoveries from spiked samples were in the range of 72.6%-109%; the precision between sample replicates was higher than 3.6% for all determinations. The detection limits were 3.543 μg L-1 for AsB, 0.426 μg L-1 for As(III), 0.216 μg L-1 for DMA, 0.211 μg L-1 for MMA, and 0.709 μg L-1 for As(V), and the linear coefficients were greater than 0.999. We also developed an application of this method for the determination of arsenic species in bonito, Euphausia superba, and Enteromorpha with satisfactory results. Therefore, it was confirmed that this method was appropriate for the detection of arsenic species in seafood.

Environmental controls of temporal and spatial variability in CO2 and CH4 fluxes in a neotropical peatland.

PubMed

Wright, Emma L; Black, Colin R; Turner, Benjamin L; Sjögersten, Sofie

2013-12-01

Tropical peatlands play an important role in the global storage and cycling of carbon (C) but information on carbon dioxide (CO2) and methane (CH4) fluxes from these systems is sparse, particularly in the Neotropics. We quantified short and long-term temporal and small scale spatial variation in CO2 and CH4 fluxes from three contrasting vegetation communities in a domed ombrotrophic peatland in Panama. There was significant variation in CO2 fluxes among vegetation communities in the order Campnosperma panamensis > Raphia taedigera > Cyperus. There was no consistent variation among sites and no discernible seasonal pattern of CH4 flux despite the considerable range of values recorded (e.g. -1.0 to 12.6 mg m(-2) h(-1) in 2007). CO2 fluxes varied seasonally in 2007, being greatest in drier periods (300-400 mg m(-2) h(-1)) and lowest during the wet period (60-132 mg m(-2) h(-1)) while very high emissions were found during the 2009 wet period, suggesting that peak CO2 fluxes may occur following both low and high rainfall. In contrast, only weak relationships between CH4 flux and rainfall (positive at the C. panamensis site) and solar radiation (negative at the C. panamensis and Cyperus sites) was found. CO2 fluxes showed a diurnal pattern across sites and at the Cyperus sp. site CO2 and CH4 fluxes were positively correlated. The amount of dissolved carbon and nutrients were strong predictors of small scale within-site variability in gas release but the effect was site-specific. We conclude that (i) temporal variability in CO2 was greater than variation among vegetation communities; (ii) rainfall may be a good predictor of CO2 emissions from tropical peatlands but temporal variation in CH4 does not follow seasonal rainfall patterns; and (iii) diurnal variation in CO2 fluxes across different vegetation communities can be described by a Fourier model. © 2013 John Wiley & Sons Ltd.

Experimental Determination of P-V-T-X Properties and Adsorption Kinetics in the CO2-CH4 System under Shale Gas Reservoir Conditions

NASA Astrophysics Data System (ADS)

Xiong, Y.; Wang, Y.

2014-12-01

Shale gas production via hydrofracturing has profoundly changed the energy portfolio in the USA and other parts of the world. Under the shale gas reservior conditions, CO2 and H2O, either in residence or being injected during hydrofracturing or both, co-exist with CH4. One important feature characteristic of shale is the presence of nanometer-scale (1-100 nm) pores in shale or mudstone. The interactions among CH4, CO2 and H2O in those nano-sized pores directly impact shale gas storage and gas release from the shale matrix. Therefore, a fundamental understanding of interactions among CH4, CO2 and H2O in nanopore confinement would provide guidance in addressing a number of problems such as rapid decline in production after a few years and low recovery rates. We are systematically investigating the P-V-T-X properties and adsorption kinetics in the CH4-CO2-H2O system under the reservior conditions. We have designed and constructed a unique high temperature and pressure experimental system that can measure both of the P-V-T-X properties and adsorption kinetics sequentially. We measure the P-V-T-X properties of CH4-CO2 mixtures with CH4 up to 95 vol. %, and adsorption kinetics of various materials, under the conditions relevant to shale gas reservoir. We use three types of materials: (I) model materials, (II) single solid phases separated from shale samples, and (III) crushed shale samples from both the known shale gas producing formations and the shale gas barren formations. The model materials are well characterized in terms of pore sizes. Therefore, the results associated with the model material serve as benchmarks for our model development. Sandia National Laboratories is a multi-program laboratory operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000. This research is supported by a Geoscience Foundation LDRD.

Polygonal tundra geomorphological change in response to warming alters future CO2 and CH4 flux on the Barrow Peninsula.

PubMed

Lara, Mark J; McGuire, A David; Euskirchen, Eugenie S; Tweedie, Craig E; Hinkel, Kenneth M; Skurikhin, Alexei N; Romanovsky, Vladimir E; Grosse, Guido; Bolton, W Robert; Genet, Helene

2015-04-01

The landscape of the Barrow Peninsula in northern Alaska is thought to have formed over centuries to millennia, and is now dominated by ice-wedge polygonal tundra that spans drained thaw-lake basins and interstitial tundra. In nearby tundra regions, studies have identified a rapid increase in thermokarst formation (i.e., pits) over recent decades in response to climate warming, facilitating changes in polygonal tundra geomorphology. We assessed the future impact of 100 years of tundra geomorphic change on peak growing season carbon exchange in response to: (i) landscape succession associated with the thaw-lake cycle; and (ii) low, moderate, and extreme scenarios of thermokarst pit formation (10%, 30%, and 50%) reported for Alaskan arctic tundra sites. We developed a 30 × 30 m resolution tundra geomorphology map (overall accuracy:75%; Kappa:0.69) for our ~1800 km² study area composed of ten classes; drained slope, high center polygon, flat-center polygon, low center polygon, coalescent low center polygon, polygon trough, meadow, ponds, rivers, and lakes, to determine their spatial distribution across the Barrow Peninsula. Land-atmosphere CO2 and CH4 flux data were collected for the summers of 2006-2010 at eighty-two sites near Barrow, across the mapped classes. The developed geomorphic map was used for the regional assessment of carbon flux. Results indicate (i) at present during peak growing season on the Barrow Peninsula, CO2 uptake occurs at -902.3 10(6) gC-CO2 day(-1) (uncertainty using 95% CI is between -438.3 and -1366 10(6) gC-CO2 day(-1)) and CH4 flux at 28.9 10(6) gC-CH4 day(-1) (uncertainty using 95% CI is between 12.9 and 44.9 10(6) gC-CH4 day(-1)), (ii) one century of future landscape change associated with the thaw-lake cycle only slightly alter CO2 and CH4 exchange, while (iii) moderate increases in thermokarst pits would strengthen both CO2 uptake (-166.9 10(6) gC-CO2 day(-1)) and CH4 flux (2.8 10(6) gC-CH4 day(-1)) with geomorphic change from low to high center polygons, cumulatively resulting in an estimated negative feedback to warming during peak growing season. © 2014 John Wiley & Sons Ltd.

Dry (CO2) reforming of methane over Pt catalysts studied by DFT and kinetic modeling

NASA Astrophysics Data System (ADS)

Niu, Juntian; Du, Xuesen; Ran, Jingyu; Wang, Ruirui

2016-07-01

Dry reforming of methane (DRM) is a well-studied reaction that is of both scientific and industrial importance. In order to design catalysts that minimize the deactivation and improve the selectivity and activity for a high H2/CO yield, it is necessary to understand the elementary reaction steps involved in activation and conversion of CO2 and CH4. In our present work, a microkinetic model based on density functional theory (DFT) calculations is applied to explore the reaction mechanism for methane dry reforming on Pt catalysts. The adsorption energies of the reactants, intermediates and products, and the activation barriers for the elementary reactions involved in the DRM process are calculated over the Pt(1 1 1) surface. In the process of CH4 direct dissociation, the kinetic results show that CH dissociative adsorption on Pt(1 1 1) surface is the rate-determining step. CH appears to be the most abundant species on the Pt(1 1 1) surface, suggesting that carbon deposition is not easy to form in CH4 dehydrogenation on Pt(1 1 1) surface. In the process of CO2 activation, three possible reaction pathways are considered to contribute to the CO2 decomposition: (I) CO2* + * → CO* + O*; (II) CO2* + H* → COOH* + * → CO* + OH*; (III) CO2* + H* → mono-HCOO* + * → bi-HCOO* + * [CO2* + H* → bi-HCOO* + *] → CHO* + O*. Path I requires process to overcome the activation barrier of 1.809 eV and the forward reaction is calculated to be strongly endothermic by 1.430 eV. In addition, the kinetic results also indicate this process is not easy to proceed on Pt(1 1 1) surface. While the CO2 activation by H adsorbed over the catalyst surface to form COOH intermediate (Path II) is much easier to be carried out with the lower activation barrier of 0.746 eV. The Csbnd O bond scission is the rate-determining step along this pathway and the process needs to overcome the activation barrier of 1.522 eV. Path III reveals the CO2 activation through H adsorbed over the catalyst surface to form HCOO intermediate firstly. This reaction requires a quite high activation barrier and is a strongly endothermic process leading to a very low forward rate constant. In conclusion, Path II is the dominant reaction pathway in CO2 activation. Additionally, there are two pathways of CH oxidation by O: (A) CH* + O* → CHO* + * → CO* + H*; (B) CH* + O* → COH* + * → CO* + H*. Both the activation barriers and kinetic results demonstrate that Path A is the prior reaction pathway. Furthermore, in the two pathways of CH oxidation by OH: (C) CH* + OH* → CHOH* + * → CHO* + H*; (D) CH* + OH* → CHOH* + * → COH* + H*. Path C is easier to proceed. In conclusion, the main reaction pathway in CH oxidation according to the mechanism: CH* + OH* → CHOH* + * → CHO* + H* → CO* + 2H*. These results could provide some useful information for the operation of DRM over Pt catalysts, and are helpful to understand the mechanisms of DRM from the atomic scale.

Single crystal X- and Q-band EPR spectroscopy of a binuclear Mn(2)(III,IV) complex relevant to the oxygen-evolving complex of photosystem II.

PubMed

Yano, Junko; Sauer, Kenneth; Girerd, Jean-Jacques; Yachandra, Vittal K

2004-06-23

The anisotropic g and hyperfine tensors of the Mn di-micro-oxo complex, [Mn(2)(III,IV)O(2)(phen)(4)](PF(6))(3).CH(3)CN, were derived by single-crystal EPR measurements at X- and Q-band frequencies. This is the first simulation of EPR parameters from single-crystal EPR spectra for multinuclear Mn complexes, which are of importance in several metalloenzymes; one of them is the oxygen-evolving complex in photosystem II (PS II). Single-crystal [Mn(2)(III,IV)O(2)(phen)(4)](PF(6))(3).CH(3)CN EPR spectra showed distinct resolved (55)Mn hyperfine lines in all crystal orientations, unlike single-crystal EPR spectra of other Mn(2)(III,IV) di-micro-oxo bridged complexes. We measured the EPR spectra in the crystal ab- and bc-planes, and from these spectra we obtained the EPR spectra of the complex along the unique a-, b-, and c-axes of the crystal. The crystal orientation was determined by X-ray diffraction and single-crystal EXAFS (Extended X-ray Absorption Fine Structure) measurements. In this complex, the three crystallographic axes, a, b, and c, are parallel or nearly parallel to the principal molecular axes of Mn(2)(III,IV)O(2)(phen)(4) as shown in the crystallographic data by Stebler et al. (Inorg. Chem. 1986, 25, 4743). This direct relation together with the resolved hyperfine lines significantly simplified the simulation of single-crystal spectra in the three principal directions due to the reduction of free parameters and, thus, allowed us to define the magnetic g and A tensors of the molecule with a high degree of reliability. These parameters were subsequently used to generate the solution EPR spectra at both X- and Q-bands with excellent agreement. The anisotropic g and hyperfine tensors determined by the simulation of the X- and Q-band single-crystal and solution EPR spectra are as follows: g(x) = 1.9887, g(y) = 1.9957, g(z) = 1.9775, and hyperfine coupling constants are A(III)(x) = |171| G, A(III)(y) = |176| G, A(III)(z) = |129| G, A(IV)(x) = |77| G, A(IV)(y) = |74| G, A(IV)(z) = |80| G.

Louisiana SIP: LAC 33:III Ch 23 Subchap B, §2303--Aluminum Plants, §2303 Standards for Horizontal Stud Soderberg Primary Aluminum Plants and Prebake Primary Aluminum Plants; SIP effective 1989-05-08 (LAc49) to 2011-08-03 (LAad34 - Revised)

EPA Pesticide Factsheets

Louisiana SIP: LAC 33:III Ch 23 Subchap B, §2303--Aluminum Plants, §2303 Standards for Horizontal Stud Soderberg Primary Aluminum Plants and Prebake Primary Aluminum Plants; SIP effective 1989-05-08 (LAc49) to 2011-08-03 (LAad34 - Revised)

Rhodium-catalyzed C-H alkynylation of arenes at room temperature.

PubMed

Feng, Chao; Loh, Teck-Peng

2014-03-03

The rhodium(III)-catalyzed ortho C-H alkynylation of non-electronically activated arenes is disclosed. This process features a straightforward and highly effective protocol for the synthesis of functionalized alkynes and represents the first example of merging a hypervalent iodine reagent with rhodium(III) catalysis. Notably, this reaction proceeds at room temperature, tolerates a variety of functional groups, and more importantly, exhibits high selectivity for monoalkynylation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rapid Evaluation of Propulsion System Effects. Volume III. Derivative Procedure (DERIVP) Users Manual

DTIC Science & Technology

1978-07-01

J4-..L&-. 3--014190-14-14-- @911*0 w9805 c9751 e96437 .9545 .*9531 a9455 99430 e9333 A666* *6462 96663 .6621 07132 .*159 .1757 0Mli . 7845 .9873 .1882...PfWWIETERS TO SE CW#4GEI INPUT TIE PARAIiETERS TO BE CH *IG*ED FLLO1UED IVB THE NEU VALUE" IN PnIZR(PAPAFMiTER N.411iEIR tEU WLUC) 1>1 .95 4 2.5 5 .03

Evaluating Impacts of CO2 and CH4 Gas Intrusion into an Unconsolidated Aquifer: Fate of As and Cd

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

Lawter, Amanda R.; Qafoku, Nikolla; Shao, Hongbo

2015-07-10

Abstract The sequestration of carbon dioxide (CO2) in deep underground reservoirs has been identified as an important strategy to decrease atmospheric CO2 levels and mitigate global warming, but potential risks on overlying aquifers currently lack a complete evaluation. In addition to CO2, other gases such as methane (CH4) may be present in storage reservoirs. This paper explores for the first time the combined effect of leaking CO2 and CH4 gasses on the fate of major, minor and trace elements in an aquifer overlying a potential sequestration site. Emphasis is placed on the fate of arsenic (As) and cadmium (Cd) releasedmore » from the sediments or present as soluble constituents in the leaking brine. Results from macroscopic batch and column experiments show that the presence of CH4 (at a concentration of 1 % in the mixture CO2/CH4) does not have a significant effect on solution pH or the concentrations of most major elements (such as Ca, Ba, and Mg). However, the concentrations of Mn, Mo, Si and Na are inconsistently affected by the presence of CH4 (i.e., in at least one sediment tested in this study). Cd is not released from the sediments and spiked Cd is mostly removed from the aqueous phase most likely via adsorption. The fate of sediment associated As [mainly sorbed arsenite or As(III) in minerals] and spiked As [i.e., As5+] is complex. Possible mechanisms that control the As behavior in this system are discussed in this paper. Results are significant for CO2 sequestration risk evaluation and site selection and demonstrate the importance of evaluating reservoir brine and gas stream composition during site selection to ensure the safest site is being chosen.« less

Grazing management contributions to net global warming potential: a long-term evaluation in the Northern Great Plains.

PubMed

Liebig, M A; Gross, J R; Kronberg, S L; Phillips, R L; Hanson, J D

2010-01-01

The role of grassland ecosystems as net sinks or sources of greenhouse gases (GHGs) is limited by a paucity of information regarding management impacts on the flux of nitrous oxide (N(2)O) and methane (CH(4)). Furthermore, no long-term evaluation of net global warming potential (GWP) for grassland ecosystems in the northern Great Plains (NGP) of North America has been reported. Given this need, we sought to determine net GWP for three grazing management systems located within the NGP. Grazing management systems included two native vegetation pastures (moderately grazed pasture [MGP], heavily grazed pasture [HGP]) and a heavily grazed crested wheatgrass [Agropyron desertorum (Fisch. ex. Link) Schult.] pasture (CWP) near Mandan, ND. Factors evaluated for their contribution to GWP included (i) CO(2) emissions associated with N fertilizer production and application, (ii) literature-derived estimates of CH(4) production for enteric fermentation, (iii) change in soil organic carbon (SOC) over 44 yr using archived soil samples, and (iv) soil-atmosphere N(2)O and CH(4) fluxes over 3 yr using static chamber methodology. Analysis of SOC indicated all pastures to be significant sinks for SOC, with sequestration rates ranging from 0.39 to 0.46 Mg C ha(-1) yr(-1). All pastures were minor sinks for CH(4) (<2.0 kg CH(4)-C ha(-1) yr(-1)). Greater N inputs within CWP contributed to annual N(2)O emission nearly threefold greater than HGP and MGP. Due to differences in stocking rate, CH(4) production from enteric fermentation was nearly threefold less in MGP than CWP and HGP. When factors contributing to net GWP were summed, HGP and MGP were found to serve as net CO(2equiv.) sinks, while CWP was a net CO(2equiv.) source. Values for GWP and GHG intensity, however, indicated net reductions in GHG emissions can be most effectively achieved through moderate stocking rates on native vegetation in the NGP.

Signatures of a quantum diffusion limited hydrogen atom tunneling reaction.

PubMed

Balabanoff, Morgan E; Ruzi, Mahmut; Anderson, David T

2017-12-20

We are studying the details of hydrogen atom (H atom) quantum diffusion in highly enriched parahydrogen (pH 2 ) quantum solids doped with chemical species in an effort to better understand H atom transport and reactivity under these conditions. In this work we present kinetic studies of the 193 nm photo-induced chemistry of methanol (CH 3 OH) isolated in solid pH 2 . Short-term irradiation of CH 3 OH at 1.8 K readily produces CH 2 O and CO which we detect using FTIR spectroscopy. The in situ photochemistry also produces CH 3 O and H atoms which we can infer from the post-photolysis reaction kinetics that display significant CH 2 OH growth. The CH 2 OH growth kinetics indicate at least three separate tunneling reactions contribute; (i) reactions of photoproduced CH 3 O with the pH 2 host, (ii) H atom reactions with the CH 2 O photofragment, and (iii) long-range migration of H atoms and reaction with CH 3 OH. We assign the rapid CH 2 OH growth to the following CH 3 O + H 2 → CH 3 OH + H → CH 2 OH + H 2 two-step sequential tunneling mechanism by conducting analogous kinetic measurements using deuterated methanol (CD 3 OD). By performing photolysis experiments at 1.8 and 4.3 K, we show the post-photolysis reaction kinetics change qualitatively over this small temperature range. We use this qualitative change in the reaction kinetics with temperature to identify reactions that are quantum diffusion limited. While these results are specific to the conditions that exist in pH 2 quantum solids, they have direct implications on the analogous low temperature H atom tunneling reactions that occur on metal surfaces and on interstellar grains.

Functionalization of carbon dioxide and carbon disulfide using a stable uranium(III) alkyl complex.

PubMed

Matson, Ellen M; Forrest, William P; Fanwick, Phillip E; Bart, Suzanne C

2011-04-06

A rare uranium(III) alkyl complex, Tp*(2)U(CH(2)Ph) (2) (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate), was synthesized by salt metathesis from Tp*(2)UI (1) and KCH(2)Ph and fully characterized using (1)H NMR, infrared, and electronic absorption spectroscopies as well as X-ray crystallography. This complex has a uranium-carbon distance of 2.57(2) Å, which is comparable to other uranium alkyls reported. Treating this compound with either carbon dioxide or carbon disulfide results in insertion into the uranium-carbon bond to generate Tp*(2)U(κ(2)-O(2)CCH(2)Ph) (3) and Tp*(2)U(SC(S)CH(2)Ph) (4), respectively. These species, characterized spectroscopically and by X-ray crystallography, feature new carboxylate and dithiocarboxylate ligands. Analysis by electronic absorption spectroscopy supports the trivalent oxidation state of the uranium center in both of these derivatives. Addition of trimethylsilylhalides (Me(3)SiX; X = Cl, I) to 3 results in the release of the free silyl ester, Me(3)SiOC(O)CH(2)Ph, forming the initial uranium monohalide species, Tp*(2)UX, which can then be used over multiple cycles for the functionalization of carbon dioxide. © 2011 American Chemical Society

Gold complexes with the selenolate ligand [2-(Me2NCH2)C6H4Se]-.

PubMed

Crespo, Olga; Gimeno, M Concepción; Laguna, Antonio; Kulcsar, Monika; Silvestru, Cristian

2009-05-04

The reaction of [2-(Me(2)NCH(2))C(6)H(4)Se]M (M = Li, K) with the gold(phosphine) complexes [AuCl(PR(3))] gives the mononuclear gold-selenolate species [Au{SeC(6)H(4)(CH(2)NMe(2))-2}(PPh(3))] (1) or [Au{SeC(6)H(4)(CH(2)NMe(2))-2}(PPh(2)py)] (2), respectively. The treatment of the [2-(Me(2)NCH(2))C(6)H(4)Se]M with [Au(2)Cl(2)(mu-P-P)] [P-P = bis(diphenylphosphino)methane (dppm), bis(diphenylphosphino)ethane (dppe), 1,1'-bis(diphenylphosphino)ferrocene (dppf)] derivatives gives complexes with stoichiometry [Au(2){SeC(6)H(4)(CH(2)NMe(2))-2}(2)(mu-P-P)] [P-P = dppm (3), dppe (4), or dppf (5)]. These complexes exhibit a different structural framework, that is, 4 crystallizes as a chain polymer with intermolecular aurophilic bonding, while 5 shows an intramolecular Au(I)...Au(I) interaction. The gold(III) derivative Bu(4)N[Au(C(6)F(5))(3){SeC(6)H(4)(CH(2)NMe(2))-2}] (6) is obtained by reaction of [2-(Me(2)NCH(2))C(6)H(4)Se]K and Bu(4)N[AuBr(C(6)F(5))(3)], in a 1:1 molar ratio. These species exhibit luminescence which probably arises from a mixed (3)LMMCT and (3)MC excited state. The emission properties in these complexes seem to be useful for structural predictions and lead to the proposal of intermolecular aggregation in the solid state and frozen solution for complexes 1, 2, 3, whose crystal structures have not been elucidated.

Direct and indirect predictions of enteric methane daily production, yield, and intensity per unit of milk and cheese, from fatty acids and milk Fourier-transform infrared spectra.

PubMed

Bittante, Giovanni; Cipolat-Gotet, Claudio

2018-05-23

Mitigating the dairy chain's contribution to climate change requires cheap, rapid methods of predicting enteric CH 4 emissions (EME) of dairy cows in the field. Such methods may also be useful for genetically improving cows to reduce EME. Our objective was to evaluate different procedures for predicting EME traits from infrared spectra of milk samples taken at routine milk recording of cows. As a reference method, we used EME traits estimated from published equations developed from a meta-analysis of data from respiration chambers through analysis of various fatty acids in milk fat by gas chromatography (FA GC ). We analyzed individual milk samples of 1,150 Brown Swiss cows from 85 farms operating different dairy systems (from very traditional to modern), and obtained the cheese yields of individual model cheeses from these samples. We also obtained Fourier-transform infrared absorbance spectra on 1,060 wavelengths (5,000 to 930 waves/cm) from the same samples. Five reference enteric CH 4 traits were calculated: CH 4 yield (CH 4 /DMI, g/kg) per unit of dry matter intake (DMI), and CH 4 intensity (CH 4 /CM, g/kg) per unit of corrected milk (CM) from the FA GC profiles; CH 4 intensity per unit of fresh cheese (CH 4 /CY CURD , g/kg) and cheese solids (CH 4 /CY SOLIDS , g/kg) from individual cheese yields (CY); and daily CH 4 production (dCH 4 , g/d). Direct infrared (IR) calibrations were obtained by BayesB modeling; the determination coefficients of cross-validation varied from 0.36 for dCH 4 to 0.57 for CH 4 /CM, and were similar to the coefficient of determination values of the equations based on FA GC used as the reference method (0.47 for CH 4 /DMI and 0.54 for CH 4 /CM). The models allowed us to select the most informative wavelengths for each EME trait and to infer the milk chemical features underlying the predictions. Aside from the 5 direct infrared prediction calibrations, we tested another 8 indirect prediction models. Using IR-predicted informative fatty acids (FA IR ) instead of FA GC , we were able to obtain indirect predictions with about the same precision (correlation with reference values) as direct IR predictions of CH 4 /DMI (0.78 vs. 0.76, respectively) and CH 4 /CM (0.82 vs. 0.83). The indirect EME predictions based on IR-predicted CY were less precise than the direct IR predictions of both CH 4 /CY CURD (0.67 vs. 0.81) and CH 4 /CY SOLIDS (0.62 vs. 0.78). Four indirect dCH 4 predictions were obtained by multiplying the measured or IR-predicted daily CM production by the direct or indirect CH 4 /CM. Combining recorded daily CM and predicted CH 4 /CM greatly increased precision over direct dCH 4 predictions (0.96-0.96 vs. 0.68). The estimates obtained from the majority of direct and indirect IR-based prediction models exhibited herd and individual cow variability and effects of the main sources of variation (dairy system, parity, days in milk) similar to the reference data. Some rapid, cheap, direct and indirect IR prediction models appear to be useful for monitoring EME in the field and possibly for genetic/genomic selection, but future studies directly measuring CH 4 with different breeds and dairy systems are needed to validate our findings. Copyright © 2018 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

CarbonSat: ESA's Earth Explorer 8 Candidate Mission

NASA Astrophysics Data System (ADS)

Meijer, Y. J.; Ingmann, P.; Löscher, A.

2012-04-01

The CarbonSat candidate mission is part of ESA's Earth Explorer Programme. In 2010, two candidate opportunity missions had been selected for feasibility and preliminary definition studies. The missions, called FLEX and CarbonSat, are now in competition to become ESA's eighth Earth Explorer, both addressing key climate and environmental change issues. In this presentation we will provide a mission overview of CarbonSat with a focus on science. CarbonSat's primary mission objective is the quantification and monitoring of CO2 and CH4 sources and sinks from the local to the regional scale for i) a better understanding of the processes that control carbon cycle dynamics and ii) an independent estimate of local greenhouse gas emissions (fossil fuel, geological CO2 and CH4, etc.) in the context of international treaties. A second priority objective is the monitoring/derivation of CO2 and CH4 fluxes on regional to global scale. These objectives will be achieved by a unique combination of frequent, high spatial resolution (2 x 2 km2) observations of XCO2 and XCH4 coupled to inverse modelling schemes. The required random error of a single measurement at ground-pixel resolution is of the order of between 1 and 3 ppm for XCO2 and between 9 and 17 ppb for XCH4. High spatial resolution is essential in order to maximize the probability for clear-sky observations and to identify flux hot spots. Ideally, CarbonSat shall have a wide swath allowing a 6-day global repeat cycle. The CarbonSat observations will enable CO2 emissions from coal-fired power plants, localized industrial complexes, cities, and other large emitters to be objectively assessed at a global scale. Similarly, the monitoring of natural gas pipelines and compressor station leakage will become feasible. The detection and quantification of the substantial geological greenhouse gas emission sources such as seeps, volcanoes and mud volcanoes will be achieved for the first time. CarbonSat's Greenhouse Gas instrument will exploit a passive observing technique measuring scattered solar light with imaging spectrometers. It will perform measurements of CO2 and CH4 in combination with O2 to yield their dry column amounts. Spectral absorptions of CO2 in the 1.6 μm and 2 μm bands, O2 in the 760 nm and CH4 in the 1.65 μm spectral ranges measured with high spectral resolution of the order of between 0.03 and 0.3 nm and a high signal-to-noise ratio. The CarbonSat mission concept builds on the heritage and lessons learned from SCIAMACHY, GOSAT and OCO(-2) to make strategically important measurements of the amounts and distribution of CO2 and CH4 in the context of Climate Change.

A Ni(iii) complex stabilized by silica nanoparticles as an efficient nanoheterogeneous catalyst for oxidative C-H fluoroalkylation.

PubMed

Khrizanforov, Mikhail N; Fedorenko, Svetlana V; Strekalova, Sofia O; Kholin, Kirill V; Mustafina, Asiya R; Zhilkin, Mikhail Ye; Khrizanforova, Vera V; Osin, Yuri N; Salnikov, Vadim V; Gryaznova, Tatyana V; Budnikova, Yulia H

2016-07-26

We have developed Ni(III)-doped silica nanoparticles ([(bpy)xNi(III)]@SiO2) as a recyclable, low-leaching, and efficient oxidative functionalization nanocatalyst for aromatic C-H bonds. The catalyst is obtained by doping the complex [(bpy)3Ni(II)] on silica nanoparticles along with its subsequent electrooxidation to [(bpy)xNi(III)] without an additional oxidant. The coupling reaction of arenes with perfluoroheptanoic acid occurs with 100% conversion of reactants in a single step at room temperature under nanoheterogeneous conditions. The catalyst content is only 1% with respect to the substrates under electrochemical regeneration conditions. The catalyst can be easily separated from the reaction mixture and reused a minimum of five times. The results emphasize immobilization on the silica support and the electrochemical regeneration of Ni(III) complexes as a facile route for developing an efficient nanocatalyst for oxidative functionalization.

Synthesis, structure and magnetic study of a novel mixed-valent Co(II)10Co(III)4 shield constructed by mixed pyridine-alcoholate ligands.

PubMed

Peng, Yan; Tian, Chong-Bin; Zhang, Hua-Bin; Li, Zhi-Hua; Lin, Ping; Du, Shao-Wu

2012-04-28

A novel tetradecanuclear mixed-valent cobalt cluster, formulated as [Co(II)(10)Co(III)(4)(OH)(2)O(6)(hmp)(10)(pdm)(4)(CH(3)OH)(2)]·5H(2)O (1), was obtained using mixed ligands of 2-(hydroxymethyl)pyridine (hmpH) and 2,6-pyridinedimethanol (pdmH(2)). The cobalt ions in 1 are connected by ten chelating hmp(-) ligands, four tris-chelating pdm(2-) ligands and six μ(3)-oxide/hydroxide anions, forming a unique shield-like planar structure that is rarely observed for Co-based clusters. Compound 1 displays slight frequency dependence at static zero field below 4.5 K, suggesting that it might be a single molecule magnet (SMM). This journal is © The Royal Society of Chemistry 2012

Impact of the heatwave in 2003 on the summer CH4 and N2O budget of a spruce forest ecosystem: A four-year comparison

NASA Astrophysics Data System (ADS)

Lamers, M.; Fiedler, S.; Jungkunst, H. F.; Stahr, K.; Streck, T.

2009-04-01

Both CH4 and N2O reduction and oxidation are highly sensitive to variation in soil moisture. Significant changes of net CH4 and total N2O fluxes from soils can therefore be expected to accompany redistribution for precipitation in the course of climate change where more extreme events are predicted for the future. The extreme summer drought in 2003 offered the unique opportunity to study the impact of such events on the emission of greenhouse gases, such as methane or nitrous oxide, under field conditions. The main objective of the present study was to evaluate the impact of the summer drought in 2003 on the net methane and nitrous oxide budget of a spruce forest ecosystem (South-West Germany) with large variation in soil drainage. During the summers of 2000-2004 we measured net CH4 and N2O fluxes (bi)-weekly using the closed-chamber technique for six different soil types ranging from well-aerated Cambisols to poorly drained Gleysols and a wet Histosol. With regard to CH4 the extreme summer draught (1) did not elevate net CH4-sink function of soils, but (2) highly reduced net CH4-source strength and (3) reversed the net CH4 source of the investigated catchment into a sink. In all four summers investigated, net ecosystem exchange of CH4 was found only in the hydromorphic soils but not in the dominant well-aerated soils. This highlighted the key role of hydromorphic soils for the investigated pedodiverse system. With regard to N2O the summer draught in 2003 significantly reduced N2O emissions at least for the Humic Gleysol and the Sapric Histosol and hence markedly reduced the net N2O source strength of the investigated ecosystem.

Relationships between milk mid-IR predicted gastro-enteric methane production and the technical and financial performance of commercial dairy herds.

PubMed

Delhez, P; Wyzen, B; Dalcq, A-C; Colinet, F G; Reding, E; Vanlierde, A; Dehareng, F; Gengler, N; Soyeurt, H

2017-12-22

Considering economic and environmental issues is important in ensuring the sustainability of dairy farms. The objective of this study was to investigate univariate relationships between lactating dairy cow gastro-enteric methane (CH4) production predicted from milk mid-IR (MIR) spectra and technico-economic variables by the use of large scale and on-farm data. A total of 525 697 individual CH4 predictions from milk MIR spectra (MIR-CH4 (g/day)) of milk samples collected on 206 farms during the Walloon milk recording scheme were used to create a MIR-CH4 prediction for each herd and year (HYMIR-CH4). These predictions were merged with dairy herd accounting data. This allowed a simultaneous study of HYMIR-CH4 and 42 technical and economic variables for 1024 herd and year records from 2007 to 2014. Pearson correlation coefficients (r) were used to assess significant relationships (P<0.05). Low HYMIR-CH4 was significantly associated with, amongst others, lower fat and protein corrected milk (FPCM) yield (r=0.18), lower milk fat and protein content (r=0.38 and 0.33, respectively), lower quantity of milk produced from forages (r=0.12) and suboptimal reproduction and health performance (e.g. longer calving interval (r=-0.21) and higher culling rate (r=-0.15)). Concerning economic results, low HYMIR-CH4 was significantly associated with lower gross margin per cow (r=0.19) and per litre FPCM (r=0.09). To conclude, this study suggested that low lactating dairy cow gastro-enteric CH4 production tended to be associated with more extensive or suboptimal management practices, which could lead to lower profitability. The observed low correlations suggest complex interactions between variables due to the use of on-farm data with large variability in technical and management practices.

Louisiana SIP: LAC 33:III Ch. 5 Section 509. Prevention of Significant Deterioration; SIP effective 1989-05-08 (LAc49) and 1989-08-14 (LAc50) and 1991-07-01 (LAc57) and 1996-12-16 (LAc69) to 2011-08-17 (LAd36 - Revised)

EPA Pesticide Factsheets

Louisiana SIP: LAC 33:III Ch. 5 Section 509. Prevention of Significant Deterioration; SIP effective 1989-05-08 (LAc49) and 1989-08-14 (LAc50) and 1991-07-01 (LAc57) and 1996-12-16 (LAc69) to 2011-08-17 (LAd36 - Revised)

Louisiana SIP: LAC 33:III Ch 61 Subchap A, §6121 to § 6131--Method 43 - Capture Efficiency Test Procedures; SIP effective 1994-06-06 (LAc60) to to 2011-08-03 (LAd34 - Moved to Chap 21 Subchap N §§ 2155-2160 and revised)

EPA Pesticide Factsheets

Louisiana SIP: LAC 33:III Ch 61 Subchap A, §6121 to § 6131--Method 43 - Capture Efficiency Test Procedures; SIP effective 1994-06-06 (LAc60) to to 2011-08-03 (LAd34 - Moved to Chap 21 Subchap N §§ 2155-2160 and revised)

Louisiana SIP: LAC 33:III Ch. 7 - Table 2 - Ambient Air--Methods of Contaminant Measurements; SIP effective 1989-05-08 (LAc49) and 1989-08-14 (LAc50) to 2011-08-03 (LAd34 - Moved to Section 711 and revised [adds PM-2.5])

EPA Pesticide Factsheets

Louisiana SIP: LAC 33:III Ch. 7 - Table 2 - Ambient Air--Methods of Contaminant Measurements; SIP effective 1989-05-08 (LAc49) and 1989-08-14 (LAc50) to 2011-08-03 (LAd34 - Moved to Section 711 and revised [adds PM-2.5])

Louisiana SIP: LAC 33:III Ch. 7 Section 709. Measurement of Concentrations PM10, SO2, Carbon Monoxide, Atmospheric Oxidants, Nitrogen Oxides, and Lead; SIP effective 1989-05-08 (LAc49) and 1989-08-14 (LAc50) to 2011-08-03 (LAd34 - Revised)

EPA Pesticide Factsheets

Louisiana SIP: LAC 33:III Ch. 7 Section 709. Measurement of Concentrations PM10, SO2, Carbon Monoxide, Atmospheric Oxidants, Nitrogen Oxides, and Lead; SIP effective 1989-05-08 (LAc49) and 1989-08-14 (LAc50) to 2011-08-03 (LAd34 - Revised)

Structural, magnetic and phonon properties of Cr(III)-doped perovskite metal formate framework [(CH{sub 3}){sub 2}NH{sub 2}][Mn(HCOO){sub 3}

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

Mączka, Mirosław, E-mail: m.maczka@int.pan.wroc.pl; Gągor, Anna; Hermanowicz, Krzysztof

2016-05-15

We have incorporated Cr(III) into [(CH{sub 3}){sub 2}NH{sub 2}][Mn(HCOO){sub 3}] (DMMn) multiferroic metal organic framework (MOF). The highest concentration of Cr(III) in the synthesized samples reached 15.9 mol%. The obtained samples were characterized by powder and single-crystal X-ray diffraction, DSC, magnetic susceptibility, dielectric, EPR, Raman and IR methods. These methods and the performed chemical analysis revealed that electrical charge neutrality after substitution of Cr(III) for Mn(II) is maintained by partial replacement of dimethylammonium (DMA{sup +}) cations by neutral HCOOH molecules. These changes in the chemical composition are responsible for weakening of the hydrogen bonds and decreased flexibility of the framework.more » This in turn leads to lowering of the ferroelectric phase transition temperature, observed around 185 K for undoped DMMn and around 155 K for the sample containing 3.1 mol% of Cr(III), and lack of macroscopic phase transition for the samples with Cr(III) content of 8.2 and 15.9 mol %. Another interesting effect observed for the studied samples is pronounced strengthening of the weak ferromagnetism of in Cr(III)-doped samples, associated with slight decrease of the ferromagnetic ordering temperature from 8.5 K for DMMn to 7.0 K for the sample with 15.9 mol % Cr(III) content. - Graphical abstract: Incorporation of Cr(III) into [(CH3)2NH2[Mn(HCOO)3] framework increases the magnetization. - Highlights: • Chromium(III) substitutes for Mn(II) in the studied MOF. • Charge neutrality is maintained by replacing DMA{sup +} cations by neutral HCOOH molecules. • Compounds with 8.2 and 15.9% of Cr(III) show no phase transition above 100 K. • Doping with Cr(III) increases magnetization.« less

Effects of single bond-ion and single bond-diradical form on the stretching vibration of Cdbnd N bridging bond in 4,4‧-disubstituted benzylidene anilines

NASA Astrophysics Data System (ADS)

Cao, Chao-Tun; Bi, Yakun; Cao, Chenzhong

2016-06-01

Fifty-seven samples of model compounds, 4,4‧-disubstituted benzylidene anilines, p-X-ArCH = NAr-p-Y were synthesized. Their infrared absorption spectra were recorded, and the stretching vibration frequencies νCdbnd N of the Cdbnd N bridging bond were determined. New stretching vibration mode was proposed by means of the analysis of the factors affecting νCdbnd N, that is there are mainly three modes in the stretching vibration of Cdbnd N bond: (I) polar double bond form Cdbnd N, (II) single bond-ion form C+-N- and (III) single bond-diradical form Crad -Nrad . The contributions of the forms (I) and (II) to the change of νCdbnd N can be quantified by using Hammett substituent constant (including substituent cross-interaction effects between X and Y groups), whereas the contribution of the form (III) can be quantified by employing the excited-state substituent constant. The most contribution of these three forms is the form (III), the next is the form (II), whose contribution difference was discussed with the viewpoint of energy requirements in vibration with the form (III) and form (II).

Prediction of enteric methane production, yield, and intensity in dairy cattle using an intercontinental database.

PubMed

Niu, Mutian; Kebreab, Ermias; Hristov, Alexander N; Oh, Joonpyo; Arndt, Claudia; Bannink, André; Bayat, Ali R; Brito, André F; Boland, Tommy; Casper, David; Crompton, Les A; Dijkstra, Jan; Eugène, Maguy A; Garnsworthy, Phil C; Haque, Md Najmul; Hellwing, Anne L F; Huhtanen, Pekka; Kreuzer, Michael; Kuhla, Bjoern; Lund, Peter; Madsen, Jørgen; Martin, Cécile; McClelland, Shelby C; McGee, Mark; Moate, Peter J; Muetzel, Stefan; Muñoz, Camila; O'Kiely, Padraig; Peiren, Nico; Reynolds, Christopher K; Schwarm, Angela; Shingfield, Kevin J; Storlien, Tonje M; Weisbjerg, Martin R; Yáñez-Ruiz, David R; Yu, Zhongtang

2018-02-16

Enteric methane (CH 4 ) production from cattle contributes to global greenhouse gas emissions. Measurement of enteric CH 4 is complex, expensive, and impractical at large scales; therefore, models are commonly used to predict CH 4 production. However, building robust prediction models requires extensive data from animals under different management systems worldwide. The objectives of this study were to (1) collate a global database of enteric CH 4 production from individual lactating dairy cattle; (2) determine the availability of key variables for predicting enteric CH 4 production (g/day per cow), yield [g/kg dry matter intake (DMI)], and intensity (g/kg energy corrected milk) and their respective relationships; (3) develop intercontinental and regional models and cross-validate their performance; and (4) assess the trade-off between availability of on-farm inputs and CH 4 prediction accuracy. The intercontinental database covered Europe (EU), the United States (US), and Australia (AU). A sequential approach was taken by incrementally adding key variables to develop models with increasing complexity. Methane emissions were predicted by fitting linear mixed models. Within model categories, an intercontinental model with the most available independent variables performed best with root mean square prediction error (RMSPE) as a percentage of mean observed value of 16.6%, 14.7%, and 19.8% for intercontinental, EU, and United States regions, respectively. Less complex models requiring only DMI had predictive ability comparable to complex models. Enteric CH 4 production, yield, and intensity prediction models developed on an intercontinental basis had similar performance across regions, however, intercepts and slopes were different with implications for prediction. Revised CH 4 emission conversion factors for specific regions are required to improve CH 4 production estimates in national inventories. In conclusion, information on DMI is required for good prediction, and other factors such as dietary neutral detergent fiber (NDF) concentration, improve the prediction. For enteric CH 4 yield and intensity prediction, information on milk yield and composition is required for better estimation. © 2018 John Wiley & Sons Ltd.

Prediction CH4 Emissions from the Wetlands in the Sanjiang Plain of Northeastern China in the 21st Century.

PubMed

Li, Tingting; Zhang, Qing; Zhang, Wen; Wang, Guocheng; Lu, Yanyu; Yu, Lijun; Zhang, Ran

2016-01-01

The Sanjiang Plain has been experienced significant wetland loss due to expanded agricultural activities, and will be potentially restored by the China National Wetland Conservation Action Plan (NWCP) in future. The objective of this study is to evaluate the impact of future climate warming and wetland restoration on wetland CH4 emissions in northeast China. We used an atmosphere-vegetation interaction model (AVIM2) to drive a modified biogeophysical model (CH4MODwetland), and projected CH4 flux variations from the Sanjiang Plain wetlands under different Representative Concentration Pathway scenarios throughout the 21st century. Model validation showed that the regressions between the observed and simulated CH4 fluxes by the modified model produced an R2 of 0.49 with a slope of 0.87 (p<0.001, n = 237). According to the AVIM2 simulation, the net primary productivity of the Sanjiang Plain wetlands will increase by 38.2 g m-2 yr-1, 116.6 g m-2 yr-1 and 250.4 g m-2 yr-1 under RCP 2.6, RCP 4.5 and RCP 8.5, respectively, by the end of this century. For RCP 2.6, 4.5 and 8.5 scenarios, the CH4 fluxes will increase by 5.7 g m-2 yr-1, 57.5 g m-2 yr-1 and 112.2 g m-2 yr-1. Combined with the wetland restoration, the regional emissions will increase by 0.18‒1.52 Tg. The CH4 emissions will be stimulated by climate change and wetland restoration. Regional wetland restoration planning should be directed against different climate scenarios in order to suppress methane emissions.

Prediction CH4 Emissions from the Wetlands in the Sanjiang Plain of Northeastern China in the 21st Century

PubMed Central

Li, Tingting; Zhang, Qing; Zhang, Wen; Wang, Guocheng; Lu, Yanyu; Yu, Lijun; Zhang, Ran

2016-01-01

The Sanjiang Plain has been experienced significant wetland loss due to expanded agricultural activities, and will be potentially restored by the China National Wetland Conservation Action Plan (NWCP) in future. The objective of this study is to evaluate the impact of future climate warming and wetland restoration on wetland CH4 emissions in northeast China. We used an atmosphere-vegetation interaction model (AVIM2) to drive a modified biogeophysical model (CH4MODwetland), and projected CH4 flux variations from the Sanjiang Plain wetlands under different Representative Concentration Pathway scenarios throughout the 21st century. Model validation showed that the regressions between the observed and simulated CH4 fluxes by the modified model produced an R2 of 0.49 with a slope of 0.87 (p<0.001, n = 237). According to the AVIM2 simulation, the net primary productivity of the Sanjiang Plain wetlands will increase by 38.2 g m-2 yr-1, 116.6 g m-2 yr-1 and 250.4 g m-2 yr-1 under RCP 2.6, RCP 4.5 and RCP 8.5, respectively, by the end of this century. For RCP 2.6, 4.5 and 8.5 scenarios, the CH4 fluxes will increase by 5.7 g m-2 yr-1, 57.5 g m-2 yr-1 and 112.2 g m-2 yr-1. Combined with the wetland restoration, the regional emissions will increase by 0.18‒1.52 Tg. The CH4 emissions will be stimulated by climate change and wetland restoration. Regional wetland restoration planning should be directed against different climate scenarios in order to suppress methane emissions. PMID:27409586

Electron Irradiation of Kuiper Belt Surface Ices: Ternary N2-CH4-CO Mixtures as a Case Study

NASA Astrophysics Data System (ADS)

Kim, Y. S.; Kaiser, R. I.

2012-10-01

The space weathering of icy Kuiper Belt Objects was investigated in this case study by exposing methane (CH4) and carbon monoxide (CO) doped nitrogen (N2) ices at 10 K to ionizing radiation in the form of energetic electrons. Online and in situ Fourier transform infrared spectroscopy was utilized to monitor the radiation-induced chemical processing of these ices. Along with isocyanic acid (HNCO), the products could be mainly derived from those formed in irradiated binary ices of the N2-CH4 and CO-CH4 systems: nitrogen-bearing products were found in the form of hydrogen cyanide (HCN), hydrogen isocyanide (HNC), diazomethane (CH2N2), and its radical fragment (HCN2); oxygen-bearing products were of acetaldehyde (CH3CHO), formyl radical (HCO), and formaldehyde (H2CO). As in the pure ices, the methyl radical (CH3) and ethane (C2H6) were also detected, as were carbon dioxide (CO2) and the azide radical (N3). Based on the temporal evolution of the newly formed products, kinetic reaction schemes were then developed to fit the temporal profiles of the newly formed species, resulting in numerical sets of rate constants. The current study highlights important constraints on the preferential formation of isocyanic acid (HNCO) over hydrogen cyanide (HCN) and hydrogen isocyanide (HNC), thus guiding the astrobiological and chemical evolution of those distant bodies.

Greenhouse Gas Emissions from U.S. Hydropower Reservoirs: FY2011 Annual Progress Report

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

Stewart, Arthur J; Mosher, Jennifer J; Mulholland, Patrick J

2012-05-01

The primary objective of this study is to quantify the net emissions of key greenhouse gases (GHG) - notably, CO{sub 2} and CH{sub 4} - from hydropower reservoirs in moist temperate areas within the U.S. The rationale for this objective is straightforward: if net emissions of GHG can be determined, it would be possible to directly compare hydropower to other power-producing methods on a carbon-emissions basis. Studies of GHG emissions from hydropower reservoirs elsewhere suggest that net emissions can be moderately high in tropical areas. In such areas, warm temperatures and relatively high supply rates of labile organic matter canmore » encourage high rates of decomposition, which (depending upon local conditions) can result in elevated releases of CO{sub 2} and CH{sub 4}. CO{sub 2} and CH{sub 4} emissions also tend to be higher for younger reservoirs than for older reservoirs, because vegetation and labile soil organic matter that is inundated when a reservoir is created can continue to decompose for several years (Galy-Lacaux et al. 1997, Barros et al. 2011). Water bodies located in climatically cooler areas, such as in boreal forests, could be expected to have lower net emissions of CO{sub 2} and CH{sub 4} because their organic carbon supplies tend to be relatively recalcitrant to microbial action and because cooler water temperatures are less conducive to decomposition.« less

Screening of Two ADH4 Variations in a Swedish Cluster Headache Case–Control Material

PubMed Central

Fourier, Carmen; Ran, Caroline; Steinberg, Anna; Sjöstrand, Christina; Waldenlind, Elisabet

2016-01-01

Background Cluster headache (CH) is a severe neurovascular disorder and an increasing amount of evidence points to a genetic contribution to this disease. When CH was first described, it was observed that alcohol may precipitate an attack during the active phase of the disease. The alcohol dehydrogenase 4 (ADH4) gene encodes an enzyme which contributes to the metabolization of alcohol and is, therefore, an interesting candidate gene for CH. Two Italian groups have reported association of the single nucleotide polymorphism (SNP) rs1126671 located in the ADH4 gene with an increased risk of CH in Italy. In addition, one of the groups found an association between the ADH4 SNP rs1800759 and CH. Objective To perform a replication study on the ADH4 SNPs rs1126671 and rs1800759 in a large homogeneous Swedish case–control cohort in order to further investigate the possible contribution of ADH4 to CH. Methods A total of 390 unrelated patients diagnosed with CH and 389 controls representing a general Swedish population were recruited to the study. DNA samples from patients and controls were genotyped for the two ADH4 SNPs rs1126671 and rs1800759 using quantitative real‐time polymerase chain reaction. Statistical analyses of genotype, allele and haplotype frequencies for the two SNPs were performed and compared between patients and controls. Results For rs1126671, the minor allele frequency (A allele) was 32.8% (n = 254) in controls compared with 31.9% (n = 249) in CH patients. The minor allele frequency (A allele) of rs1800759 was 42.3% (n = 324) in controls and 41.9% (n = 327) in CH patients. Statistical analysis showed no significant differences in allele as well as in genotype or haplotype frequencies between the patient and control group for either SNP. This was also seen after stratifying the patient group for experiencing alcohol as a trigger factor. Conclusions The data did not support an association of the ADH4 SNPs rs1126671 and rs1800759 with CH. A comparison with previous studies revealed variance in genotype, allele, and haplotype frequencies among the different populations which might contribute to the contradictory results. Although a significant association with CH in Swedish case–control group was not found, ADH4 as a candidate gene for CH could not be excluded. PMID:27041676

Microbial Diversity Associated With Geochemical Changes in a Deep Subsurface Aquifer

NASA Astrophysics Data System (ADS)

Davidson, M. M.; Onstott, T. C.; Pratt, L. M.; Boice, E.; Southam, G.; Wanger, G.; Sherwood-Lollar, B.; Lippmann, J.; Seymoor, W.

2003-12-01

The microbial diversity of a 1.83km deep, thermophilic, fluid-filled subterranean fracture was monitored over a three and a half month period and correlated to observed changes in the geochemistry of the system. Three water samples were analyzed using 16S rDNA molecular techniques for microbial diversity, isotopic and geochemical composition. Gibbs' free energy of microbial redox reactions predicted that at in situ conditions sulfate reduction, methanogenesis and acetogenesis should be dominant metabolic pathways utilized by microbes, whereas Fe(III)-reduction should only have been favorable in the last sample. Noble gas isotopic data yielded a subsurface residence time of ˜10-100 Myr. and the non-meteoric δ D vs. δ 18O values were indicative of water-rock alteration at <100° C. δ 34S of sulfide and sulfate differed by 15‰ , consistent with fractionation by sulfate reducing bacteria. H2 concentrations declined with time, which in conjunction with the δ 34S data, suggested that hydrogenotrophic sulfate reducing bacteria dominate the community. This was compatible with 16S rDNA analysis, which yielded clones similar to Desulfotomaculum and Desulfofustis species appearing in the three 16S libraries. δ 13C and δ D values of CH4 and light hydrocarbons indicated methanogenic CH4 was mixing with abiogenically formed CH4. This is consistent with the presence of Archaeal 16S sequences similar to Methanosaeta and Methanosarcina species. The temporal increase in acetate concentration could be attributed to clone types similar to known acetogenic bacteria such as Moorella glycerini, which were present in the last sample. Clones similar to known Fe(III)-reducing bacteria such as Geovibrio species were observed in the first and last samples.

Control of Methane Production and Exchange in Northern Peatlands

NASA Technical Reports Server (NTRS)

Crill, Patrick

1997-01-01

This proposal has successfully supported studies that have developed unique long ten-n datasets of methane (CH4) emissions and carbon dioxide (CO2) exchange in order to quantify the controls on CH4 production and exchange especially the linkages to the carbon cycle in northern peatlands. The primary research site has been a small fen in southeastern New Hampshire where a unique multi-year data baseline of CH4 flux measurements was begun (with NASA funding) in 1989. The fen has also been instrumented for continuous hydrological and meteorological observations and year-round porewater sampling. Multiyear datasets of methane flux are very valuable and very rare. Datasets using the same sampling techniques at the same sites are the only way to assess the effect of the integrated ecosystem response to climatological variability. The research has had two basic objectives: 1. To quantify the effect of seasonal and interannual variability on CH4flux. 2. To examine process level controls on methane dynamics.

Seasonal and diel variations of ammonia and methane emissions from a naturally ventilated dairy building and the associated factors influencing emissions.

PubMed

Saha, C K; Ammon, C; Berg, W; Fiedler, M; Loebsin, C; Sanftleben, P; Brunsch, R; Amon, T

2014-01-15

Understanding seasonal and diel variations of ammonia (NH3) and methane (CH4) emissions from a naturally ventilated dairy (NVD) building may lead to develop successful control strategies for reducing emissions throughout the year. The main objective of this study was to quantify seasonal and diel variations of NH3 and CH4 emissions together with associated factors influencing emissions. Measurements were carried out with identical experimental set-up to cover three winter, spring and summer seasons, and two autumn seasons in the years 2010, 2011, and 2012. The data from 2010 and 2011 were used for developing emission prediction models and the data from 2012 were used for model validation. The results showed that NH3 emission varied seasonally following outside temperature whereas CH4 emission did not show clear seasonal trend. Diel variation of CH4 emission was less pronounced than NH3. The average NH3 and CH4 emissions between 6a.m. and 6p.m. were 66% and 33% higher than the average NH3 and CH4 emissions between 6p.m. and 6a.m., respectively for all seasons. The significant relationships (P<0.0001) between NH3 and influencing factors were found including outside temperature, humidity, wind speed and direction, hour of the day and day of the year. The significant effect (P<0.0001) of climate factors, hours of the day and days of the year on CH4 emission might be directly related to activities of the cows. © 2013.

Development of equations for predicting methane emissions from ruminants.

PubMed

Ramin, M; Huhtanen, P

2013-04-01

Ruminants contribute to global warming by releasing methane (CH4) gas by enteric fermentation. This has increased interest among animal scientists to develop and improve equations predicting CH4 production. The objectives of the current study were to collect a data set from respiration studies and to evaluate the effects of dietary and animal factors on CH4 production from diets that can safely be fed to dairy cows, using a mixed model regression analysis. Therefore, diets containing more than 75% concentrate on a dry matter (DM) basis were excluded from the analysis. The final data set included a total of 298 treatment means from 52 published papers with 207 cattle and 91 sheep diets. Dry matter intake per kilogram of body weight (DMIBW), organic matter digestibility estimated at the maintenance level of feeding (OMDm), and dietary concentrations of neutral detergent fiber (NDF), nonfiber carbohydrates (NFC), and ether extract (EE) were the variables of the best-fit equation predicting CH4 energy (CH4-E) as a proportion of gross energy intake (GE): CH4-E/GE (kJ/MJ)=-0.6 (±12.76) - 0.70 (±0.072) × DMIBW (g/kg) + 0.076 (±0.0118) × OMDm (g/kg) - 0.13 (±0.020) × EE (g/kg of DM) + 0.046 (±0.0097) × NDF (g/kg of DM) + 0.044 (±0.0094) × NFC (g/kg of DM), resulting in the lowest root mean square error adjusted for random study effect (adj. RMSE=3.26 kJ/MJ). Total CH4 production (L/d) in the cattle data set was closely related to DM intake. However, further inclusion of other variables improved the model: CH4 (L/d)=-64.0 (±35.0) + 26.0 (±1.02) × DM intake (kg/d) - 0.61 (±0.132) × DMI(2)(centered) + 0.25 (±0.051) × OMDm (g/kg) - 66.4 (±8.22) × EE intake (kg of DM/d) - 45.0 (±23.50) × NFC/(NDF + NFC), with adj. RMSE of 21.1 L/d. Cross-validation of the CH4-E/GE equation [observed CH4-E/GE=0.96 (±0.103) × predicted CH4-E/GE + 2.3 (±7.05); R(2)=0.85, adj. RMSE=3.38 kJ/MJ] indicated that differences in CH4 production between the diets could be predicted accurately. We conclude that feed intake is the main determinant of total CH4 production and that CH4-E/GE is negatively related to feeding level and dietary fat concentration and positively to diet digestibility, whereas dietary carbohydrate composition has only minor effects. Copyright © 2013 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Effects of Adding Corn Dried Distiller Grains with Solubles (DDGS) to the Dairy Cow Diet and Effects of Bedding in Dairy Cow Slurry on Fugitive Methane Emissions

PubMed Central

Massé, Daniel I.; Jarret, Guillaume; Benchaar, Chaouki; Hassanat, Fadi

2014-01-01

Simple Summary The objectives of this experiment were to investigate the effects of adding corn DDGS to the dairy cow diet as well as the bedding types (wood shavings, straw or peat moss) on manure fugitive CH4 emissions. The incorporation of DDGS in the diet has increased manure methane emission by 15% and the use of peat moss as bedding has increased manure methane emission by 27%. Abstract The specific objectives of this experiment were to investigate the effects of adding 10% or 30% corn dried distillers grains with solubles (DDGS) to the dairy cow diet and the effects of bedding type (wood shavings, straw or peat moss) in dairy slurry on fugitive CH4 emissions. The addition of DDGS10 to the dairy cow diet significantly increased (29%) the daily amount of fat excreted in slurry compared to the control diet. The inclusion of DDGS30 in the diet increased the daily amounts of excreted DM, volatile solids (VS), fat, neutral detergent fiber (NDF), acid detergent fiber (ADF) and hemicellulose by 18%, 18%, 70%, 30%, 15% and 53%, respectively, compared to the control diet. During the storage experiment, daily fugitive CH4 emissions showed a significant increase of 15% (p < 0.05) for the slurry resulting from the corn DDGS30 diet. The addition of wood shavings and straw did not have a significant effect on daily fugitive CH4 emissions relative to the control diet, whereas the addition of peat moss caused a significant increase of 27% (p < 0.05) in fugitive CH4 emissions. PMID:26479012

Pig feeding strategy coupled with effluent management - fresh or stored slurry, solid phase separation - on methane potential and methane conversion factors during storage

NASA Astrophysics Data System (ADS)

Jarret, Guillaume; Martinez, José; Dourmad, Jean-Yves

2011-11-01

In the guideline for the determination of methane (CH 4) emission from animal manure (IPCC) the amount of CH 4 emitted is generally calculated according to an equation combining the amount of organic matter (OM) or volatile solids excreted, the ultimate CH 4 potential ( B0) of excreta and a system-specific methane conversion factor (MCF, %) that reflects the portion of B0 that is really converted into CH 4. The objective of the present study was to investigate the effect of the modification of dietary crude protein and fibre levels on B0 of pig slurry and on subsequent MCF according to different strategies of slurry management. Five experimental diets differing mainly in their crude protein and fibre content were compared. Two types of measurement of CH 4 emission were performed. The first was the measurement of B0 of slurry using biomethanogene potential (BMP) test. The second consisted in a storage simulation, which was performed on different kinds of effluents: fresh slurry (FSl), stored slurry (SSl), and faeces mixed with water (FaW). The type of diet and the type of effluent affected ( P < 0.001) CH 4 production after 30, 50 and 100 days. Moreover, the interaction between type of effluent and type of diet was significant for CH 4 emission and for MCF. CH 4 production was the highest for BMP, the average production of CH 4 during storage from FaW, FSl and SSl samples representing 77%, 58% and 64% of the B0 value. The dynamic of CH 4 production during BMP tests was rather similar for all dietary treatments whereas it differed for storage simulation studies with significant effects of dietary CP and fibre contents. The results from this study indicate that the type of diet has a significant but rather limited effect on B0 value of effluent. The effect of diet is much more marked on MCF, with lower values for high protein diets, and higher values for high fibre diets. MCF is also affected by manure management, the values measured on separated faeces from urine being much higher than for slurry.

Light-driven, proton-controlled, catalytic aerobic C-H oxidation mediated by a Mn(III) porphyrinoid complex.

PubMed

Neu, Heather M; Jung, Jieun; Baglia, Regina A; Siegler, Maxime A; Ohkubo, Kei; Fukuzumi, Shunichi; Goldberg, David P

2015-04-15

The visible light-driven, catalytic aerobic oxidation of benzylic C-H bonds was mediated by a Mn(III) corrolazine complex. To achieve catalytic turnovers, a strict selective requirement for the addition of protons was established. The resting state of the catalyst was unambiguously characterized by X-ray diffraction as [Mn(III)(H2O)(TBP8Cz(H))](+), in which a single, remote site on the ligand is protonated. If two remote sites are protonated, however, reactivity with O2 is shut down. Spectroscopic methods revealed that the related Mn(V)(O) complex is also protonated at the same remote site at -60 °C, but undergoes valence tautomerization upon warming.

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.

Process for alkane group dehydrogenation with organometallic catalyst

DOEpatents

Kaska, William C.; Jensen, Craig M.

1998-01-01

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.

Methane emissions from a Californian landfill, determined from airborne remote sensing and in situ measurements

NASA Astrophysics Data System (ADS)

Krautwurst, Sven; Gerilowski, Konstantin; Jonsson, Haflidi H.; Thompson, David R.; Kolyer, Richard W.; Iraci, Laura T.; Thorpe, Andrew K.; Horstjann, Markus; Eastwood, Michael; Leifer, Ira; Vigil, Samuel A.; Krings, Thomas; Borchardt, Jakob; Buchwitz, Michael; Fladeland, Matthew M.; Burrows, John P.; Bovensmann, Heinrich

2017-09-01

Fugitive emissions from waste disposal sites are important anthropogenic sources of the greenhouse gas methane (CH4). As a result of the growing world population and the recognition of the need to control greenhouse gas emissions, this anthropogenic source of CH4 has received much recent attention. However, the accurate assessment of the CH4 emissions from landfills by modeling and existing measurement techniques is challenging. This is because of inaccurate knowledge of the model parameters and the extent of and limited accessibility to landfill sites. This results in a large uncertainty in our knowledge of the emissions of CH4 from landfills and waste management. In this study, we present results derived from data collected during the research campaign COMEX (CO2 and MEthane eXperiment) in late summer 2014 in the Los Angeles (LA) Basin. One objective of COMEX, which comprised aircraft observations of methane by the remote sensing Methane Airborne MAPper (MAMAP) instrument and a Picarro greenhouse gas in situ analyzer, was the quantitative investigation of CH4 emissions. Enhanced CH4 concentrations or CH4 plumes were detected downwind of landfills by remote sensing aircraft surveys. Subsequent to each remote sensing survey, the detected plume was sampled within the atmospheric boundary layer by in situ measurements of atmospheric parameters such as wind information and dry gas mixing ratios of CH4 and carbon dioxide (CO2) from the same aircraft. This was undertaken to facilitate the independent estimation of the surface fluxes for the validation of the remote sensing estimates. During the COMEX campaign, four landfills in the LA Basin were surveyed. One landfill repeatedly showed a clear emission plume. This landfill, the Olinda Alpha Landfill, was investigated on 4 days during the last week of August and first days of September 2014. Emissions were estimated for all days using a mass balance approach. The derived emissions vary between 11.6 and 17.8 kt CH4 yr-1 with related uncertainties in the range of 14 to 45 %. The comparison of the remote sensing and in situ based CH4 emission rate estimates reveals good agreement within the error bars with an average of the absolute differences of around 2.4 kt CH4 yr-1 (±2. 8 kt CH4 yr-1). The US Environmental Protection Agency (EPA) reported inventory value is 11.5 kt CH4 yr-1 for 2014, on average 2.8 kt CH4 yr-1 (±1. 6 kt CH4 yr-1) lower than our estimates acquired in the afternoon in late summer 2014. This difference may in part be explained by a possible leak located on the southwestern slope of the landfill, which we identified in the observations of the Airborne Visible/Infrared Imaging Spectrometer - Next Generation (AVIRIS-NG) instrument, flown contemporaneously aboard a second aircraft on 1 day.

Effects of warming and nitrogen fertilization on GHG flux in the permafrost region of an alpine meadow

NASA Astrophysics Data System (ADS)

Chen, Xiaopeng; Wang, Genxu; Zhang, Tao; Mao, Tianxu; Wei, Da; Hu, Zhaoyong; Song, Chunlin

2017-05-01

The limited number of in situ measurements of greenhouse gas (GHG) flux during soil freeze-thaw cycles in permafrost regions limits our ability to accurately predict how the alpine ecosystem carbon sink or source function will vary under future warming and increased nitrogen (N) deposition. An alpine meadow in the permafrost region of the Qinghai-Tibet Plateau was selected, and a simulated warming with N fertilization experiment was carried out to investigate the key GHG fluxes (ecosystem respiration [Re], CH4 and N2O) in the early (EG), mid (MG) and late (LG) growing seasons. The results showed that: (i) warming (4.5 °C) increased the average seasonal Re, CH4 uptake and N2O emission by 73.5%, 65.9% and 431.6%, respectively. N fertilization (4 g N m-2) alone had no significant effect on GHG flux; the interaction of warming and N fertilization enhanced CH4 uptake by 10.3% and N2O emissions by 27.2% than warming, while there was no significant effect on the Re; (ii) the average seasonal fluxes of Re, CH4 and N2O were MG > LG > EG, and Re and CH4 uptake were most sensitive to the soil freezing process instead of soil thawing process; (iii) surface soil temperature was the main driving factor of the Re and CH4 fluxes, and the N2O flux was mainly affected by daily rainfall; (iv) in the growing season, warming increased greenhouse warming potential (GWP) of the alpine meadow by 74.5%, the N fertilization decreased GWP of the warming plots by 13.9% but it was not statistically significant. These results indicate that (i) relative to future climate warming (or permafrost thawing), there could be a hysteresis of GHG flux in the alpine meadow of permafrost region; (ii) under the scenario of climate warming, increasing N deposition has limited impacts on the feedback of GHG flux of the alpine meadow.

Clinical Characteristics and Treatment Patterns Among Patients Diagnosed With Cluster Headache in U.S. Healthcare Claims Data

PubMed Central

Ford, Janet H.; Nyhuis, Allen W.; Joshi, Shivang G.; Robinson, Rebecca L.; Aurora, Sheena K.; Martinez, James M.

2017-01-01

Objective To characterize demographics, clinical characteristics, and treatment patterns of patients with cluster headache (CH). Background CH is an uncommon trigeminal autonomic cephalalgia with limited evidence‐based treatment options. Patients suffer from extremely painful unilateral headache attacks and autonomic symptoms with episodic and chronic cycles. Design/Methods This retrospective analysis used insurance claims from Truven Health Analytics MarketScan® research databases from 2009 to 2014. Two cohorts were compared: CH patients (with ≥2 CH claims) were propensity score matched with 4 non‐headache controls, all with continuous enrollment for 12 months before and after the date of first CH claim or matched period among controls. Results CH patients (N = 7589) were mainly male (57.4%) and 35‐64 years old (73.2%), with significantly more claims for comorbid conditions vs controls (N = 30,341), including depressive disorders (19.8% vs 10.0%), sleep disturbances (19.7% vs 9.1%), anxiety disorders (19.2% vs 8.7%), and tobacco use disorders (12.8% vs 5.3%), with 2.5 times greater odds of suicidal ideation (all P < .0001). Odds of drug dependence were 3‐fold greater among CH patients (OR = 2.8 [95% CI 2.3‐3.4, P < .0001]). CH patients reported significantly greater use of prescription medications compared with controls; 25% of CH patients had >12 unique prescription drug claims. Most commonly prescribed drug classes for CH patients included: opiate agonists (41%), corticosteroids (34%), 5HT‐1 agonists (32%), antidepressants (31%), NSAIDs (29%), anticonvulsants (28%), calcium antagonists (27%), and benzodiazepines (22%). Only 30.4% of CH patients received recognized CH treatments without opioids during the 12‐month post‐index period. These patients were less likely to visit emergency departments or need hospitalizations (26.8%) as compared to CH patients with no pharmacy claims for recognized CH treatments or opioids (33.6%; P < .0001). Conclusions The burden of CH is associated with significant co‐morbidity, including substance use disorders and suicidal ideation, and treatment patterns indicating low use of recognized CH treatments. PMID:28581025

UV-visible spectroscopy of macrocyclic alkyl, nitrosyl and halide complexes of cobalt and rhodium. Experiment and calculation.

PubMed

Hull, Emily A; West, Aaron C; Pestovsky, Oleg; Kristian, Kathleen E; Ellern, Arkady; Dunne, James F; Carraher, Jack M; Bakac, Andreja; Windus, Theresa L

2015-02-28

Transition metal complexes (NH3)5CoX(2+) (X = CH3, Cl) and L(H2O)MX(2+), where M = Rh or Co, X = CH3, NO, or Cl, and L is a macrocyclic N4 ligand are examined by both experiment and computation to better understand their electronic spectra and associated photochemistry. Specifically, irradiation into weak visible bands of nitrosyl and alkyl complexes (NH3)5CoCH3(2+) and L(H2O)M(III)X(2+) (X = CH3 or NO) leads to photohomolysis that generates the divalent metal complex and ˙CH3 or ˙NO, respectively. On the other hand, when X = halide or NO2, visible light photolysis leads to dissociation of X(-) and/or cis/trans isomerization. Computations show that visible bands for alkyl and nitrosyl complexes involve transitions from M-X bonding orbitals and/or metal d orbitals to M-X antibonding orbitals. In contrast, complexes with X = Cl or NO2 exhibit only d-d bands in the visible, so that homolytic cleavage of the M-X bond requires UV photolysis. UV-Vis spectra are not significantly dependent on the structure of the equatorial ligands, as shown by similar spectral features for (NH3)5CoCH3(2+) and L(1)(H2O)CoCH3(2+).

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Native defect-assisted enhanced response to CH4 near room temperature by Al0.07Ga0.93N nanowires.

PubMed

Parida, Santanu; Das, A; Prasad, Arun K; Ghatak, Jay; Dhara, Sandip

2018-06-26

Gas sensors at low operating temperature with high sensitivity require group III nitrides owing to their high chemical and thermal stabilities. For the first time, Al0.07Ga0.93N nanowires (NWs) have been utilized in CH4 sensing, and it has been demonstrated that they exhibit an improved response compared to GaN NWs at the low operating temperature of 50 °C. Al0.07Ga0.93N NWs have been synthesized via the ion beam mixing process using inert gas ion irradiation on the bilayer of Al/GaN NWs. The sensing mechanism is explained with the help of native defects present in the system. The number of shallow acceptors created by Ga vacancies (VGa) is found to be higher in Al0.07Ga0.93N NWs than in as-grown GaN NWs. The role of the O antisite defect (ON) for the formation of shallow VGa is inferred from photoluminescence spectroscopic analysis. These native defects strongly influence the gas sensing behaviour, which results in enhanced and low-temperature CH4 sensing.

A Discussion of Upper Stratospheric Ozone Asymmetry and Ozone Trend Changes

NASA Technical Reports Server (NTRS)

Li, Jinlong; Cunnold, Derek M.; Wang, Hsiang-Jui; Yang, Eun-Su; Newchurch, Mike J.

2002-01-01

Analyses from SAGE I/II version 6.0 data exhibit upper stratospheric ozone trends which are not significantly different from those in version 5.96 data. Trend calculations show larger downward trends at mid-high latitudes in the Southern Hemisphere than in the Northern Hemisphere, particularly in 1980s. There are also indications of decreasing downward trends with time from 1979 to 1999. We have used a chemical box model and the UARS measurements of long lived gases, CH4, H2O, NO(x), and temperature to show that, with a constant Cl(sub y) trend, a hemispheric ozone trend asymmetry of 1%/decade at 45 deg. around 43 km is expected due to the hemispheric differences of temperature and CH4 during late winter/early. Also ozone trends should have been approximately 1%/decade more negative from 1979-1989 than from 1989-1999 because of the chemical feedbacks. The model results further indicate that both the reported decrease in CH4 and the increase in H2O in HALOE measurements will result in a larger downward ozone trend and a decrease in the hemispheric ozone trend asymmetry.

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.

9,10-phenanthrenesemiquinone radical complexes of ruthenium(III), osmium(III) and rhodium(III) and redox series.

PubMed

Biswas, Manas Kumar; Patra, Sarat Chandra; Maity, Amarendra Nath; Ke, Shyue-Chu; Weyhermüller, Thomas; Ghosh, Prasanta

2013-05-14

Reactions of 9,10-phenanthrenequinone (PQ) in toluene with [M(II)(PPh3)3X2] at 298 K afford green complexes, trans-[M(PQ)(PPh3)2X2] (M = Ru, X = Cl, 1; M = Os, X = Br, 2) in moderate yields. Reaction of anhydrous RhCl3 with PQ and PPh3 in boiling ethanol affords the dark brown paramagnetic complex, cis-[Rh(PQ)(PPh3)2Cl2] (3) in good yields. Diffusion of iodine solution in n-hexane to the trans-[Os(PQ) (PPh3)2(CO)(Br)] solution in CH2Cl2 generates the crystals of trans-[Os(PQ)(PPh3)2(CO)(Br)](+)I3(-), (4(+))I3(-)), in lower yields. Single crystal X-ray structure determinations of 1·2toluene, 2·CH2Cl2 and 4(+)I3(-), UV-vis/NIR absorption spectra, EPR spectra of 3, electrochemical activities and DFT calculations on 1, 2, trans-[Ru(PQ)(PMe3)2Cl2] (1Me), trans-[Os(PQ)(PMe3)2Br2] (2Me), cis-[Rh(PQ)(PMe3)2Cl2] (3Me) and their oxidized and reduced analogues including trans-[Os(PQ)(PMe3)2(CO)(Br)](+) (4Me(+)) substantiated that 1-3 are the 9,10-phenanthrenesemiquinone radical (PQ(˙-)) complexes of ruthenium(III), osmium(III) and rhodium(III) and are defined as trans/cis-[M(III)(PQ(˙-))(PPh3)2X2] with a minor contribution of the resonance form trans/cis-[M(II)(PQ)(PPh3)2X2]. Two comparatively longer C-O (1.286(4) Å) and the shorter C-C lengths (1.415(7) Å) of the OO-chelate of 1·2toluene and 2·CH2Cl2 and the isotropic fluid solution EPR signal at g = 1.999 of 3 are consistent with the existence of the reduced PQ(˙-) ligand in 1-3 complexes. Anisotropic EPR spectra of the frozen glasses (g11 = g22 = 2.0046 and g33 = 1.9874) and solids (g11 = g22 = 2.005 and g33 = 1.987) instigate the contribution of the resonance form, cis-[Rh(II)(PQ)(PPh3)2Cl2] in 3. DFT calculations established that the closed shell singlet (CSS) solutions of 1Me and 2Me are unstable due to open shell singlet (OSS) perturbation. However, the broken symmetry (BS) (1,1) Ms = 0 solutions of 1Me and 2Me are respectively 22.6 and 24.2 kJ mole(-1) lower in energy and reproduced the experimental bond parameters well prompting the coordination of PQ(˙-) to the M(III) ions. The comparatively shorter C-O lengths, 1.268(4) and 1.266(5) Å and the longer C-C length, 1.466(6) Å, are consistent with the PQ chelation to osmium(II) ion in 4(+). The reversible anodic waves at 0.22, 0.22, and 0.18 V of 1-3, referenced by the Fc(+)/Fc couple, are assigned to the PQ(˙-)/PQ couple forming PQ complexes as trans/cis-[M(III)(PQ)(PPh3)2X2](+) while the cathodic waves at -0.92 and -0.89 V of 2 and 3 are due to formations of PQ(2-) complexes as trans-[M(III)(PQ(2-))(PPh3)2X2](-). 1 displays two overlapping cathodic waves at -0.72(89), -1.0(120) V. EPR spectrum of the frozen glass of 1(-) along with DFT calculations detected the contribution of both the valence tautomers, trans-[Ru(III)(PQ(2-))(PPh3)2Cl2](-) (g1 = g2 = 2.456; g3 = 1.983) and trans-[Ru(II)(PQ(˙-))(PPh3)2X2](-) (g(iso) = 1.999) in the anion. The characteristic lower energy absorption bands of 1 and 2 at 700 nm were assigned to CSS-OSS perturbation MLCT those are absent in paramagnetic 3, 1(+), 2(+), 1(-), 2(-) and 4(+) complexes, investigated by spectro-electrochemical measurements and time dependent (TD) DFT calculations on 1Me, 2Me, 1Me(+) and 1Me(-).

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

PubMed

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

2004-11-19

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

Synthesis of carbon nanoparticles from commercially available liquified petroleum gas

NASA Astrophysics Data System (ADS)

Nandiyanto, A. B. D.; Fadhlulloh, M. A.; Rahman, T.; Mudzakir, A.

2016-04-01

The aim of this study was to synthesize carbon nanoparticles (CNPs) from commercially available liquefied petroleum gas (LPG). In the research procedure, LPG was reacted with air to construct CNPs. To confirm the successful synthesis of CNPs, we conducted several sample analyses: Gas Chromatography-Mass Spectrometry (GC-MS), Transmission Electron Microscope (TEM), X-ray Diffraction (XRD), and Infrared Spectra (FTIR). We also varied LPG and oxygen mole ratios at 0.8; 2.4; 4.8; and 7.2. The GC-MS results indicated the composition of LPG was propane (58.90%), isobutane (18.35%), butane (22.26%), and butane, 2-methyl (0.48%). The TEM results showed that the particles were spheres with sizes of between 25 and 35 nm. The sizes of particles were controllable, depending on the mole ratio. The XRD results showed mole ratios of LPG and oxygen of 0.80 and 2.40 were natural graphite, whereas the mole ratios of 4.80 and 7.20 were hexagonal graphite. FT-IR results showed CNPs have absorption peaks at wave number (i) 752 (C-H bend sp2); (ii) 835 (C=C); (iii) 1274 (C-O-C vibration); (iv) 1400 and 1600 (C-C stretch aromatic); (v) 2800 (C-H sp2); (vi) 2900 (CH sp3); (vii) 3100 (C-H aromatic); and (viii) 3400 cm-1 (O-H). From the FTIR analysis results, the sample contained allotrope graphite due to detection of peaks at 1400 and 1600 cm-1 (C-C stretch aromatic) and 3100 cm-1 (C-H aromatic).

Iodometric determination of peroxydiphosphate in the presence of copper(II) or iron(II) as catalyst.

PubMed

Kapoor, S; Sharma, P D; Gupta, Y K

1975-09-01

Peroxydiphosphate can be determined iodometrically in the presence of a large excess of potassium iodide with copper(II) or iron(II) as catalyst through the operation of the Cu(II)/Cu(I) or Fe(II)/Fe(III) cycle. The method is applicable in HClO(4), H(2)SO(4), HCl and CH(3)COOH acid media in the range 0.1-1.0M studied. Nickel, manganese(II), cobalt(II), silver, chloride and phosphate are without effect.

A Highly Reactive Dicationic Iridium(III) Catalyst for Polarized Nazarov Cyclization

PubMed Central

Vaidya, Tulaza; Atesin, Abdurrahman C.; Herrick, Ildiko R.; Frontier, Alison J.; Eisenberg, Richard

2010-01-01

Pushing the Nazarov Envelope A new electrophilic complex [IrBr(CO)(diethylisopropylidene malonate)((R)-(+)-BINAP)](SbF6)2 (2) exhibits unusual activity in the catalysis of polarized Nazarov cyclization. Aryl vinyl ketones that show poor reactivity with well-known catalysts such as [Ir(CH3)(CO)(1,2-diiodobenzene)(dppe)](B(Arf)4−)2 (1), Sc(OTf)3 + LiClO4 and Cu(ClO4)2, can be cyclized with 2 + AgSbF6 (1:1) under mild conditions with concurrent AgBr precipitation. PMID:20358570

Predicting enteric methane emission of dairy cows with milk Fourier-transform infrared spectra and gas chromatography-based milk fatty acid profiles.

PubMed

van Gastelen, S; Mollenhorst, H; Antunes-Fernandes, E C; Hettinga, K A; van Burgsteden, G G; Dijkstra, J; Rademaker, J L W

2018-06-01

The objective of the present study was to compare the prediction potential of milk Fourier-transform infrared spectroscopy (FTIR) for CH 4 emissions of dairy cows with that of gas chromatography (GC)-based milk fatty acids (MFA). Data from 9 experiments with lactating Holstein-Friesian cows, with a total of 30 dietary treatments and 218 observations, were used. Methane emissions were measured for 3 consecutive days in climate respiration chambers and expressed as production (g/d), yield (g/kg of dry matter intake; DMI), and intensity (g/kg of fat- and protein-corrected milk; FPCM). Dry matter intake was 16.3 ± 2.18 kg/d (mean ± standard deviation), FPCM yield was 25.9 ± 5.06 kg/d, CH 4 production was 366 ± 53.9 g/d, CH 4 yield was 22.5 ± 2.10 g/kg of DMI, and CH 4 intensity was 14.4 ± 2.58 g/kg of FPCM. Milk was sampled during the same days and analyzed by GC and by FTIR. Multivariate GC-determined MFA-based and FTIR-based CH 4 prediction models were developed, and subsequently, the final CH 4 prediction models were evaluated with root mean squared error of prediction and concordance correlation coefficient analysis. Further, we performed a random 10-fold cross validation to calculate the performance parameters of the models (e.g., the coefficient of determination of cross validation). The final GC-determined MFA-based CH 4 prediction models estimate CH 4 production, yield, and intensity with a root mean squared error of prediction of 35.7 g/d, 1.6 g/kg of DMI, and 1.6 g/kg of FPCM and with a concordance correlation coefficient of 0.72, 0.59, and 0.77, respectively. The final FTIR-based CH 4 prediction models estimate CH 4 production, yield, and intensity with a root mean squared error of prediction of 43.2 g/d, 1.9 g/kg of DMI, and 1.7 g/kg of FPCM and with a concordance correlation coefficient of 0.52, 0.40, and 0.72, respectively. The GC-determined MFA-based prediction models described a greater part of the observed variation in CH 4 emission than did the FTIR-based models. The cross validation results indicate that all CH 4 prediction models (both GC-determined MFA-based and FTIR-based models) are robust; the difference between the coefficient of determination and the coefficient of determination of cross validation ranged from 0.01 to 0.07. The results indicate that GC-determined MFA have a greater potential than FTIR spectra to estimate CH 4 production, yield, and intensity. Both techniques hold potential but may not yet be ready to predict CH 4 emission of dairy cows in practice. Additional CH 4 measurements are needed to improve the accuracy and robustness of GC-determined MFA and FTIR spectra for CH 4 prediction. Copyright © 2018 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

A start-up of psychrophilic anaerobic sequence batch reactor digesting a 35 % total solids feed of dairy manure and wheat straw.

PubMed

Saady, Noori M Cata; Massé, Daniel I

2015-12-01

Zero liquid discharge is currently an objective in livestock manure management to minimize water pollution. This paper reports the start-up phase of a novel psychrophilic (20 °C) dry anaerobic digestion of dairy manure with bedding fed at 35 % total solids and an organic loading rate of 3.0 g total chemical oxygen demand kg(-1) inoculum day(-1) in anaerobic sequence batch reactors. The specific methane (CH4) yield ranged from 165.4 ± 9.8 to 213.9 ± 13.6 NL CH4 kg(-1) volatile solids (VS) with an overall average of 188 ± 17 NL CH4 kg(-1) VS during 11 successive start-up cycles (231 days) and a maximum CH4 production rate of 10.2 ± 0.6 NL CH4 kg(-1) VS day(-1). The inoculum-to-substrate (VS-based) ratio ranged from 4.06 to 4.47. Although methanogenesis proceeded fairly well the hydrolysis seemed to be the rate limiting step. It is possible start up psychrophilic dry anaerobic digestion of cow feces and wheat straw at feed TS of 35 % within 7-10 successive cycles (147-210 days).

Polygonal tundra geomorphological change in response to warming alters future CO2 and CH4 flux on the Barrow Peninsula

USGS Publications Warehouse

Lara, Mark J.; McGuire, A. David; Euskirchen, Eugénie S.; Tweedie, Craig E.; Hinkel, Kenneth M.; Skurikhin, Alexei N.; Romanovsky, Vladimir E.; Grosse, Guido; Bolton, W. Robert; Genet, Helene

2015-01-01

The landscape of the Barrow Peninsula in northern Alaska is thought to have formed over centuries to millennia, and is now dominated by ice-wedge polygonal tundra that spans drained thaw-lake basins and interstitial tundra. In nearby tundra regions, studies have identified a rapid increase in thermokarst formation (i.e., pits) over recent decades in response to climate warming, facilitating changes in polygonal tundra geomorphology. We assessed the future impact of 100 years of tundra geomorphic change on peak growing season carbon exchange in response to: (i) landscape succession associated with the thaw-lake cycle; and (ii) low, moderate, and extreme scenarios of thermokarst pit formation (10%, 30%, and 50%) reported for Alaskan arctic tundra sites. We developed a 30 × 30 m resolution tundra geomorphology map (overall accuracy:75%; Kappa:0.69) for our ~1800 km² study area composed of ten classes; drained slope, high center polygon, flat-center polygon, low center polygon, coalescent low center polygon, polygon trough, meadow, ponds, rivers, and lakes, to determine their spatial distribution across the Barrow Peninsula. Land-atmosphere CO2 and CH4 flux data were collected for the summers of 2006–2010 at eighty-two sites near Barrow, across the mapped classes. The developed geomorphic map was used for the regional assessment of carbon flux. Results indicate (i) at present during peak growing season on the Barrow Peninsula, CO2 uptake occurs at -902.3 106gC-CO2 day−1(uncertainty using 95% CI is between −438.3 and −1366 106gC-CO2 day−1) and CH4 flux at 28.9 106gC-CH4 day−1(uncertainty using 95% CI is between 12.9 and 44.9 106gC-CH4 day−1), (ii) one century of future landscape change associated with the thaw-lake cycle only slightly alter CO2 and CH4 exchange, while (iii) moderate increases in thermokarst pits would strengthen both CO2uptake (−166.9 106gC-CO2 day−1) and CH4 flux (2.8 106gC-CH4 day−1) with geomorphic change from low to high center polygons, cumulatively resulting in an estimated negative feedback to warming during peak growing season.

Programmatic Summary: Self-Regulating, Self-Pressurizing Tubules for Integrated Circulatory Systems

DTIC Science & Technology

2009-02-01

Conditions: (i) 3- aminopropyl silane; (ii) 2-furoyl chloride, Et3N, CH2Cl2, 0 C to RT, 24 h; (iii) Compound 2, THF, RT, 24 h.; and (iv) Toluene, reflux... aminopropyl )trimethoxy silane. Next, we treated the amino-terminated slides with a solution of 2-furoyl chloride to yield furan functionalized slides...Conditions: (i) 3- aminopropyl silane; (ii) 2-furoyl chloride, Et3N, CH2Cl2, 0 C to RT, 24 h; (iii) Compound 2, THF, RT, 24 h.; and (iv) Toluene, reflux

Rh(III)-Catalyzed Synthesis of N-Unprotected Indoles from Imidamides and Diazo Ketoesters via C-H Activation and C-C/C-N Bond Cleavage.

PubMed

Qi, Zisong; Yu, Songjie; Li, Xingwei

2016-02-19

The synthesis of N-unprotected indoles has been realized via Rh(III)-catalyzed C-H activation/annulation of imidamides with α-diazo β-ketoesters. The reaction occurs with the release of an amide coproduct, which originates from both the imidamide and the diazo as a result of C═N cleavage of the imidamide and C-C(acyl) cleavage of the diazo. A rhodacyclic intermediate has been isolated and a plausible mechanism has been proposed.

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

PubMed

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

2006-01-11

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

Mitigation of methane emissions in cities: How new measurements and partnerships can contribute to emissions reduction strategies

DOE PAGES

Hopkins, Francesca M.; Ehleringer, James R.; Bush, Susan E.; ...

2016-09-10

Cities generate 70% of anthropogenic greenhouse gas emissions, a fraction that is grow-ing with global urbanization. While cities play an important role in climate change mitigation, there has been little focus on reducing urban methane (CH4) emissions. Here, we develop a conceptual framework for CH 4 mitigation in cities by describing emission processes, the role of measurements, and a need for new institutional partnerships. Urban CH 4 emissions are likely to grow with expanding use of natural gas and organic waste disposal systems in growing population centers; however, we currently lack the ability to quantify this increase. We also lackmore » systematic knowledge of the relative contribution of these distinct source sectors on emissions. We present new observations from four North American cities to demonstrate that CH4 emissions vary in magnitude and sector from city to city and hence require different mitigation strategies. Detections of fugitive emissions from these systems suggest that current mitiga- tion approaches are absent or ineffective. These findings illustrate that tackling urban CH 4 emissions will require research efforts to identify mitigation targets, develop and implement new mitigation strategies, and monitor atmospheric CH 4 levels to ensure the success of mitigation efforts. This research will require a variety of techniques to achieve these objectives and should be deployed in cities globally. In conclusion, we suggest that metropolitan scale partnerships may effectively coordinate systematic measurements and actions focused on emission reduction goals.« less

Mitigation of methane emissions in cities: How new measurements and partnerships can contribute to emissions reduction strategies

NASA Astrophysics Data System (ADS)

Hopkins, Francesca M.; Ehleringer, James R.; Bush, Susan E.; Duren, Riley M.; Miller, Charles E.; Lai, Chun-Ta; Hsu, Ying-Kuang; Carranza, Valerie; Randerson, James T.

2016-09-01

Cities generate 70% of anthropogenic greenhouse gas emissions, a fraction that is growing with global urbanization. While cities play an important role in climate change mitigation, there has been little focus on reducing urban methane (CH4) emissions. Here, we develop a conceptual framework for CH4 mitigation in cities by describing emission processes, the role of measurements, and a need for new institutional partnerships. Urban CH4 emissions are likely to grow with expanding use of natural gas and organic waste disposal systems in growing population centers; however, we currently lack the ability to quantify this increase. We also lack systematic knowledge of the relative contribution of these distinct source sectors on emissions. We present new observations from four North American cities to demonstrate that CH4 emissions vary in magnitude and sector from city to city and hence require different mitigation strategies. Detections of fugitive emissions from these systems suggest that current mitigation approaches are absent or ineffective. These findings illustrate that tackling urban CH4 emissions will require research efforts to identify mitigation targets, develop and implement new mitigation strategies, and monitor atmospheric CH4 levels to ensure the success of mitigation efforts. This research will require a variety of techniques to achieve these objectives and should be deployed in cities globally. We suggest that metropolitan scale partnerships may effectively coordinate systematic measurements and actions focused on emission reduction goals.

Mitigation of methane emissions in cities: How new measurements and partnerships can contribute to emissions reduction strategies

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

Hopkins, Francesca M.; Ehleringer, James R.; Bush, Susan E.

Cities generate 70% of anthropogenic greenhouse gas emissions, a fraction that is grow-ing with global urbanization. While cities play an important role in climate change mitigation, there has been little focus on reducing urban methane (CH4) emissions. Here, we develop a conceptual framework for CH 4 mitigation in cities by describing emission processes, the role of measurements, and a need for new institutional partnerships. Urban CH 4 emissions are likely to grow with expanding use of natural gas and organic waste disposal systems in growing population centers; however, we currently lack the ability to quantify this increase. We also lackmore » systematic knowledge of the relative contribution of these distinct source sectors on emissions. We present new observations from four North American cities to demonstrate that CH4 emissions vary in magnitude and sector from city to city and hence require different mitigation strategies. Detections of fugitive emissions from these systems suggest that current mitiga- tion approaches are absent or ineffective. These findings illustrate that tackling urban CH 4 emissions will require research efforts to identify mitigation targets, develop and implement new mitigation strategies, and monitor atmospheric CH 4 levels to ensure the success of mitigation efforts. This research will require a variety of techniques to achieve these objectives and should be deployed in cities globally. In conclusion, we suggest that metropolitan scale partnerships may effectively coordinate systematic measurements and actions focused on emission reduction goals.« less

A family of acetato-diphenoxo triply bridged dimetallic Zn(II)Ln(III) complexes: SMM behavior and luminescent properties.

PubMed

Oyarzabal, Itziar; Artetxe, Beñat; Rodríguez-Diéguez, Antonio; García, JoséÁngel; Seco, José Manuel; Colacio, Enrique

2016-06-21

Eleven dimetallic Zn(II)-Ln(III) complexes of the general formula [Zn(µ-L)(µ-OAc)Ln(NO3)2]·CH3CN (Ln(III) = Pr (1), Nd (2), Sm (3), Eu (4), Gd (5), Tb (6), Dy (7), Ho (8), Er (9), Tm (10), Yb (11)) have been prepared in a one-pot reaction from the compartmental ligand N,N'-dimethyl-N,N'-bis(2-hydroxy-3-formyl-5-bromo-benzyl)ethylenediamine (H2L). In all these complexes, the Zn(II) ions occupy the internal N2O2 site whereas the Ln(III) ions show preference for the O4 external site. Both metallic ions are bridged by an acetate bridge, giving rise to triple mixed diphenoxido/acetate bridged Zn(II)Ln(III) compounds. The Nd, Dy, Er and Yb complexes exhibit field induced single-ion magnet (SIM) behaviour, with Ueff values ranging from 14.12 to 41.55 K. The Er complex shows two relaxation processes, but only the second relaxation process with an energy barrier of 21.0 K has been characterized. The chromophoric L(2-) ligand is able to act as an "antenna" group, sensitizing the near-infrared (NIR) Nd(III) and Yb(III)-based luminescence in complexes 2 and 11 and therefore, both compounds can be considered as magneto-luminescent materials. In addition, the Sm(III), Eu(III) and Tb(III) derivatives exhibit characteristic emissions in the visible region.

Diurnal Dynamics of Gaseous and Dissolved Metabolites and Microbiota Composition in the Bovine Rumen

PubMed Central

van Lingen, Henk J.; Edwards, Joan E.; Vaidya, Jueeli D.; van Gastelen, Sanne; Saccenti, Edoardo; van den Bogert, Bartholomeus; Bannink, André; Smidt, Hauke; Plugge, Caroline M.; Dijkstra, Jan

2017-01-01

Diurnal patterns of ruminal fermentation metabolites and microbial communities are not commonly assessed when investigating variation in ruminal CH4 production. The aims of this study were to monitor diurnal patterns of: (i) gaseous and dissolved metabolite concentrations in the bovine rumen, (ii) H2 and CH4 emitted, and (iii) the rumen microbiota. Furthermore, the effect of dietary inclusion of linseed oil on these patterns was assessed. Four rumen cannulated multiparous cows were used in a cross-over design with two 17 days periods and two dietary treatments: a control diet and a linseed oil supplemented diet [40% maize silage, 30% grass silage, 30% concentrate on dry matter (DM) basis for both diets; fat contents of 33 vs. 56 g/kg of DM]. On day 11, rumen contents were sampled for 10 h after morning feeding to profile gaseous and dissolved metabolite concentrations and microbiota composition. H2 and CH4 emission (mass per unit of time) was measured in respiration chambers from day 13 to 17. A 100-fold increase in ruminal H2 partial pressure (contribution to the total pressure of rumen headspace gases) was observed at 0.5 h after feeding. This peak was followed by a decline to basal level. Qualitatively similar patterns after feeding were also observed for H2 and CH4 emission, ethanol and lactate concentrations, and propionate molar proportion, although the opposite pattern was seen for acetate molar proportion. Associated with these patterns, a temporal biphasic change in the microbial composition was observed as based on 16S ribosomal RNA with certain taxa specifically associated with each phase. Bacterial concentrations (log10 16S ribosomal RNA gene copies based) were affected by time, and were increased by linseed oil supplementation. Archaeal concentrations (log10 16S ribosomal RNA gene copies based) tended to be affected by time and were not affected by diet, despite linseed oil supplementation decreasing CH4 emission, tending to decrease the partial pressure of CH4, and tending to increase propionate molar proportion. Linseed oil supplementation affected microbiota composition, and was most associated with an uncultivated Bacteroidales taxon. In summary, our findings support the importance of diurnal dynamics for the understanding of VFA, H2, and CH4 production. PMID:28367142

Structural evidence of [Rh(Thio) 6] 3+ and [Rh(Thio) 5Cl] 2+ cations in three novel ionic systems based on Co(III) dioximates

NASA Astrophysics Data System (ADS)

Bourosh, Paulina N.; Coropceanu, Eduard B.; Rija, Andrei P.; Bologa, Olga A.; Gdaniec, Maria; Bulhac, Ion I.

2011-07-01

Multicomponent mixed metal ionic-type dioximates, [Со(DH) 2(Thio) 2][Rh(Thio) 6][BF 4] 4 ( 1), [Со(DH) 2(Thio) 2][Rh(Thio) 6][TiF 6] 2·H 2O ( 2) and [Со(NioxH) 2(Thio) 2] 2[Rh(Thio) 5Cl][TiF 6] 2·CH 3OH·3H 2O ( 3), where DH 2 is dimethylglyoxime, NioxH 2 is 1.2-cyclohexanedionedioxime, and Thio is thiourea, were synthesized and their structures were determined by an X-ray method. Compounds 1-3 consist of two different mononuclear coordination cations with cobalt(III) and rhodium(III) as octahedrally coordinated metal centers and fluorine-containing anions as counterions. In the studied systems, Rh(III) mostly binds Thio ligands instead of dioximes, while a typical bis-dioximate in trans geometry is formed by Co(III) with two Thio ligands placed in axial positions. A structural characterization of coordination cations [Rh(Thio) 6] 3+ and [Rh(Thio) 5Cl] 2+ is given for the first time. The interactions and arrangement of the components in crystals 1-3 are discussed.

Direct C-H alkylation and indole formation of anilines with diazo compounds under rhodium catalysis.

PubMed

Mishra, Neeraj Kumar; Choi, Miji; Jo, Hyeim; Oh, Yongguk; Sharma, Satyasheel; Han, Sang Hoon; Jeong, Taejoo; Han, Sangil; Lee, Seok-Yong; Kim, In Su

2015-12-18

The rhodium(III)-catalyzed direct functionalization of aniline C-H bonds with α-diazo compounds is described. These transformations provide a facile construction of ortho-alkylated anilines with diazo malonates or highly substituted indoles with diazo acetoacetates.

Can Supported Reduced Vanadium Oxides form H2 from CH3OH? A Computational Gas-Phase Mechanistic Study.

PubMed

González-Navarrete, Patricio; Andrés, Juan; Calatayud, Monica

2018-02-01

A detailed density functional theory study is presented to clarify the mechanistic aspects of the methanol (CH 3 OH) dehydrogenation process to yield hydrogen (H 2 ) and formaldehyde (CH 2 O). A gas-phase vanadium oxide cluster is used as a model system to represent reduced V(III) oxides supported on TiO 2 catalyst. The theoretical results provide a complete scenario, involving several reaction pathways in which different methanol adsorption sites are considered, with presence of hydride and methoxide intermediates. Methanol dissociative adsorption process is both kinetically and thermodynamically feasible on V-O-Ti and V═O sites, and it might lead to form hydride species with interesting catalytic reactivity. The formation of H 2 and CH 2 O on reduced vanadium sites, V(III), is found to be more favorable than for oxidized vanadium species, V(V), taking place along energy barriers of 29.9 and 41.0 kcal/mol, respectively.

Antiviral Activity of Lambda Interferon in Chickens

PubMed Central

Reuter, Antje; Soubies, Sebastien; Härtle, Sonja; Schusser, Benjamin; Kaspers, Bernd

2014-01-01

Interferons (IFNs) are essential components of the antiviral defense system of vertebrates. In mammals, functional receptors for type III IFN (lambda interferon [IFN-λ]) are found mainly on epithelial cells, and IFN-λ was demonstrated to play a crucial role in limiting viral infections of mucosal surfaces. To determine whether IFN-λ plays a similar role in birds, we produced recombinant chicken IFN-λ (chIFN-λ) and we used the replication-competent retroviral RCAS vector system to generate mosaic-transgenic chicken embryos that constitutively express chIFN-λ. We could demonstrate that chIFN-λ markedly inhibited replication of various virus strains, including highly pathogenic influenza A viruses, in ovo and in vivo, as well as in epithelium-rich tissue and cell culture systems. In contrast, chicken fibroblasts responded poorly to chIFN-λ. When applied in vivo to 3-week-old chickens, recombinant chIFN-λ strongly induced the IFN-responsive Mx gene in epithelium-rich organs, such as lungs, tracheas, and intestinal tracts. Correspondingly, these organs were found to express high transcript levels of the putative chIFN-λ receptor alpha chain (chIL28RA) gene. Transfection of chicken fibroblasts with a chIL28RA expression construct rendered these cells responsive to chIFN-λ treatment, indicating that receptor expression determines cell type specificity of IFN-λ action in chickens. Surprisingly, mosaic-transgenic chickens perished soon after hatching, demonstrating a detrimental effect of constitutive chIFN-λ expression. Our data highlight fundamental similarities between the IFN-λ systems of mammals and birds and suggest that type III IFN might play a role in defending mucosal surfaces against viral intruders in most if not all vertebrates. PMID:24371053

The application of chiroptical spectroscopy (circular dichroism) in quantifying binding events in lanthanide directed synthesis of chiral luminescent self-assembly structures† †Electronic supplementary information (ESI) available. CCDC 999267–999270 and 1026036. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4sc02474e Click here for additional data file. Click here for additional data file.

PubMed Central

Blasco, Salvador; Twamley, Brendan; O'Brien, John; Peacock, Robert D.; Kitchen, Jonathan A.; Martínez-Calvo, Miguel

2015-01-01

The binding of asymmetrical and optically pure tridentate ligands (L = 1(S) and 1(R)) containing one carboxylic group and 2-naphthyl as an antenna to lanthanide ions (M = La(iii) and Eu(iii)) was studied in CH3CN, showing the successive formation of M:L, M:L2 and M:L3 stoichiometric species in solution. The europium complexes EuL3 were also synthesised, structurally characterised and their photophysical properties probed in CH3OH and CH3CN. The changes in the chiroptical properties of both 1(S) and 1(R) were used (by circular dichroism (CD) spectroscopy) to monitor the formation of these chiral self-assemblies in solution. While circularly polarised luminescence (CPL) showed the formation of Eu(1(S))3 and Eu(1(R))3 as enantiomers, with high luminescence dissymmetry factors (g lum), fitting the CD changes allowed for binding constants to be determined that were comparable to those seen in the analyses of absorbance and luminescence changes. PMID:28936303

Tuning anisotropy barriers in a family of tetrairon(III) single-molecule magnets with an S = 5 ground state.

PubMed

Accorsi, Stefania; Barra, Anne-Laure; Caneschi, Andrea; Chastanet, Guillaume; Cornia, Andrea; Fabretti, Antonio C; Gatteschi, Dante; Mortalo, Cecilia; Olivieri, Emiliano; Parenti, Francesca; Rosa, Patrick; Sessoli, Roberta; Sorace, Lorenzo; Wernsdorfer, Wolfgang; Zobbi, Laura

2006-04-12

Tetrairon(III) Single-Molecule Magnets (SMMs) with a propeller-like structure exhibit tuneable magnetic anisotropy barriers in both height and shape. The clusters [Fe4(L1)2(dpm)6] (1), [Fe4(L2)2(dpm)6] (2), [Fe4(L3)2(dpm)6].Et2O (3.Et2O), and [Fe4(OEt)3(L4)(dpm)6] (4) have been prepared by reaction of [Fe4(OMe)6(dpm)6] (5) with tripodal ligands R-C(CH2OH)3 (H3L1, R = Me; H3L2, R = CH2Br; H3L3, R = Ph; H3L4, R = tBu; Hdpm = dipivaloylmethane). The iron(III) ions exhibit a centered-triangular topology and are linked by six alkoxo bridges, which propagate antiferromagnetic interactions resulting in an S = 5 ground spin state. Single crystals of 4 reproducibly contain at least two geometric isomers. From high-frequency EPR studies, the axial zero-field splitting parameter (D) is invariably negative, as found in 5 (D = -0.21 cm(-1)) and amounts to -0.445 cm(-1) in 1, -0.432 cm(-1) in 2, -0.42 cm(-1) in 3.Et2O, and -0.27 cm(-1) in 4 (dominant isomer). The anisotropy barrier Ueff determined by AC magnetic susceptibility measurements is Ueff/kB = 17.0 K in 1, 16.6 K in 2, 15.6 K in 3.Et2O, 5.95 K in 4, and 3.5 K in 5. Both |D| and U(eff) are found to increase with increasing helical pitch of the Fe(O2Fe)3 core. The fourth-order longitudinal anisotropy parameter B4(0), which affects the shape of the anisotropy barrier, concomitantly changes from positive in 1 ("compressed parabola") to negative in 5 ("stretched parabola"). With the aid of spin Hamiltonian calculations the observed trends have been attributed to fine modulation of single-ion anisotropies induced by a change of helical pitch.

Clinical management and hospital outcomes of acute coronary syndrome patients in Mexico: The Third National Registry of Acute Coronary Syndromes (RENASICA III).

PubMed

Martinez-Sanchez, Carlos; Borrayo, Gabriela; Carrillo, Jorge; Juarez, Ursulo; Quintanilla, Juan; Jerjes-Sanchez, Carlos

2016-01-01

To describe current management and clinical outcomes in patients hospitalized with an acute coronary syndrome (ACS) in Mexico. RENASICA III was a prospective multicenter registry of consecutive patients hospitalized with an ACS. Patients had objective evidence of ischemic heart disease; those with type II infarction or secondary ischemic were excluded. Study design conformed to current quality recommendations. A total of 123 investigators at 29 tertiary and 44 community hospitals enrolled 8296 patients with an ACS (4038 with non-ST-elevation myocardial infarction/unstable angina [NSTEMI/UA], 4258 with ST-elevation myocardial infarction [STEMI]). The majority were younger (62±12years) and 76.0% were male. On admission 80.5% had ischemic chest pain lasting >20min and clinical stability. Left ventricular dysfunction was more frequent in NSTEMI/UA than in those with STEMI (30.0% vs. 10.7%, p<0.0001). In STEMI 37.6% received thrombolysis and 15.0% primary PCI. PCI was performed in 39.6% of NSTEMI/UA (early strategy in 10.8%, urgent strategy in 3.0%). Overall hospital death rate was 6.4% (8.7% in STEMI vs. 3.9% in NSTEMI/UA, p<0.001). The strongest independent predictors of hospital mortality were cardiogenic shock (odds ratio 22.4, 95% confidence interval 18.3-27.3) and ventricular fibrillation (odds ratio 12.5, 95% confidence interval 9.3-16.7). The results from RENASICA III establish the urgent need to develop large-scale regional programs to improve adherence to guideline recommendations in ACS, including rates of pharmacological thrombolysis and increasing the ratio of PCI to thrombolysis. Copyright © 2016 Instituto Nacional de Cardiología Ignacio Chávez. Publicado por Masson Doyma México S.A. All rights reserved.

Unimolecular Thermal Fragmentation of Ortho-Benzyne

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

Zhang, X.; Maccarone, A. T.; Nimlos, M. R.

2007-01-01

The ortho-benzyne diradical, o-C{sub 6}H{sub 4} has been produced with a supersonic nozzle and its subsequent thermal decomposition has been studied. As the temperature of the nozzle is increased, the benzyne molecule fragments: o-C{sub 6}H{sub 4} + {Delta} {yields} products. The thermal dissociation products were identified by three experimental methods: (i) time-of-flight photoionization mass spectrometry, (ii) matrix-isolation Fourier transform infrared absorption spectroscopy, and (iii) chemical ionization mass spectrometry. At the threshold dissociation temperature, o-benzyne cleanly decomposes into acetylene and diacetylene via an apparent retro-Diels-Alder process: o-C{sub 6}H{sub 4} + {Delta} {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH. The experimentalmore » {Delta}{sub rxn}H{sub 298}(o-C{sub 6}H{sub 4} {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH) is found to be 57 {+-} 3 kcal mol{sup -1}. Further experiments with the substituted benzyne, 3,6-(CH{sub 3}){sub 2}-o-C{sub 6}H{sub 2}, are consistent with a retro-Diels-Alder fragmentation. But at higher nozzle temperatures, the cracking pattern becomes more complicated. To interpret these experiments, the retro-Diels-Alder fragmentation of o-benzyne has been investigated by rigorous ab initio electronic structure computations. These calculations used basis sets as large as [C(7s6p5d4f3g2h1i)/H(6s5p4d3f2g1h)] (cc-pV6Z) and electron correlation treatments as extensive as full coupled cluster through triple excitations (CCSDT), in cases with a perturbative term for connected quadruples [CCSDT(Q)]. Focal point extrapolations of the computational data yield a 0 K barrier for the concerted, C{sub 2v}-symmetric decomposition of o-benzyne, E{sub b}(o-C{sub 6}H{sub 4} {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH) = 88.0 {+-} 0.5 kcal mol{sup -1}. A barrier of this magnitude is consistent with the experimental results. A careful assessment of the thermochemistry for the high temperature fragmentation of benzene is presented: C{sub 6}H{sub 6} {yields} H+[C{sub 6}H{sub 5}] {yields} H+[o-C{sub 6}H{sub 4}] {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH. Benzyne may be an important intermediate in the thermal decomposition of many alkylbenzenes (arenes). High engine temperatures above 1500 K may crack these alkylbenzenes to a mixture of alkyl radicals and phenyl radicals. The phenyl radicals will then dissociate first to benzyne and then to acetylene and diacetylene.« less

Unimolecular thermal fragmentation of ortho-benzene.

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

Zhang, X.; Maccarone, A. T.; Nimlos, M. R.

2007-01-01

The ortho-benzyne diradical, o-C{sub 6}H{sub 4} has been produced with a supersonic nozzle and its subsequent thermal decomposition has been studied. As the temperature of the nozzle is increased, the benzyne molecule fragments o-C{sub 6}H{sub 4}{sup +} {Delta} {yields} products. The thermal dissociation products were identified by three experimental methods: (i) time-of-flight photoionization mass spectrometry, (ii) matrix-isolation Fourier transform infrared absorption spectroscopy, and (iii) chemical ionization mass spectrometry. At the threshold dissociation temperature, o-benzyne cleanly decomposes into acetylene and diacetylene via an apparent retro-Diels-Alder process: o-C{sub 6}H{sub 4}{sup +}{Delta}{yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH. The experimental {Delta}{sub rxn}H{submore » 298}(o-C{sub 6}H{sub 4} {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH) is found to be 57 {+-} 3 kcal mol{sup -1}. Further experiments with the substituted benzyne, 3,6-(CH{sub 3}){sub 2}-o-C{sub 6}H{sub 2}, are consistent with a retro-Diels-Alder fragmentation. But at higher nozzle temperatures, the cracking pattern becomes more complicated. To interpret these experiments, the retro-Diels-Alder fragmentation of o-benzyne has been investigated by rigorous ab initio electronic structure computations. These calculations used basis sets as large as [C(7s6p5d4f3g2h1i)/H(6s5p4d3f2g1h)] (cc-pV6Z) and electron correlation treatments as extensive as full coupled cluster through triple excitations (CCSDT), in cases with a perturbative term for connected quadruples [CCSDT(Q)]. Focal point extrapolations of the computational data yield a 0 K barrier for the concerted, C{sub 2v}-symmetric decomposition of o-benzyne, E{sub b}(o-C{sub 6}H{sub 4} {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH) = 88.0 {+-} 0.5 kcal mol{sup -1}. A barrier of this magnitude is consistent with the experimental results. A careful assessment of the thermochemistry for the high temperature fragmentation of benzene is presented: C{sub 6}H{sub 6} {yields} H+[C{sub 6}H{sub 5}] {yields} H+[o-C{sub 6}H{sub 4}] {yields} HC {triple_bond} CH-HC {triple_bond} C-C {triple_bond} CH. Benzyne may be an important intermediate in the thermal decomposition of many alkylbenzenes (arenes). High engine temperatures above 1500 K may crack these alkylbenzenes to a mixture of alkyl radicals and phenyl radicals. The phenyl radicals will then dissociate first to benzyne and then to acetylene and diacetylene.« less

Single and double C-Cl-activation of methylene chloride by P,N-ligand coordinated rhodium complexes.

PubMed

Blank, Benoît; Glatz, Germund; Kempe, Rhett

2009-02-02

Two in one: The simultaneous formation of bimetallic mu-methylene bridged Rh(III) complexes as well as dimeric Rh(III) complexes with terminal chloromethyl groups is observed for P,N-ligand stabilized Rh(I) complexes by C-Cl bond activation of methylene chloride. A mechanistic proposal for the formation of both activation products is also discussed. The synthesis of Rh(I) complexes with P-functionalized aminopyridine ligands is reported as well as the first simultaneous observation of a single and double activation of C-Cl bonds of methylene chloride affording both a dimeric Rh(III) complex bearing terminal CH(2)Cl groups in addition to a binuclear Rh(III) complex with a bridging mu-CH(2) group. The structures of the oxidative addition products were obtained by X-ray diffraction studies and NMR experiments were performed to elucidate some aspects of the reaction pathway.

Stimulation of methane oxidation potential and effects on vegetation growth by bottom ash addition in a landfill final evapotranspiration cover.

PubMed

Kim, Gil Won; Ho, Adrian; Kim, Pil Joo; Kim, Sang Yoon

2016-09-01

The landfilling of municipal solid waste is a significant source of atmospheric methane (CH4), contributing up to 20% of total anthropogenic CH4 emissions. The evapotranspiration (ET) cover system, an alternative final cover system in waste landfills, has been considered to be a promising way to mitigate CH4 emissions, as well as to prevent water infiltration using vegetation on landfill cover soils. In our previous studies, bottom ash from coal-fired power plants was selected among several industrial residues (blast furnace slag, bottom ash, construction waste, steel manufacture slag, stone powder sludge, and waste gypsum) as the best additive for ET cover systems, with the highest mechanical performance achieved for a 35% (wtwt(-1)) bottom ash content in soil. In this study, to evaluate the field applicability of bottom ash mixed soil as ET cover, four sets of lysimeters (height 1.2m×width 2m×length 6m) were constructed in 2007, and four different treatments were installed: (i) soil+bottom ash (35% wtwt(-1)) (SB); (ii) soil+compost (2% wtwt(-1), approximately corresponding to 40Mgha(-1) in arable field scale) (SC); (iii) soil+bottom ash+compost (SBC); and (iv) soil only as the control (S). The effects of bottom ash mixing in ET cover soil on CH4 oxidation potential and vegetation growth were evaluated in a pilot ET cover system in the 5th year after installation by pilot experiments using the treatments. Our results showed that soil properties were significantly improved by bottom ash mixing, resulting in higher plant growth. Bottom ash addition significantly increased the CH4 oxidation potential of the ET cover soil, mainly due to improved organic matter and available copper concentration, enhancing methanotrophic abundances in soil amended with bottom ash. Conclusively, bottom ash could be a good alternative as a soil additive in the ET cover system to improve vegetation growth and mitigate CH4 emission impact in the waste landfill system. Copyright © 2016 Elsevier Ltd. All rights reserved.

Development of methane emission factors for enteric fermentation in cattle from Benin using IPCC Tier 2 methodology.

PubMed

Kouazounde, J B; Gbenou, J D; Babatounde, S; Srivastava, N; Eggleston, S H; Antwi, C; Baah, J; McAllister, T A

2015-03-01

The objective of this study was to develop emission factors (EF) for methane (CH4) emissions from enteric fermentation in cattle native to Benin. Information on livestock characteristics and diet practices specific to the Benin cattle population were gathered from a variety of sources and used to estimate EF according to Tier 2 methodology of the 2006 Intergovernmental Panel on Climate Change (IPCC) Guidelines for National Greenhouse Gas Inventories. Most cattle from Benin are Bos taurus represented by Borgou, Somba and Lagune breeds. They are mainly multi-purpose, being used for production of meat, milk, hides and draft power and grazed in open pastures and crop lands comprising tropical forages and crops. Estimated enteric CH4 EFs varied among cattle breeds and subcategory owing to differences in proportions of gross energy intake expended to meet maintenance, production and activity. EFs ranged from 15.0 to 43.6, 16.9 to 46.3 and 24.7 to 64.9 kg CH4/head per year for subcategories of Lagune, Somba and Borgou cattle, respectively. Average EFs for cattle breeds were 24.8, 29.5 and 40.2 kg CH4/head per year for Lagune, Somba and Borgou cattle, respectively. The national EF for cattle from Benin was 39.5 kg CH4/head per year. This estimated EF was 27.4% higher than the default EF suggested by IPCC for African cattle with the exception of dairy cattle. The outcome of the study underscores the importance of obtaining country-specific EF to estimate global enteric CH4 emissions.

Thermochemical and mechanistic studies of electrocatalytic hydrogen production by cobalt complexes containing pendant amines.

PubMed

Wiedner, Eric S; Appel, Aaron M; DuBois, Daniel L; Bullock, R Morris

2013-12-16

Two cobalt(tetraphosphine) complexes [Co(P(nC-PPh2)2N(Ph)2)(CH3CN)](BF4)2 with a tetradentate phosphine ligand (P(nC-PPh2)2N(Ph)2 = 1,5-diphenyl-3,7-bis((diphenylphosphino)alkyl)-1,5-diaza-3,7-diphosphacyclooctane; alkyl = (CH2)2, n = 2 (L2); (CH2)3, n = 3 (L3)) have been studied for electrocatalytic hydrogen production using 1:1 [(DMF)H](+):DMF. A turnover frequency (TOF) of 980 s(-1) with an overpotential at Ecat/2 of 1210 mV was measured for [Co(II)(L2)(CH3CN)](2+), and a TOF of 980 s(-1) with an overpotential at Ecat/2 of 930 mV was measured for [Co(II)(L3)(CH3CN)](2+). Addition of water increases the TOF of [Co(II)(L2)(CH3CN)](2+) to 18,000 s(-1). The catalytic wave for each of these complexes occurs at the reduction potential of the corresponding HCo(III) complex. Comprehensive thermochemical studies of [Co(II)(L2)(CH3CN)](2+) and [Co(II)(L3)(CH3CN)](2+) and species derived from them by addition/removal of protons/electrons were carried out using values measured experimentally and calculated using density functional theory (DFT). Notably, HCo(I)(L2) and HCo(I)(L3) were found to be remarkably strong hydride donors, with HCo(I)(L2) being a better hydride donor than BH4(-). Mechanistic studies of these catalysts reveal that H2 formation can occur by protonation of a HCo(II) intermediate, and that the pendant amines of these complexes facilitate proton delivery to the cobalt center. The rate-limiting step for catalysis is a net intramolecular isomerization of the protonated pendant amine from the nonproductive exoisomer to the productive endo isomer.

Electrical properties and Raman studies of phase transitions in ferroelectric [N(CH3)4]2CoCl2Br2

NASA Astrophysics Data System (ADS)

Ben Mohamed, C.; Karoui, K.; Bulou, A.; Ben Rhaiem, A.

2018-03-01

The present paper accounted for the synthesis, electric properties and vibrational spectroscopy of [N(CH3)4]2CoCl2Br2. The dielectric spectra were measured in the frequency range 10-1-105 Hz and temperature interval from 223 to 393 K. The dielectical properties confirm the ferroelectric-paraelectric phase transition at 290 K, which is reported by Abdallah Ben Rhaiem et al. (2013). The equivalent circuit based on the Z-View-software was proposed and the conduction mechanisms were determined. The obtained results have been discussed in terms of the correlated barrier hopping model (CBH) in phase I and non-overlapping small polaron tunneling model (NSPT) in phases II and III. Raman spectra as function temperature have been used to characterize the phase transitions and their nature, which indicates a change of the some peak near the transitions phase.

Effect of Alum Additions to Poultry Litter on In-House Ammonia and Greenhouse Gas Concentrations and Emissions.

PubMed

Eugene, Branly; Moore, Philip A; Li, Hong; Miles, Dana; Trabue, Steven; Burns, Robert; Buser, Michael

2015-09-01

Alum [Al(SO4) ·14HO] addition to poultry litter has been shown to reduce ammonia (NH) concentrations in poultry houses; however, its effects on greenhouse gas (GHG; NO, CH, and CO) emissions is unknown. The objectives of this study were to determine the effects of alum additions on (i) in-house NH and GHG concentrations, (ii) NH and GHG emissions, and (iii) litter chemical properties. Two identical broiler houses located in northwest Arkansas were used for this study: one house was a control and the other was treated with alum between each flock of birds. Ventilation rates were coupled with in-house NH and GHG measurements to determine emission rates. Overall, alum additions significantly reduced the daily average in-house NH concentration by 42% (8.9 vs. 15.4 μL L), and the overall NH emission rate was reduced by 47% (7.2 vs. 13.4 kg d house). The average cumulative NH emission for the three flocks was 330 kg house flock for the alum-treated house and 617 kg house flock for the control. Concentrations and emissions of nitrous oxide (NO) and methane (CH) from the alum-treated house were not significantly different than the untreated house. However, carbon dioxide (CO) emissions were significantly higher from the untreated house than the alum-treated house. Alum also significantly increased litter N content and reduced the C/N ratio. These results indicate that the addition of alum to poultry litter is not only an effective management practice for reducing in-house NH concentrations and emissions but also significantly reduces CO emissions from poultry facilities. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Formal oxidative addition of a C-H bond by a 16e iridium(i) complex involves metal-ligand cooperation.

PubMed

Kumar, Amit; Feller, Moran; Ben-David, Yehoshoa; Diskin-Posner, Yael; Milstein, David

2018-05-10

The first example of oxidative addition of a C-H bond to a square planar d8-Iridium complex, without any external additive, such as an acid, is described. Our mechanistic investigations show that metal-ligand cooperation through aromatization-dearomatization of the lutidine backbone is involved in this process, and that the actual C-H activation step occurs through an Ir(iii) intermediate.

Chemical reactions in the nitrogen-acetone ice induced by cosmic ray analogues: relevance for the Solar system

NASA Astrophysics Data System (ADS)

de Barros, A. L. F.; Andrade, D. P. P.; da Silveira, E. F.; Alcantara, K. F.; Boduch, P.; Rothard, H.

2018-02-01

The radiolysis of 10:1 nitrogen:acetone mixture, condensed at 11 K, by 40 MeV 58Ni11 + ions is studied. These results are representative of studies concerning Solar system objects, such as transneptunian objects, exposed to cosmic rays. Bombardment by cosmic rays triggers chemical reactions leading to synthesis of larger molecules. In this work, destruction cross-sections of acetone and nitrogen molecules in solid phase are determined and compared with those for pure acetone. The N2 column density decreases very fast indicating that, under irradiation, nitrogen leaves quickly a porous sample. The most abundant molecular species formed in the radiolysis are C3H6, C2H6, N3, CO, CH4 and CO2. Some N-bearing species are also formed, but with low production yield. Dissolving acetone in nitrogen decreases the formation cross-sections of CH4, CO2 and H2CO, while increases those for CO and C2H6 species. This fact may explain the presence of C2H6 in Pluto's surface where CH4 is not pure, but diluted in an N2 matrix. The formation of more complex molecules, such as HNCO and, possibly, glycine is observed, suggesting the formation of small prebiotic species in objects beyond Neptune from acetone diluted in a N2 matrix irradiated by cosmic rays.

Biogeochemical modeling of CO2 and CH4 production in anoxic Arctic soil microcosms

NASA Astrophysics Data System (ADS)

Tang, Guoping; Zheng, Jianqiu; Xu, Xiaofeng; Yang, Ziming; Graham, David E.; Gu, Baohua; Painter, Scott L.; Thornton, Peter E.

2016-09-01

Soil organic carbon turnover to CO2 and CH4 is sensitive to soil redox potential and pH conditions. However, land surface models do not consider redox and pH in the aqueous phase explicitly, thereby limiting their use for making predictions in anoxic environments. Using recent data from incubations of Arctic soils, we extend the Community Land Model with coupled carbon and nitrogen (CLM-CN) decomposition cascade to include simple organic substrate turnover, fermentation, Fe(III) reduction, and methanogenesis reactions, and assess the efficacy of various temperature and pH response functions. Incorporating the Windermere Humic Aqueous Model (WHAM) enables us to approximately describe the observed pH evolution without additional parameterization. Although Fe(III) reduction is normally assumed to compete with methanogenesis, the model predicts that Fe(III) reduction raises the pH from acidic to neutral, thereby reducing environmental stress to methanogens and accelerating methane production when substrates are not limiting. The equilibrium speciation predicts a substantial increase in CO2 solubility as pH increases, and taking into account CO2 adsorption to surface sites of metal oxides further decreases the predicted headspace gas-phase fraction at low pH. Without adequate representation of these speciation reactions, as well as the impacts of pH, temperature, and pressure, the CO2 production from closed microcosms can be substantially underestimated based on headspace CO2 measurements only. Our results demonstrate the efficacy of geochemical models for simulating soil biogeochemistry and provide predictive understanding and mechanistic representations that can be incorporated into land surface models to improve climate predictions.

Methane absorption in the visible spectra of the outer planets and Titan

NASA Technical Reports Server (NTRS)

Owen, T.; Cess, R. D.

1975-01-01

New spectra of Jupiter, Saturn, and Titan show weak methane bands in the region below 6000 A which have been known for many years in the spectra of Uranus and Neptune. Adopting the known abundance of methane on Jupiter, we have used a band model to determine CH4 abundances and broadening pressures for the other objects. The results indicate high values of the CH4 to H2 concentration ratio for Uranus and Neptune; for Titan, a surface pressure in excess of 1 atm is implied.

Comparative efficacy of photo-activated disinfection and calcium hydroxide for disinfection of remaining carious dentin in deep cavities: a clinical study

PubMed Central

Sharma, Sidhartha; Shah, Naseem

2014-01-01

Objectives To comparatively evaluate the efficacy of photo-activated disinfection (PAD), calcium hydroxide (CH) and their combination on the treatment outcome of indirect pulp treatment (IPT). Materials and Methods Institutional ethical clearance and informed consent of the patients were taken. The study was also registered with clinical registry of India. Sixty permanent molars exhibiting deep occlusal carious lesion in patients with the age range of 18 - 22 yr were included. Clinical and radiographic evaluation and set inclusion and exclusion criteria's were followed. Gross caries excavation was accomplished. In group I (n = 20) PAD was applied for sixty seconds. In group II (n = 20), CH was applied to the remaining carious dentin, while in group III (n = 20), PAD application was followed by CH placement. The teeth were permanently restored. They were clinically and radiographically followed-up at 45 day, 6 mon and 12 mon. Relative density of the remaining affected dentin was measured by 'Radiovisiography (RVG) densitometric' analysis. Results Successful outcome with an increase in radiographic grey values were observed in all three groups. However, on inter-group comparison, this change was not significant (p > 0.05). Conclusions PAD and CH both have equal disinfection efficacy in the treatment of deep carious dentin. PAD alone is as effective for treatment of deep carious lesion as calcium hydroxide and hence can be used as an alternative to CH. They can be used independently in IPT, since combining both does not offer any additional therapeutic benefits. PMID:25110643

Rh2(II,III) Catalysts with Chelating Carboxylate and Carboxamidate Supports: Electronic Structure and Nitrene Transfer Reactivity.

PubMed

Varela-Álvarez, Adrián; Yang, Tzuhsiung; Jennings, Heather; Kornecki, Katherine P; Macmillan, Samantha N; Lancaster, Kyle M; Mack, James B C; Du Bois, J; Berry, John F; Musaev, Djamaladdin G

2016-02-24

Dirhodium-catalyzed C-H amination is hypothesized to proceed via Rh2-nitrene intermediates in either the Rh2(II,II) or Rh2(II,III) redox state. Herein, we report joint theoretical and experimental studies of the ground electronic state (GES), redox potentials, and C-H amination of [Rh2(II,III)(O2CCH3)4(L)n](+) (1_L) (L = none, Cl(-), and H2O), [Rh2(esp)2](+) (2), and Rh2(espn)2Cl (3) (esp = α,α,α',α'-tetramethyl-1,3-benzenedipropanoate and espn = α,α,α',α'-tetramethyl-1,3-benzenedipropanamidate). CASSCF calculations on 1_L yield a wave function with two closely weighted configurations, (δ*)(2)(π1*)(2)(π2*)(1) and (δ*)(2)(π1*)(1)(π2*)(2), consistent with reported EPR g values [Chem. Phys. Lett. 1986, 130, 20-23]. In contrast, EPR spectra of 2 show g values consistent with the DFT-computed (π*)(4)(δ*)(1) GES. EPR spectra and Cl K-edge XAS for 3 are consistent with a (π*)(4)(δ*)(1) GES, as supported by DFT. Nitrene intermediates 2N_L and 3N_L are also examined by DFT (the nitrene is an NSO3R species). DFT calculations suggest a doublet GES for 2N_L and a quartet GES for 3N_L. CASSCF calculations describe the GES of 2N as Rh2(II,II) with a coordinated nitrene radical cation, (π*)(4)(δ*)(2)(π(nitrene,1))(1)(π(nitrene,2))(0). Conversely, the GES of 3N is Rh2(II,III) with a coordinated triplet nitrene, (π*)(4)(δ*)(1)(π(nitrene,1))(1)(π(nitrene,2))(1). Quartet transition states ((4)TSs) are found to react via a stepwise radical mechanism, whereas (2)TSs are found to react via a concerted mechanism that is lower in energy compared to (4)TSs for both 2N_L and 3N_L. The experimental (determined by intramolecular competition) and (2)TS-calculated kinetic isotopic effect (KIE) shows a KIE ∼ 3 for both 2N and 3N, which is consistent with a concerted mechanism.

Saturation kinetics in phenolic O-H bond oxidation by a mononuclear Mn(III)-OH complex derived from dioxygen.

PubMed

Wijeratne, Gayan B; Corzine, Briana; Day, Victor W; Jackson, Timothy A

2014-07-21

The mononuclear hydroxomanganese(III) complex, [Mn(III)(OH)(dpaq)](+), which is supported by the amide-containing N5 ligand dpaq (dpaq = 2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate) was generated by treatment of the manganese(II) species, [Mn(II)(dpaq)](OTf), with dioxygen in acetonitrile solution at 25 °C. This oxygenation reaction proceeds with essentially quantitative yield (greater than 98% isolated yield) and represents a rare example of an O2-mediated oxidation of a manganese(II) complex to generate a single product. The X-ray diffraction structure of [Mn(III)(OH)(dpaq)](+) reveals a short Mn-OH distance of 1.806(13) Å, with the hydroxo moiety trans to the amide function of the dpaq ligand. No shielding of the hydroxo group is observed in the solid-state structure. Nonetheless, [Mn(III)(OH)(dpaq)](+) is remarkably stable, decreasing in concentration by only 10% when stored in MeCN at 25 °C for 1 week. The [Mn(III)(OH)(dpaq)](+) complex participates in proton-coupled electron transfer reactions with substrates with relatively weak O-H and C-H bonds. For example, [Mn(III)(OH)(dpaq)](+) oxidizes TEMPOH (TEMPOH = 2,2'-6,6'-tetramethylpiperidine-1-ol), which has a bond dissociation free energy (BDFE) of 66.5 kcal/mol, in MeCN at 25 °C. The hydrogen/deuterium kinetic isotope effect of 1.8 observed for this reaction implies a concerted proton-electron transfer pathway. The [Mn(III)(OH)(dpaq)](+) complex also oxidizes xanthene (C-H BDFE of 73.3 kcal/mol in dimethylsulfoxide) and phenols, such as 2,4,6-tri-t-butylphenol, with BDFEs of less than 79 kcal/mol. Saturation kinetics were observed for phenol oxidation, implying an initial equilibrium prior to the rate-determining step. On the basis of a collective body of evidence, the equilibrium step is attributed to the formation of a hydrogen-bonding complex between [Mn(III)(OH)(dpaq)](+) and the phenol substrates.

General synthesis of (salen)ruthenium(III) complexes via N...N coupling of (salen)ruthenium(VI) nitrides.

PubMed

Man, Wai-Lun; Kwong, Hoi-Ki; Lam, William W Y; Xiang, Jing; Wong, Tsz-Wing; Lam, Wing-Hong; Wong, Wing-Tak; Peng, Shie-Ming; Lau, Tai-Chu

2008-07-07

Reaction of [Ru (VI)(N)(L (1))(MeOH)] (+) (L (1) = N, N'-bis(salicylidene)- o-cyclohexylenediamine dianion) with excess pyridine in CH 3CN produces [Ru (III)(L (1))(py) 2] (+) and N 2. The proposed mechanism involves initial equilibrium formation of [Ru (VI)(N)(L (1))(py)] (+), which undergoes rapid N...N coupling to produce [(py)(L (1))Ru (III) N N-Ru (III)(L (1))(py)] (2+); this is followed by pyridine substituion to give the final product. This ligand-induced N...N coupling of Ru (VI)N is utilized in the preparation of a series of new ruthenium(III) salen complexes, [Ru (III)(L)(X) 2] (+/-) (L = salen ligand; X = H 2O, 1-MeIm, py, Me 2SO, PhNH 2, ( t )BuNH 2, Cl (-) or CN (-)). The structures of [Ru (III)(L (1))(NH 2Ph) 2](PF 6) ( 6), K[Ru (III)(L (1))(CN) 2] ( 9), [Ru (III)(L (2))(NCCH 3) 2][Au (I)(CN) 2] ( 11) (L (2) = N, N'-bis(salicylidene)- o-phenylenediamine dianion) and [N ( n )Bu 4][Ru (III)(L (3))Cl 2] ( 12) (L (3) = N, N'-bis(salicylidene)ethylenediamine dianion) have been determined by X-ray crystallography.

Mechanistic Studies of Cobalt-Catalyzed C(sp2)-H Borylation of Five-Membered Heteroarenes with Pinacolborane.

PubMed

Obligacion, Jennifer V; Chirik, Paul J

2017-07-07

Studies into the mechanism of cobalt-catalyzed C(sp 2 )-H borylation of five-membered heteroarenes with pinacolborane (HBPin) as the boron source established the catalyst resting state as the trans -cobalt(III) dihydride boryl, ( iPr PNP)Co(H) 2 (BPin) ( iPr PNP = 2,6-( i Pr 2 PCH 2 ) 2 (C 5 H 3 N)), at both low and high substrate conversions. The overall first-order rate law and observation of a normal deuterium kinetic isotope effect on the borylation of benzofuran versus benzofuran-2- d 1 support H 2 reductive elimination from the cobalt(III) dihydride boryl as the turnover-limiting step. These findings stand in contrast to that established previously for the borylation of 2,6-lutidine with the same cobalt precatalyst, where borylation of the 4-position of the pincer occurred faster than the substrate turnover and arene C-H activation by a cobalt(I) boryl is turnover-limiting. Evaluation of the catalytic activity of different cobalt precursors in the C-H borylation of benzofuran with HBPin established that the ligand design principles for C- H borylation depend on the identities of both the arene and the boron reagent used: electron-donating groups improve catalytic activity of the borylation of pyridines and arenes with B 2 Pin 2 , whereas electron-withdrawing groups improve catalytic activity of the borylation of five-membered heteroarenes with HBPin. Catalyst deactivation by P-C bond cleavage from a cobalt(I) hydride was observed in the C-H borylation of arene substrates with C-H bonds that are less acidic than those of five-membered heteroarenes using HBPin and explains the requirement of B 2 Pin 2 to achieve synthetically useful yields with these arene substrates.

Context-dependent activation of Wnt signaling by tumor suppressor RUNX3 in gastric cancer cells

PubMed Central

Ju, Xiaoli; Ishikawa, Tomo-o; Naka, Kazuhito; Ito, Kosei; Ito, Yoshiaki; Oshima, Masanobu

2014-01-01

RUNX3 is a tumor suppressor for a variety of cancers. RUNX3 suppresses the canonical Wnt signaling pathway by binding to the TCF4/β-catenin complex, resulting in the inhibition of binding of the complex to the Wnt target gene promoter. Here, we confirmed that RUNX3 suppressed Wnt signaling activity in several gastric cancer cell lines; however, we found that RUNX3 increased the Wnt signaling activity in KatoIII and SNU668 gastric cancer cells. Notably, RUNX3 expression increased the ratio of the Wnt signaling-high population in the KatoIII cells. although the maximum Wnt activation level of individual cells was similar to that in the control. As found previously, RUNX3 also binds to TCF4 and β-catenin in KatoIII cells, suggesting that these molecules form a ternary complex. Moreover, the ChIP analyses revealed that TCF4, β-catenin and RUNX3 bind the promoter region of the Wnt target genes, Axin2 and c-Myc, and the occupancy of TCF4 and β-catenin in these promoter regions is increased by the RUNX3 expression. These results suggest that RUNX3 stabilizes the TCF4/β-catenin complex on the Wnt target gene promoter in KatoIII cells, leading to activation of Wnt signaling. Although RUNX3 increased the Wnt signaling activity, its expression resulted in suppression of tumorigenesis of KatoIII cells, indicating that RUNX3 plays a tumor-suppressing role in KatoIII cells through a Wnt-independent mechanism. These results indicate that RUNX3 can either suppress or activate the Wnt signaling pathway through its binding to the TCF4/β-catenin complex by cell context-dependent mechanisms. PMID:24447505

Reactivity of a Cobalt(III)–Hydroperoxo Complex in Electrophilic Reactions

DOE PAGES

Shin, Bongki; Sutherlin, Kyle D.; Ohta, Takehiro; ...

2016-11-15

The reactivity of mononuclear metal-hydroperoxo adducts has fascinated researchers in many areas due to their diverse biological and catalytic processes. In this study, a mononuclear cobalt(III)-peroxo complex bearing a tetradentate macrocyclic ligand, [Co III(Me 3-TPADP)(O 2)] + (Me 3-TPADP = 3,6,9-trimethyl-3,6,9-triaza-1(2,6)-pyridinacyclodecaphane), was prepared by reacting [Co II(Me 3-TPADP)(CH 3CN) 2] 2+ with H 2O 2 in the presence of triethylamine. Upon protonation, the cobalt(III)- peroxo intermediate was converted into a cobalt(III)-hydroperoxo complex, [Co III(Me 3-TPADP)(O 2H)(CH 3CN)] 2+. The mononuclear cobalt(III)-peroxo and -hydroperoxo intermediates were characterized by a variety of physicochemical methods. Results of electrospray ionization mass spectrometry clearly showmore » the transformation of the intermediates: the peak at m/z 339.2 assignable to the cobalt(III)-peroxo species disappears with concomitant growth of the peak at m/z 190.7 corresponding to the cobalt(III)-hydroperoxo complex (with bound CH 3CN). Isotope labeling experiments further support the existence of the cobalt(III)-peroxo and -hydroperoxo complexes. In particular, the O-O bond stretching frequency of the cobalt(III)-hydroperoxo complex was determined to be 851 cm -1 for 16O 2H samples (803 cm -1 for 18O 2H samples) and its Co-O vibrational energy was observed at 571 cm -1 for 16O 2H samples (551 cm -1 for 18O 2H samples; 568 cm -1 for 16O 2 2H samples) by resonance Raman spectroscopy. Reactivity studies performed with the cobalt(III)-peroxo and -hydroperoxo complexes in organic functionalizations reveal that the latter is capable of conducting oxygen atom transfer with an electrophilic character, whereas the former exhibits no oxygen atom transfer reactivity under the same reaction conditions. Alternatively, the cobalt(III)-hydroperoxo complex does not perform hydrogen atom transfer reactions, while analogous low-spin Fe(III)-hydroperoxo complexes are capable of this reactivity. Density function theory calculations indicate that this lack of reactivity is due to the high free energy cost of O-O bond homolysis that would be required to produce the hypothetical Co(IV)-oxo product.« less

Reactivity of a Cobalt(III)–Hydroperoxo Complex in Electrophilic Reactions

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

Shin, Bongki; Sutherlin, Kyle D.; Ohta, Takehiro

The reactivity of mononuclear metal-hydroperoxo adducts has fascinated researchers in many areas due to their diverse biological and catalytic processes. In this study, a mononuclear cobalt(III)-peroxo complex bearing a tetradentate macrocyclic ligand, [Co III(Me 3-TPADP)(O 2)] + (Me 3-TPADP = 3,6,9-trimethyl-3,6,9-triaza-1(2,6)-pyridinacyclodecaphane), was prepared by reacting [Co II(Me 3-TPADP)(CH 3CN) 2] 2+ with H 2O 2 in the presence of triethylamine. Upon protonation, the cobalt(III)- peroxo intermediate was converted into a cobalt(III)-hydroperoxo complex, [Co III(Me 3-TPADP)(O 2H)(CH 3CN)] 2+. The mononuclear cobalt(III)-peroxo and -hydroperoxo intermediates were characterized by a variety of physicochemical methods. Results of electrospray ionization mass spectrometry clearly showmore » the transformation of the intermediates: the peak at m/z 339.2 assignable to the cobalt(III)-peroxo species disappears with concomitant growth of the peak at m/z 190.7 corresponding to the cobalt(III)-hydroperoxo complex (with bound CH 3CN). Isotope labeling experiments further support the existence of the cobalt(III)-peroxo and -hydroperoxo complexes. In particular, the O-O bond stretching frequency of the cobalt(III)-hydroperoxo complex was determined to be 851 cm -1 for 16O 2H samples (803 cm -1 for 18O 2H samples) and its Co-O vibrational energy was observed at 571 cm -1 for 16O 2H samples (551 cm -1 for 18O 2H samples; 568 cm -1 for 16O 2 2H samples) by resonance Raman spectroscopy. Reactivity studies performed with the cobalt(III)-peroxo and -hydroperoxo complexes in organic functionalizations reveal that the latter is capable of conducting oxygen atom transfer with an electrophilic character, whereas the former exhibits no oxygen atom transfer reactivity under the same reaction conditions. Alternatively, the cobalt(III)-hydroperoxo complex does not perform hydrogen atom transfer reactions, while analogous low-spin Fe(III)-hydroperoxo complexes are capable of this reactivity. Density function theory calculations indicate that this lack of reactivity is due to the high free energy cost of O-O bond homolysis that would be required to produce the hypothetical Co(IV)-oxo product.« less

Antibacterial activity and spectral studies of trivalent chromium, manganese, iron macrocyclic complexes derived from oxalyldihydrazide and glyoxal.

PubMed

Singh, D P; Kumar, Ramesh; Singh, Jitender

2009-06-01

A new series of complexes is synthesized by template condensation of oxalyldihydrazide and glyoxal in methanolic medium in the presence of trivalent chromium, manganese and iron salts forming complexes of the type: [M(C(8)H(8)N(8)O(4))X]X(2) where M = Cr(III), Mn(III), Fe(III) and X = Cl(-1), NO(-1)(3), CH(3)COO(-1). The complexes have been characterized with the help of elemental analyses, conductance measurements, magnetic susceptibility measurements, electronic, NMR, infrared and far infrared spectral studies. On the basis of these studies, a five coordinate square pyramidal geometry for these complexes has been proposed. The biological activities of the metal complexes were tested in vitro against a number of pathogenic bacteria and some of the complexes exhibited remarkable antibacterial activities.

Systematic syntheses and metalloligand doping of flexible porous coordination polymers composed of a Co(III)-metalloligand.

PubMed

Kobayashi, Atsushi; Suzuki, Yui; Ohba, Tadashi; Ogawa, Tomohiro; Matsumoto, Takeshi; Noro, Shin-ichiro; Chang, Ho-Chol; Kato, Masako

2015-03-16

A series of flexible porous coordination polymers (PCPs) RE-Co, composed of a Co(III)-metalloligand [Co(dcbpy)3](3-) (Co; H2dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) and lanthanide cations (RE(3+) = La(3+), Ce(3+), Pr(3+), Nd(3+), Sm(3+), Eu(3+), Gd(3+), Tb(3+), Er(3+)), was systematically synthesized. X-ray crystallographic analysis revealed that the six carboxylates at the top of each coordination octahedron of Co(III)-metalloligand were commonly bound to RE(3+) cations to form a rock-salt-type porous coordination framework. When RE-Co contains a smaller and heavier RE(3+) cation than Nd(3+), the RE-Co crystallized in the cubic Fm-3m space group, whereas the other three RE-Co with larger RE(3+) crystallized in the lower symmetrical orthorhombic Fddd space group, owing to the asymmetric 10-coordinated bicapped square antiprism structure of the larger RE(3+) cation. Powder X-ray diffraction and vapor-adsorption isotherm measurements revealed that all synthesized RE-Co PCPs show reversible amorphous-crystalline transitions, triggered by water-vapor-adsorption/desorption. This transition behavior strongly depends on the kind of RE(3+); the transition of orthorhombic RE-Co was hardly observed under exposure to CH3OH vapor, but the RE-Co with smaller cations such as Gd(3+) showed the transition under exposure to CH3OH vapors. Further tuning of vapor-adsorption property was examined by doping of Ru(II)-metalloligands, [Ru(dcbpy)3](4-), [Ru(dcbpy)2Cl2](4-), [Ru(dcbpy)(tpy)Cl](-), and [Ru(dcbpy)(dctpy)](3-) (abbreviated as RuA, RuB, RuC, and RuD, respectively; tpy = 2,2':6',2″-terpyridine, H2dctpy = 4,4″-dicarboxy-2,2':6',2″-terpyridine), into the Co(III)-metalloligand site of Gd-Co to form the Ru(II)-doped PCP RuX@Gd-Co (X = A, B, C, or D). Three Ru(II)-metalloligands, RuA, RuB, and RuD dopants, were found to be uniformly incorporated into the Gd-Co framework by replacing the original Co(III)-metalloligand, whereas the doping of RuC failed probably because of the less number of coordination sites. In addition, we found that the RuA doping into the Gd-Co PCP had a large effect on vapor-adsorption due to the electrostatic interaction originating from the negatively charged RuA sites in the framework and the charge-compensating Li(+) cations in the porous channel.

Testing For Ecological Correlations between Greenhouse Gas ...

EPA Pesticide Factsheets

The role of coastal wetlands in ameliorating the plight of climate change is well documented. Per unit area, coastal wetlands are among the largest natural carbon sinks, taking up abundant carbon dioxide (CO2) and emitting minimal methane (CH4). While the role of coastal marsh vegetation in mediating CO2 and CH4 flux dynamics has been well-studied, less is known about effects that other biotic drivers, including marsh invertebrates, exert on GHG fluxes. Crabs and mollusks may directly alter soil biogeochemistry and GHG fluxes by bioturbation and deposition of nutrient-rich feces, and indirectly through impacts to vegetation. The objective of this research was to survey GHG fluxes along a gradient of fiddler crab (Uca pugnax) and ribbed mussel (Geukensia demissa) densities. Surveys were performed in a Rhode Island salt marsh at randomly-chosen points in both the Spartina alterniflora-vegetated low marsh and the unvegetated creek bank. During the peak growing season, GHG (CO2 and CH4) fluxes and S. alterniflora, live and dead mussel, and crab burrow densities were measured. GHG fluxes differed substantially between the S. alterniflora marsh and creek bank, with greater CO2 uptake and CH4 emission in the S. alterniflora marsh than along the creek bank. In the S. alterniflora marsh, Spearman’s Correlation Analysis revealed a significant positive correlation between density of dead mussels and CH4 emission. However, none of the measured variables correlat

Effects of tillage and nitrogen fertilizers on CH4 and CO2 emissions and soil organic carbon in paddy fields of central China.

PubMed

Cheng-Fang, Li; Dan-Na, Zhou; Zhi-Kui, Kou; Zhi-Sheng, Zhang; Jin-Ping, Wang; Ming-Li, Cai; Cou-Gui, Cao

2012-01-01

Quantifying carbon (C) sequestration in paddy soils is necessary to help better understand the effect of agricultural practices on the C cycle. The objective of the present study was to assess the effects of tillage practices [conventional tillage (CT) and no-tillage (NT)] and the application of nitrogen (N) fertilizer (0 and 210 kg N ha(-1)) on fluxes of CH(4) and CO(2), and soil organic C (SOC) sequestration during the 2009 and 2010 rice growing seasons in central China. Application of N fertilizer significantly increased CH(4) emissions by 13%-66% and SOC by 21%-94% irrespective of soil sampling depths, but had no effect on CO(2) emissions in either year. Tillage significantly affected CH(4) and CO(2) emissions, where NT significantly decreased CH(4) emissions by 10%-36% but increased CO(2) emissions by 22%-40% in both years. The effects of tillage on the SOC varied with the depth of soil sampling. NT significantly increased the SOC by 7%-48% in the 0-5 cm layer compared with CT. However, there was no significant difference in the SOC between NT and CT across the entire 0-20 cm layer. Hence, our results suggest that the potential of SOC sequestration in NT paddy fields may be overestimated in central China if only surface soil samples are considered.

Correction of Quenching Errors in Analytical Fluorimetry through Use of Time Resolution.

DTIC Science & Technology

1980-05-27

QUENCHING ERRORS IN ANALYTICAL FLUORIMETRY THROUGH USE OF TIME RESOLUTION by Gary M. Hieftje and Gilbert R. Haugen Prepared for Publication in... HIEFTJE , 6 R HAUGEN NOCOIT1-6-0638 UCLASSIFIED TR-25 NL ///I//II IIIII I__I. 111122 Z .. ..12 1.~l8 .2 -4 SECuRITY CLSIIAI1 orTI PAGE MWhno. ee...in Analytical and Clinical Chemistry, vol. 3, D. M. Hercules, G. M. Hieftje , L. R. Snyder, and M4. A. Evenson, eds., Plenum Press, N.Y., 1978, ch. S

Species-Specific Involvement of Integrin αIIbβ3 in a Monoclonal Antibody CH12 Triggers Off-Target Thrombocytopenia in Cynomolgus Monkeys.

PubMed

Zhang, Yiting; Sun, Jianhua; Tan, Minjia; Liu, Yongzhen; Li, Qian; Jiang, Hua; Wang, Huamao; Li, Zonghai; Wan, Wei; Jiang, Hualiang; Lu, Henglei; Wang, Bingshun; Ren, Jin; Gong, Likun

2018-04-07

CH12 is a novel humanized monoclonal antibody against epidermal growth factor receptor variant III (EGFRvIII) for cancer treatment. Unfortunately, in pre-clinical safety evaluation studies, acute thrombocytopenia was observed after administration of CH12 in cynomolgus monkeys, but not rats. More importantly, in vitro experiments found that CH12 can bind and activate platelets in cynomolgus monkey, but not human peripheral blood samples. Cynomolgus monkey-specific thrombocytopenia has been reported previously; however, the underlying mechanism remains unclear. Here, we first showed that CH12 induced thrombocytopenia in cynomolgus monkeys through off-target platelet binding and activation, resulting in platelet destruction. We subsequently found that integrin αIIbβ3 (which is expressed on platelets) contributed to this off-target toxicity. Furthermore, three-dimensional structural modeling of the αIIbβ3 molecules in cynomolgus monkeys, humans, and rats suggested that an additional unique loop exists in the ligand-binding pocket of the αIIb subunit in cynomolgus monkeys, which may explain why CH12 binds to platelets only in cynomolgus monkeys. Moreover, this study supported the hypothesis that the minor differences between cynomolgus monkeys and humans can confuse human risk assessments and suggests that species differences can help the prediction of human risks and avoid losses in drug development. Copyright © 2018. Published by Elsevier Inc.

[Raman Characterization of Hydrate Crystal Structure Influenced by Mine Gas Concentration].

PubMed

Zhang, Bao-yong; Zhou, Hong-ji; Wu, Qiang; Gao, Xia

2016-01-01

CH4 /C2H6/N2 mixed hydrate formation experiments were performed at 2 degrees C and 5 MPa for three different mine gas concentrations (CH4/C2H6/N2, G1 = 54 : 36 : 10, G2 = 67.5 : 22.5 : 10, G3 = 81 : 9 : 10). Raman spectra for hydration products were obtained by using Microscopic Raman Spectrometer. Hydrate structure is determined by the Raman shift of symmetric C-C stretching vibration mode of C2H6 in the hydrate phase. This work is focused on the cage occupancies and hydration numbers, calculated by the fitting methods of Raman peaks. The results show that structure I (s I) hydrate forms in the G1 and G2 gas systems, while structure II (s II) hydrate forms in the G3 gas system, concentration variation of C2H6 in the gas samples leads to a change in hydrate structure from s I to s II; the percentages of CH4 and C2H6 in s I hydrate phase are less affected by the concentration of gas samples, the percentages of CH4 are respectively 34.4% and 35.7%, C2H6 are respectively 64.6% and 63.9% for gas systems of G1 and G2, the percentages of CH4 and 2 H6 are respectively 73.5% and 22.8% for gas systems of G3, the proportions of object molecules largely depend on the hydrate structure; CH4 and C2H6 molecules occupy 98%, 98% and 92% of the large cages and CH4 molecules occupy 80%, 60% and 84% of the small cages for gas systems of G1, G2 and G3, respectively; additionally, N2 molecules occupy less than 5% of the small cages is due to its weak adsorption ability and the lower partial pressure.

Supplementation with whole cottonseed causes long-term reduction of methane emissions from lactating dairy cows offered a forage and cereal grain diet.

PubMed

Grainger, C; Williams, R; Clarke, T; Wright, A-D G; Eckard, R J

2010-06-01

The objective of our work was to supplement a forage and cereal diet of lactating dairy cows with whole cottonseed (WCS) for 12 wk and to determine whether the expected reduction in CH(4) would persist. A secondary objective was to determine the effect of supplementing the diet with WCS on milk yield and rumen function over the 12-wk feeding period. Fifty lactating cows were randomly allocated to 1 of 2 diets (control or WCS). The 2 separate groups were each offered, on average, 4.2 kg of DM/cow per day of alfalfa hay (a.m.) and 6.6 kg of DM/cow per day of ryegrass silage (p.m.) on the ground in bare paddocks each day for 12 wk. Cows in each group were also individually offered dietary supplements for 12 wk in a feed trough at milking times of 5.4 kg of DM/cow per day of cracked wheat grain and 0.5 kg of DM/cow per day of cottonseed meal (control) or 2.8 kg of DM/cow per day of cracked wheat grain and 2.61 kg of DM/cow per day of WCS. The 2 diets were formulated to be similar in their concentrations of CP and ME, but the WCS diet was designed to have a higher fat concentration. Samples of rumen fluid were collected per fistula from the rumen approximately 4 h after grain feeding in the morning. Samples were taken from 8 cows (4 cows/diet) on 2 consecutive days in wk 2 of the covariate and wk 3, 6, 10, and 12 of treatment and analyzed for volatile fatty acids, ammonia-N, methanogens, and protozoa. The reduction in CH(4) emissions (g/d) because of WCS supplementation increased from 13% in wk 3 to 23% in wk 12 of treatment. Similarly, the reduction in CH(4) emissions (g/kg of DMI) increased from 5.1% in wk 3 to 14.5% in wk 12 of treatment. It was calculated that the average reduction in CH(4) emissions over the 12-wk period was 2.9% less CH(4) per 1% added fat, increasing from 1.5% in wk 3 to 4.4% less CH(4) in wk 12. There was no effect of WCS supplementation on rumen ammonia-N, rumen volatile fatty acids, rumen methanogens, and rumen protozoa. On average over the 12-wk period, supplementation with WCS decreased the yield of milk (10%), fat (11%), protein (14%), lactose (11%), and fat plus protein (12%) and BW gain (31%). The WCS supplementation had no effect on milk fat concentration but resulted in a decrease in concentration of protein (5%) and lactose (11%). The major finding from this study is that addition of WCS to the diet of lactating dairy cows resulted in a persistent reduction in CH(4) emissions (g of CH(4)/kg of DMI) over a 12-wk period and that these reductions in CH(4) are consistent with previous work that has studied the addition of oilseeds to ruminant diets. 2010 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Comparison of methods to determine methane emissions from dairy cows in farm conditions.

PubMed

Huhtanen, P; Cabezas-Garcia, E H; Utsumi, S; Zimmerman, S

2015-05-01

Nutritional and animal-selection strategies to mitigate enteric methane (CH4) depend on accurate, cost-effective methods to determine emissions from a large number of animals. The objective of the present study was to compare 2 spot-sampling methods to determine CH4 emissions from dairy cows, using gas quantification equipment installed in concentrate feeders or automatic milking stalls. In the first method (sniffer method), CH4 and carbon dioxide (CO2) concentrations were measured in close proximity to the muzzle of the animal, and average CH4 concentrations or CH4/CO2 ratio was calculated. In the second method (flux method), measurement of CH4 and CO2 concentration was combined with an active airflow inside the feed troughs for capture of emitted gas and measurements of CH4 and CO2 fluxes. A muzzle sensor was used allowing data to be filtered when the muzzle was not near the sampling inlet. In a laboratory study, a model cow head was built that emitted CO2 at a constant rate. It was found that CO2 concentrations using the sniffer method decreased up to 39% when the distance of the muzzle from the sampling inlet increased to 30cm, but no muzzle-position effects were observed for the flux method. The methods were compared in 2 on-farm studies conducted using 32 (experiment 1) or 59 (experiment 2) cows in a switch-back design of 5 (experiment 1) or 4 (experiment 2) periods for replicated comparisons between methods. Between-cow coefficient of variation (CV) in CH4 was smaller for the flux than the sniffer method (experiment 1, CV=11.0 vs. 17.5%, and experiment 2, 17.6 vs. 28.0%). Repeatability of the measurements from both methods were high (0.72-0.88), but the relationship between the sniffer and flux methods was weak (R(2)=0.09 in both experiments). With the flux method CH4 was found to be correlated to dry matter intake or body weight, but this was not the case with the sniffer method. The CH4/CO2 ratio was more highly correlated between the flux and sniffer methods (R(2)=0.30), and CV was similar (6.4-8.8%). In experiment 2, cow muzzle position was highly repeatable (0.82) and influenced sniffer and flux method results when not filtered for muzzle position. It was concluded that the flux method provides more reliable estimates of CH4 emissions than the sniffer method. The sniffer method appears to be affected by variable air-mixing conditions created by geometry of feed trough, muzzle movement, and muzzle position. Copyright © 2015 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Effects of dietary forage-to-concentrate ratio on nutrient digestibility and enteric methane production in growing goats (Capra hircus hircus) and Sika deer (Cervus nippon hortulorum)

PubMed Central

Na, Youngjun; Li, Dong Hua; Lee, Sang Rak

2017-01-01

Objective Two experiments were conducted to determine the effects of forage-to-concentrate (F:C) ratio on the nutrient digestibility and enteric methane (CH4) emission in growing goats and Sika deer. Methods Three male growing goats (body weight [BW] = 19.0±0.7 kg) and three male growing deer (BW = 19.3±1.2 kg) were respectively allotted to a 3×3 Latin square design with an adaptation period of 7 d and a data collection period of 3 d. Respiration-metabolism chambers were used for measuring the enteric CH4 emission. Treatments of low (25:75), moderate (50:50), and high (73:27) F:C ratios were given to both goats and Sika deer. Results Dry matter (DM) and organic matter (OM) digestibility decreased linearly with increasing F:C ratio in both goats and Sika deer. In both goats and Sika deer, the CH4 emissions expressed as g/d, g/kg BW0.75, % of gross energy intake, g/kg DM intake (DMI), and g/kg OM intake (OMI) decreased linearly as the F:C ratio increased, however, the CH4 emissions expressed as g/kg digested DMI and OMI were not affected by the F:C ratio. Eight equations were derived for predicting the enteric CH4 emission from goats and Sika deer. For goat, equation 1 was found to be of the highest accuracy: CH4 (g/d) = 3.36+4.71×DMI (kg/d)−0.0036×neutral detergent fiber concentrate (NDFC, g/kg)+0.01563×dry matter digestibility (DMD, g/kg)−0.0108×neutral detergent fiber digestibility (NDFD, g/kg). For Sika deer, equation 5 was found to be of the highest accuracy: CH4 (g/d) = 66.3+27.7×DMI (kg/d)−5.91×NDFC (g/kg)−7.11× DMD (g/kg)+0.0809×NDFD (g/kg). Conclusion Digested nutrient intake could be considered when determining the CH4 generation factor in goats and Sika deer. Finally, the enteric CH4 prediction model for goats and Sika deer were estimated. PMID:28335097

Data Build-up for the Construction of Korean Specific Greenhouse Gas Emission Inventory in Livestock Categories.

PubMed

Won, S G; Cho, W S; Lee, J E; Park, K H; Ra, C S

2014-03-01

Many studies on methane (CH4) and nitrous oxide (N2O) emissions from livestock industries have revealed that livestock production directly contributes to greenhouse gas (GHG) emissions through enteric fermentation and manure management, which causes negative impacts on animal environment sustainability. In the present study, three essential values for GHG emission were measured; i.e., i) maximum CH4 producing capacity at mesophilic temperature (37°C) from anaerobically stored manure in livestock category (B0,KM, Korean livestock manure for B0), ii) EF3(s) value representing an emission factor for direct N2O emissions from manure management system S in the country, kg N2O-N kg N(-1), at mesophilic (37°C) and thermophilic (55°C) temperatures, and iii) Nex(T) emissions showing annual N excretion for livestock category T, kg N animal(-1) yr(-1), from different livestock manure. Static incubation with and without aeration was performed to obtain the N2O and CH4 emissions from each sample, respectively. Chemical compositions of pre- and post-incubated manure were analyzed. Contents of total solids (% TS) and volatile solid (% VS), and the ratio of carbon to nitrogen (C/N) decrease significantly in all the samples by C-containing biogas generation, whereas moisture content (%) and pH increased after incubation. A big difference of total nitrogen content was not observed in pre- and post-incubation during CH4 and N2O emissions. CH4 emissions (g CH4 kg VS(-1)) from all the three manures (sows, layers and Korean cattle) were different and high C/N ratio resulted in high CH4 emission. Similarly, N2O emission was found to be affected by % VS, pH, and temperature. The B0,KM values for sows, layers, and Korean cattle obtained at 37°C are 0.0579, 0.0006, and 0.0828 m(3) CH4 kg VS(-1), respectively, which are much less than the default values in IPCC guideline (GL) except the value from Korean cattle. For sows and Korean cattle, Nex(T) values of 7.67 and 28.19 kg N yr(-1), respectively, are 2.5 fold less than those values in IPCC GL as well. However, Nex(T) value of layers 0.63 kg N yr(-1) is very similar to the default value of 0.6 kg N yr(-1) in IPCC GLs for National greenhouse gas inventories for countries such as South Korea/Asia. The EF3(s) value obtained at 37°C and 55°C were found to be far less than the default value.

Mapping soil-landscape elements and the wetland in dambos and estimating CH4 and CO2 emissions from a dambo-terminated catena

NASA Astrophysics Data System (ADS)

Sebadduka, Jerome

Dambos are seasonally saturated grassy valleys mainly found on the central African plateau. They are usually sub-divided into three catenary units - gleyed and frequently inundated bottoms, flat and rarely inundated floors, and sloping sandy margins - fringed at the interfluve by the well-drained uplands. Since dambos constitute ˜11% of Africa's arable land, soil information is required to guide sustainable use of the land. Further, it is important to determine the extent of the wetland environment in these landscapes so as to avoid miss-use of the land, which could arise because of varying definitions of the wetland in these landscapes. In addition, lack of knowledge about the true nature of dambo wetlands limits our understanding of their greenhouse gas (GHG) source and sinks strengths, which prevents projection of future GHG scenarios accompanying dambo use. This study was conducted so as to address these inadequacies, and is guided by the following specific objectives: (i) delineate dambo soil-landscape elements using aerial gamma-ray and terrain data; (ii) characterize a dambo wetland; and (iii) determine CH4 and CO2 sources and sinks in a dambo landscape. The area Hansen et al. (2009) studied was revisited. For objective 1, their model training and validation data were used. For objectives 2 and 3, data (e.g., soil, water table and gas samples) were collected from experimental plots in the four landscape positions, geographically constrained around dambo bottom pixels. Data used were collected during the main (March to July 2008) and short rainfall (October and November 2009) seasons in the area. An ANOVA analysis showed landscape position to have a proportionate influence on the variability of eU (46%), K% (28%) and eTh (27%); owing to the differences in soil properties along dambo cross-profiles. The results based on random forests (RF) and multinomial-ISODATA modeling, where gamma-ray and derivatives of a Shuttle Radar Topography Mission (SRTM) digital elevation model (DEM) were used to classify dambo catenary units, were accurate, but only slightly better than the method which made no use of gamma-ray (e.g., conditional inference tree) . It was concluded that dambo landscape elements can be mapped by using these two data sources; although terrain data provides more information. Based upon a combination of hydrology and soil properties, dambo bottoms were the only element shown to constitute the dambo wetland. This zone is inundated for at least three-quarters of the main rainfall season and soils are hydric. Using the landscape map created by Hansen et al. (2009), the wetland was found to constitute only ˜15% of the dambo. This is smaller than what was mapped by FAO-Africover and the Department of Survey and Mapping, Uganda (DSM). The wetland was also found to be the main source of CH 4 and sink of CO2, with additional strengths attributed to the neighboring floor. Given that these constitute less than 20% of the landscape, dambo net contribution to the regional CH4 budget is insignificant because 80% of the landscape is a sink. The worry, though, is the ongoing degradation, with the impact this has on the release of CO2.

Room-Temperature C-H Functionalization Sequence under Benchtop Conditions for the Undergraduate Chemistry Laboratory

ERIC Educational Resources Information Center

Chen, Shuming

2018-01-01

An iridium(III)-mediated C-H functionalization sequence involving a concerted cyclometalation-deprotonation/migratory insertion pathway is reported for the undergraduate chemistry laboratory. The air- and water-stable iridacycle intermediates are readily isolated and characterized by NMR spectroscopy. Both steps of the experiment are performed at…

Synthesis, spectroscopic, and antibacterial activity of tetraazamacrocyclic complexes of trivalent chromium, manganese, and iron.

PubMed

Singh, D P; Malik, Vandna; Kumar, Ramesh; Singh, Jitender

2009-10-01

A new series of macrocyclic complexes of type [M(TML)X]X(2), where M = Cr(III), Mn(III), or Fe(III), TML is tetradentate macrocyclic ligand, and X = Cl(-), NO(3)(-), CH(3)COO(-) for Cr(III), Fe(III) and X = CH(3)COO(-) for Mn (III), has been synthesized by condensation of benzil and succinyldihydrazide in the presence of metal salt. The complexes have been so formulated due to the 1:2 electrolytic nature of these complexes as shown by conductivity measurements. The complexes have been characterized with the help of various physicochemical techniques such as elemental analysis, molar conductance, electronic and infrared spectral studies, and magnetic susceptibility. On the basis of these studies, a five-coordinate distorted square pyramidal geometry, in which two nitrogens and two carbonyl oxygen atoms are suitably placed for coordination toward the metal ion, has been proposed for all the complexes. The complexes have been tested for their in vitro antibacterial activity. Some of the complexes show remarkable antibacterial activities against some selected bacterial strains. The minimum inhibitory concentrations shown by these complexes have been compared with those shown by some standard antibiotics such as linezolid and cefaclor.

Computational Insight into the Mechanism of Alkane Hydroxylation by Non-heme Fe(PyTACN) Iron Complexes. Effects of the Substrate and Solvent.

PubMed

Postils, Verònica; Company, Anna; Solà, Miquel; Costas, Miquel; Luis, Josep M

2015-09-08

The reaction mechanisms for alkane hydroxylation catalyzed by non-heme Fe(V)O complexes presented in the literature vary from rebound stepwise to concerted highly asynchronous processes. The origin of these important differences is still not completely understood. Herein, in order to clarify this apparent inconsistency, the hydroxylation of a series of alkanes (methane and substrates bearing primary, secondary, and tertiary C-H bonds) through a Fe(V)O species, [Fe(V)(O)(OH)(PyTACN)](2+) (PyTACN = 1-(2'-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane), has been computationally examined at the gas phase and in acetonitrile solution. The initial breaking of the C-H bond can occur via hydrogen atom transfer (HAT), leading to an intermediate where there is an interaction between the radical substrate and [Fe(IV)(OH)2(PyTACN)](2+), or through hydride transfer to form a cationic substrate interacting with the [Fe(III)(OH)2(PyTACN)](+) species. Our calculations show the following: (i) except for methane in the rest of the alkanes studied, the intermediate formed by R(+) and [Fe(III)(OH)2(PyTACN)](+) is more stable than that involving the alkyl radical and the [Fe(IV)(OH)2(PyTACN)](2+) complex; (ii) in spite of (i), the first step of the reaction mechanism for all substrates is a HAT instead of hydride abstraction; (iii) the HAT is the rate-determining step for all analyzed cases; and (iv) the barrier for the HAT decreases along methane → primary → secondary → tertiary carbon. The second part of the reaction mechanism corresponds to the rebound process. Therefore, the stereospecific hydroxylation of alkane C-H bonds by non-heme Fe(V)(O) species occurs through a rebound stepwise mechanism that resembles that taking place at heme analogues. Finally, our study also shows that, to properly describe alkane hydroxylation processes mediated by Fe(V)O species, it is essential to consider the solvent effects during geometry optimizations. The use of gas-phase geometries explains the variety of mechanisms for the hydroxylation of alkanes reported in the literature.

pH and calcium ion release evaluation of pure and calcium hydroxide-containing Epiphany for use in retrograde filling

PubMed Central

TANOMARU-FILHO, Mário; SAÇAKI, Juliana Nogueira; FALEIROS, Frederico Bordini Chaves; GUERREIRO-TANOMARU, Juliane Maria

2011-01-01

Objective Hydroxyl (OH-) and calcium (Ca++) ion release was evaluated in six materials: G1) Sealer 26, G2) White mineral trioxide aggregate (MTA), G3) epiphany, G4) epiphany + 10% calcium hydroxide (CH), G5) epiphany + 20% CH, and G6) zinc oxide and eugenol. Material and Methods Specimens were placed in polyethylene tubes and immersed in distilled water. After 3, 6, 12, 24, and 48 h, 7, 14, and 28 days, the water was assessed for pH with a pH meter and for Ca++ release by atomic absorption spectrophotometry. Results G1, G2, G4, and G5 had the highest pH until 14 days (p<0.05). G1 presented the highest Ca++ release until 6 h, and G4 and G5, from 12 h through 14 days. Ca++ release was greater for G1 and G2 at 28 days. G6 released the least Ca++. Conclusion MTA, Sealer 26, epiphany, and epiphany + CH release OH - and Ca++ ions. Epiphany + CH may be an alternative as retrofilling material. PMID:21437461

A General Cp*CoIII -Catalyzed Intramolecular C-H Activation Approach for the Efficient Total Syntheses of Aromathecin, Protoberberine, and Tylophora Alkaloids.

PubMed

Lerchen, Andreas; Knecht, Tobias; Koy, Maximilian; Daniliuc, Constantin G; Glorius, Frank

2017-09-07

Herein, we report a Cp*Co III -catalyzed C-H activation approach as the key step to create highly valuable isoquinolones and pyridones as building blocks that can readily be applied in the total syntheses of a variety of aromathecin, protoberberine, and tylophora alkaloids. This particular C-H activation/annulation reaction was achieved with several terminal as well as internal alkyne coupling partners delivering a broad scope with excellent functional group tolerance. The synthetic applicability of this protocol reported herein was demonstrated in the total syntheses of two Topo-I-Inhibitors and two 8-oxyprotoberberine cores that can be further elaborated into the tetrahydroprotoberberine and the protoberberine alkaloid core. Moreover these building blocks were also transformed to six different tylophora alkaloids in expedient fashion. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

QUENCHING OF CARBON MONOXIDE AND METHANE IN THE ATMOSPHERES OF COOL BROWN DWARFS AND HOT JUPITERS

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

Visscher, Channon; Moses, Julianne I., E-mail: visscher@lpi.usra.edu, E-mail: jmoses@spacescience.org

We explore CO{r_reversible}CH{sub 4} quench kinetics in the atmospheres of substellar objects using updated timescale arguments, as suggested by a thermochemical kinetics and diffusion model that transitions from the thermochemical-equilibrium regime in the deep atmosphere to a quench-chemical regime at higher altitudes. More specifically, we examine CO quench chemistry on the T dwarf Gliese 229B and CH{sub 4} quench chemistry on the hot-Jupiter HD 189733b. We describe a method for correctly calculating reverse rate coefficients for chemical reactions, discuss the predominant pathways for CO{r_reversible}CH{sub 4} interconversion as indicated by the model, and demonstrate that a simple timescale approach can bemore » used to accurately describe the behavior of quenched species when updated reaction kinetics and mixing-length-scale assumptions are used. Proper treatment of quench kinetics has important implications for estimates of molecular abundances and/or vertical mixing rates in the atmospheres of substellar objects. Our model results indicate significantly higher K{sub zz} values than previously estimated near the CO quench level on Gliese 229B, whereas current-model-data comparisons using CH{sub 4} permit a wide range of K{sub zz} values on HD 189733b. We also use updated reaction kinetics to revise previous estimates of the Jovian water abundance, based upon the observed abundance and chemical behavior of carbon monoxide. The CO chemical/observational constraint, along with Galileo entry probe data, suggests a water abundance of approximately 0.51-2.6 x solar (for a solar value of H{sub 2}O/H{sub 2} = 9.61 x 10{sup -4}) in Jupiter's troposphere, assuming vertical mixing from the deep atmosphere is the only source of tropospheric CO.« less

Redox reactions of V(III) and Cr(III)picolinate complexes in aqueous solutions

NASA Astrophysics Data System (ADS)

Vinayakumar, C. K.; Dey, G. R.; Kishore, K.; Moorthy, P. N.

1996-12-01

Reactions of e aq-, H-atoms, OH, (CH 3) 2COH, and CO 2- radicals with V(III)picolinate and Cr(III)picolinate have been studied by the pulse radiolysis technique. The spectra of V(II)picolinate, V(IV)picolinate, Cr(II)picolinate, OH adduct of Cr(III)picolinate and Cr(IV)picolinate have been obtained and the rate constants of the reactions of various radicals with V(III) and Cr(III)picolinate have been determined. The implications of these results to the chemical decontamination of nuclear reactor systems are discussed.

Phase diagram calculations and high pressure Raman spectroscopy studies of organic "plastic crystal" thermal energy storage materials

NASA Astrophysics Data System (ADS)

Chellappa, Raja S.

This dissertation presents the phase diagram calculations and high pressure Raman spectroscopy studies on organic "plastic crystal" thermal storage materials. The organic "plastic crystals" that were studied include pentaerythritol [PE:C(CH 2OH)4], neopentylglycol [NPG:(CH3)2C(CH 2OH)2], tris(hydroxymethyl)-aminomethane [TRIS:(NH2 )C(CH2OH)3], and 2-amino-2-methyl-1,3-propanediol [AMPL: (NH2)(CH3)C(CH2OH)2]. Thermodynamic optimization of the experimental data of AMPL-NPG and PE-AMPL binary system was performed and the calculated phase diagrams are presented. A preliminary calculated phase diagram of the TRIS-NPG binary system is also presented. A thorough reevaluation of the existing calorimetric and x-ray diffraction data of the PE-AMPL binary system is also presented. This analysis resulted in the correct interpretation of the phase boundaries and a revised phase diagram has been drawn. The results of high pressure Raman spectroscopy experiments on neopentylglycol and pentaerythritol presented. The phase transformation pressures were determined by analyzing the frequency shifts as a function of pressure as well as the changes in the internal modes of vibration for these compounds. A simplified assignment of the vibrational modes for NPG at ambient pressure is presented. The results indicate experiments were carried out using Diamond Anvil Cell (DAC) and the pressure induced transformations were studied by Raman spectroscopy. In NPG, a phase transition occurs at ˜3.6 GPa from Phase I (Monoclinic) to Phase II (unknown structure). In PE, the proposed phase transformation pressures are ˜4.8 GPa (Phase I to Phase II), ˜6.9 GPa (Phase II to Phase III), ˜9.5 GPa (Phase III to Phase IV), and ˜15 GPa (Phase IV to Amorphous). The results of a critical assessment of the vapor pressure data of solid metal carbonyls. The vapor pressure data of Chromium Carbonyl (Cr(CO)6), Tungsten Carbonyl (W(CO)6 ), Osmium Carbonyl (Os3(CO)12), Molybdenum Carbonyl (MO(CO)6). Rhenium Carbonyl (Re2(CO)10), and Manganese Carbonyl (Mn(CO)5) were assessed using the "Oonk Methodology". The sublimation properties using the assessed data (Delta subGo,DeltasubH o and Deltasub Cop,m ) of these compounds have been evaluated and a discussion on the mutual consistency of various data sets for each compound over a wide range of temperature is also presented.

Nitrate loading and CH4 and N2O Flux from headwater streams

NASA Astrophysics Data System (ADS)

Sousa, C. H. R. D.; Hilker, T.; Hall, F. G.; Moura, Y. M.; McAdam, E.

2014-12-01

Freshwater ecosystems transport and process significant amounts of terrestrial carbon and can be considerable sources of CO2, CH4, and N2O. A great deal of uncertainty, however, remains in both global estimates and our understanding of drivers of freshwater greenhouse gas emissions. Furthermore, small headwater streams have received insufficient attention to date and may contribute disproportionately to global GHG flux. Our objective was to quantify GHG flux and assess the impact of changes in DOC and NO3 concentrations in surface and subsurface water on flux rates in three streams in the Lamprey River watershed in New Hampshire, USA, that contrast in surface water DOC:NO3. We measured DOC, NO3 and dissolved gas concentrations in surface waters of each stream monthly from May 2011 to April 2012. Empirical measurements of reaeration coefficients were used to convert dissolved gas concentrations to fluxes. We found higher GHG concentrations and fluxes in the two streams with high DOC concentrations, particularly gases produced by anaerobic metabolism (CH4, N2O from methanogenesis and denitrification, respectively). The stream with high DOC and high NO3 showed high N2O and low CH4 flux, while the high DOC, low NO3 stream showed high CH4 and low N2O flux. Our results are consistent with a model in which C inputs drive total GHG production, while NO3 input regulates the relative importance of CH4 and N2O by suppressing methanogenesis and stimulating denitrification. The magnitude of GHG fluxes suggests that streams in this region are likely to be small sources of CO2, but potentially important sources of CH4 and N2O. Since CH4 and N2O are many times more powerful than CO2 at trapping heat in the atmosphere, freshwater emissions of these gases have the potential to offset a significant proportion of the climate benefits of the terrestrial carbon sink, a possibility that has not been sufficiently incorporated into climate models.

Nitrate loading and CH4 and N2O Flux from headwater streams

NASA Astrophysics Data System (ADS)

Schade, J. D.; Bailio, J.; McDowell, W. H.

2015-12-01

Freshwater ecosystems transport and process significant amounts of terrestrial carbon and can be considerable sources of CO2, CH4, and N2O. A great deal of uncertainty, however, remains in both global estimates and our understanding of drivers of freshwater greenhouse gas emissions. Furthermore, small headwater streams have received insufficient attention to date and may contribute disproportionately to global GHG flux. Our objective was to quantify GHG flux and assess the impact of changes in DOC and NO3 concentrations in surface and subsurface water on flux rates in three streams in the Lamprey River watershed in New Hampshire, USA, that contrast in surface water DOC:NO3. We measured DOC, NO3 and dissolved gas concentrations in surface waters of each stream monthly from May 2011 to April 2012. Empirical measurements of reaeration coefficients were used to convert dissolved gas concentrations to fluxes. We found higher GHG concentrations and fluxes in the two streams with high DOC concentrations, particularly gases produced by anaerobic metabolism (CH4, N2O from methanogenesis and denitrification, respectively). The stream with high DOC and high NO3 showed high N2O and low CH4 flux, while the high DOC, low NO3 stream showed high CH4 and low N2O flux. Our results are consistent with a model in which C inputs drive total GHG production, while NO3 input regulates the relative importance of CH4 and N2O by suppressing methanogenesis and stimulating denitrification. The magnitude of GHG fluxes suggests that streams in this region are likely to be small sources of CO2, but potentially important sources of CH4 and N2O. Since CH4 and N2O are many times more powerful than CO2 at trapping heat in the atmosphere, freshwater emissions of these gases have the potential to offset a significant proportion of the climate benefits of the terrestrial carbon sink, a possibility that has not been sufficiently incorporated into climate models.

Sunflower Oil and Nannochloropsis oculata Microalgae as Sources of Unsaturated Fatty Acids for Mitigation of Methane Production and Enhancing Diets' Nutritive Value.

PubMed

Gomaa, Ali S; Kholif, Ahmed E; Kholif, Abdelkader M; Salama, Reda; El-Alamy, Hamza A; Olafadehan, Olurotimi A

2018-02-28

The objective of this assay was to investigate the effect of adding sunflower oil, Nannochloropsis oculata microalgae and their mixture at 0, 1, 2, 3, 4, and 5% to three total mixed rations (TMRs) with different concentrate:forage ratios (40C:60F, 50C:50F, and 60C:40F) on in vitro gas production (GP), methane (CH 4 ) production, and nutrient degradability. Asymptotic GP, GP rate, CH 4 concentration/g acid detergent fiber (ADF), dry matter (DM) degradability (DMD), short chain fatty acids (SCFAs), and ruminal bacteria population increased, but neutral detergent fiber (NDF) degradability (NDFD), ADF degradability (ADFD), and protozoa count decreased with increasing concentrate level in the TMR. Methane production/g DM and NDF was higher for 50C:50F TMR. Sunflower oil reduced asymptotic GP, lag time, CH 4 production/g ADF, ammonia-N (NH 3 -N), and SCFA. Compared to the control treatments, additives decreased GP rate, while sunflower oil/N. oculata mixture increased DMD and NDFD. All additives at 5% increased GP rate and lag time and decreased CH 4 production/g DM, ADF, and NDF, ruminal NH 3 -N, and protozoa count. All additives at 2% increased DMD, NDFD and ADFD, SCFA, and bacteria population. Supplementation of TMR, containing different concentrate:forage ratios, with sunflower oil, N. oculata, and sunflower oil/N. oculata mixture at different doses modified in vitro GP, CH 4 production, and nutrient degradability.

Laboratory estimates of trace gas emissions following surface application and injection of cattle slurry

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

Flessa, H.; Beese, F.

2000-02-01

Applying cattle slurry to soil may induce emissions of the greenhouse gases N{sub 2}O and CH{sub 4}. Their objective was to determine the effects of different application techniques (surface application and slit injection) of cattle (Bostaurus) slurry on the decomposition of slurry organic matter and the emissions of N{sub 2}O and CH{sub 4}. The effects of slurry application (43.6 m{sup 3} ha{sup {minus}1}) were studied for 9 wk under controlled laboratory conditions using a soil microcosm system with automated monitoring of the CO{sub 2}, N{sub 2}O, and CH{sub 4} fluxes. The soil used was a silty loam (Ap horizon ofmore » a cambisol) with a constant water-filled pore space of 67% during the experiment. About 38% of the organic matter applied with the slurry was decomposed within 9 wk. Production of CO{sub 2} was not affected by the application technique. Emissions of N{sub 2}O and CH{sub 4} from the injected slurry were significantly higher than from the surface-applied slurry, probably because of restricted aeration at the injected-slurry treatment. Total N{sub 2}O-N emissions were 0.2% (surface application) and 3.3% (slit injection) of the slurry N added. Methane emission occurred only during the first few days following application. The total net flux of CH{sub 4}-C for 2 wk was {minus}12 g ha{sup {minus}1} for the control (CH{sub 4} uptake), 2 g ha{sup {minus}1} for the surface-applied slurry, and 39 g ha{sup {minus}1} for the injected slurry. Slurry injection, which is recommended to reduce NH{sub 3} volatilization, appears to increase emissions of the greenhouse gases N{sub 2}O and CH{sub 4} from the fertilized fields.« less

Emissions of CH4 and N2O under Different Tillage Systems from Double-Cropped Paddy Fields in Southern China

PubMed Central

Zhang, Hai-Lin; Bai, Xiao-Lin; Xue, Jian-Fu; Chen, Zhong-Du; Tang, Hai-Ming; Chen, Fu

2013-01-01

Understanding greenhouse gases (GHG) emissions is becoming increasingly important with the climate change. Most previous studies have focused on the assessment of soil organic carbon (SOC) sequestration potential and GHG emissions from agriculture. However, specific experiments assessing tillage impacts on GHG emission from double-cropped paddy fields in Southern China are relatively scarce. Therefore, the objective of this study was to assess the effects of tillage systems on methane (CH4) and nitrous oxide (N2O) emission in a double rice (Oryza sativa L.) cropping system. The experiment was established in 2005 in Hunan Province, China. Three tillage treatments were laid out in a randomized complete block design: conventional tillage (CT), rotary tillage (RT) and no-till (NT). Fluxes of CH4 from different tillage treatments followed a similar trend during the two years, with a single peak emission for the early rice season and a double peak emission for the late rice season. Compared with other treatments, NT significantly reduced CH4 emission among the rice growing seasons (P<0.05). However, much higher variations in N2O emission were observed across the rice growing seasons due to the vulnerability of N2O to external influences. The amount of CH4 emission in paddy fields was much higher relative to N2O emission. Conversion of CT to NT significantly reduced the cumulative CH4 emission for both rice seasons compared with other treatments (P<0.05). The mean value of global warming potentials (GWPs) of CH4 and N2O emissions over 100 years was in the order of NT

In vitro evaluation, in vivo quantification, and microbial diversity studies of nutritional strategies for reducing enteric methane production.

PubMed

Abdalla, Adibe Luiz; Louvandini, Helder; Sallam, Sobhy Mohamed Abdallah Hassan; Bueno, Ives Cláudio da Silva; Tsai, Siu Mui; Figueira, Antonio Vargas de Oliveira

2012-06-01

The main objective of the present work was to study nutritive strategies for lessening the CH(4) formation associated to ruminant tropical diets. In vitro gas production technique was used for evaluating the effect of tannin-rich plants, essential oils, and biodiesel co-products on CH(4) formation in three individual studies and a small chamber system to measure CH(4) released by sheep for in vivo studies was developed. Microbial rumen population diversity from in vitro assays was studied using qPCR. In vitro studies with tanniniferous plants, herbal plant essential oils derived from thyme, fennel, ginger, black seed, and Eucalyptus oil (EuO) added to the basal diet and cakes of oleaginous plants (cotton, palm, castor plant, turnip, and lupine), which were included in the basal diet to replace soybean meal, presented significant differences regarding fermentation gas production and CH(4) formation. In vivo assays were performed according to the results of the in vitro assays. Mimosa caesalpineaefolia, when supplemented to a basal diet (Tifton-85 hay Cynodon sp, corn grain, soybean meal, cotton seed meal, and mineral mixture) fed to adult Santa Ines sheep reduced enteric CH(4) emission but the supplementation of the basal diet with EuO did not affect (P > 0.05) methane released. Regarding the microbial studies of rumen population diversity using qPCR with DNA samples collected from the in vitro trials, the results showed shifts in microbial communities of the tannin-rich plants in relation to control plant. This research demonstrated that tannin-rich M. caesepineapholia, essential oil from eucalyptus, and biodiesel co-products either in vitro or in vivo assays showed potential to mitigate CH(4) emission in ruminants. The microbial community study suggested that the reduction in CH(4) production may be attributed to a decrease in fermentable substrate rather than to a direct effect on methanogenesis.

Emissions of CH4 and N2O under different tillage systems from double-cropped paddy fields in Southern China.

PubMed

Zhang, Hai-Lin; Bai, Xiao-Lin; Xue, Jian-Fu; Chen, Zhong-Du; Tang, Hai-Ming; Chen, Fu

2013-01-01

Understanding greenhouse gases (GHG) emissions is becoming increasingly important with the climate change. Most previous studies have focused on the assessment of soil organic carbon (SOC) sequestration potential and GHG emissions from agriculture. However, specific experiments assessing tillage impacts on GHG emission from double-cropped paddy fields in Southern China are relatively scarce. Therefore, the objective of this study was to assess the effects of tillage systems on methane (CH4) and nitrous oxide (N2O) emission in a double rice (Oryza sativa L.) cropping system. The experiment was established in 2005 in Hunan Province, China. Three tillage treatments were laid out in a randomized complete block design: conventional tillage (CT), rotary tillage (RT) and no-till (NT). Fluxes of CH4 from different tillage treatments followed a similar trend during the two years, with a single peak emission for the early rice season and a double peak emission for the late rice season. Compared with other treatments, NT significantly reduced CH4 emission among the rice growing seasons (P<0.05). However, much higher variations in N2O emission were observed across the rice growing seasons due to the vulnerability of N2O to external influences. The amount of CH4 emission in paddy fields was much higher relative to N2O emission. Conversion of CT to NT significantly reduced the cumulative CH4 emission for both rice seasons compared with other treatments (P<0.05). The mean value of global warming potentials (GWPs) of CH4 and N2O emissions over 100 years was in the order of NT

Activation of carbon-hydrogen bonds via 1,2-addition across M-X (X = OH or NH(2)) bonds of d(6) transition metals as a potential key step in hydrocarbon functionalization: a computational study.

PubMed

Cundari, Thomas R; Grimes, Thomas V; Gunnoe, T Brent

2007-10-31

Recent reports of 1,2-addition of C-H bonds across Ru-X (X = amido, hydroxo) bonds of TpRu(PMe3)X fragments {Tp = hydridotris(pyrazolyl)borate} suggest opportunities for the development of new catalytic cycles for hydrocarbon functionalization. In order to enhance understanding of these transformations, computational examinations of the efficacy of model d6 transition metal complexes of the form [(Tab)M(PH3)2X]q (Tab = tris-azo-borate; X = OH, NH2; q = -1 to +2; M = TcI, Re(I), Ru(II), Co(III), Ir(III), Ni(IV), Pt(IV)) for the activation of benzene C-H bonds, as well as the potential for their incorporation into catalytic functionalization cycles, are presented. For the benzene C-H activation reaction steps, kite-shaped transition states were located and found to have relatively little metal-hydrogen interaction. The C-H activation process is best described as a metal-mediated proton transfer in which the metal center and ligand X function as an activating electrophile and intramolecular base, respectively. While the metal plays a primary role in controlling the kinetics and thermodynamics of the reaction coordinate for C-H activation/functionalization, the ligand X also influences the energetics. On the basis of three thermodynamic criteria characterizing salient energetic aspects of the proposed catalytic cycle and the detailed computational studies reported herein, late transition metal complexes (e.g., Pt, Co, etc.) in the d6 electron configuration {especially the TabCo(PH3)2(OH)+ complex and related Co(III) systems} are predicted to be the most promising for further catalyst investigation.

Synthesis and characterization of monomeric Mn (IV) and pseudo-tetrameric Mn (III) complexes: magnetic properties of Mn (III) complex.

PubMed

Yahsi, Yasemin; Kara, Hulya

2014-06-05

Two novel monomer Mn (IV) [Mn(3,5-ClL1)2]⋅(CH3OH), (1), [3,5-ClL1H2=N-(2-hydroxyethyl)-3,5-dichlorosalicylaldimine] (1) and hydrogen-bonded pseudo-tetramer Mn (III) [Mn(5-BrL2)(H2O)2]2⋅[Mn(5-BrL2)(H2O)]2⋅2⋅(ClO4), (2), [5-BrL2H2=N,N'-bis(5-bromosalicylidenato)-1,2-diamino-2-methylpropane)] (2) Schiff base complexes have been synthesized and their crystal structures have been determined by single crystal X-ray diffraction analysis. A variable temperature magnetic susceptibility measurement study has been performed for complex (2) and the result indicates there is a very weak antiferromagnetic interaction (J=-0.40±0.016cm(-1)) between the two manganese (III) centers. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis and oxidation of CpIrIII compounds: functionalization of a Cp methyl group.

PubMed

Park-Gehrke, Lisa S; Freudenthal, John; Kaminsky, Werner; Dipasquale, Antonio G; Mayer, James M

2009-03-21

[CpIrCl(2)](2) () and new CpIr(III)(L-L)X complexes (L-L = N-O or C-N chelating ligands; X = Cl, I, Me) have been prepared and their reactivity with two-electron chemical oxidants explored. Reaction of with PhI(OAc)(2) in wet solvents yields a new chloro-bridged dimer in which each of the Cp ligands has been singly acetoxylated to form [Cp(OAc)Ir(III)Cl(2)](2) () (Cp(OAc) = eta(5)-C(5)Me(4)CH(2)OAc). Complex and related carboxy- and alkoxy-functionalized Cp(OR) complexes can also be prepared from plus (PhIO)(n) and ROH. [Cp(OAc)Ir(III)Cl(2)](2) () and the methoxy analogue [Cp(OMe)Ir(III)Cl(2)](2) () have been structurally characterized. Treatment of [CpIrCl(2)](2) () with 2-phenylpyridine yields CpIr(III)(ppy)Cl () (ppy = cyclometallated 2-phenylpyridyl) which is readily converted to its iodide and methyl analogues CpIr(III)(ppy)I and CpIr(III)(ppy)Me (). CpIr(III) complexes were also prepared with N-O chelating ligands derived from anthranilic acid (2-aminobenzoic acid) and alpha-aminoisobutyric acid (H(2)NCMe(2)COOH), ligands chosen to be relatively oxidation resistant. These complexes and were reacted with potential two-electron oxidants including PhI(OAc)(2), hexachlorocyclohexadienone (C(6)Cl(6)O), N-fluoro-2,4,6-trimethylpyridinium (Me(3)pyF(+)), [Me(3)O]BF(4) and MeOTf (OTf = triflate, CF(3)SO(3)). Iridium(V) complexes were not observed or implicated in these reactions, despite the similarity of the potential products to known CpIr(V) species. The carbon electrophiles [Me(3)O]BF(4) and MeOTf appear to react preferentially at the N-O ligands, to give methyl esters in some cases. Overall, the results indicate that Cp is not inert under oxidizing conditions and is therefore not a good supporting ligand for oxidizing organometallic complexes.

Evaluation and characterization of the methane-carbon dioxide decomposition reaction

NASA Technical Reports Server (NTRS)

Davenport, R. J.; Schubert, F. H.; Shumar, J. W.; Steenson, T. S.

1975-01-01

A program was conducted to evaluate and characterize the carbon dioxide-methane (CO2-CH4) decomposition reaction, i.e., CO2 + CH4 = 2C + 2H2O. The primary objective was to determine the feasibility of applying this reaction at low temperatures as a technique for recovering the oxygen (O2) remaining in the CO2 which exits mixed with CH4 from a Sabatier CO2 reduction subsystem (as part of an air revitalization system of a manned spacecraft). A test unit was designed, fabricated, and assembled for characterizing the performance of various catalysts for the reaction and ultraviolet activation of the CH4 and CO2. The reactor included in the test unit was designed to have sufficient capacity to evaluate catalyst charges of up to 76 g (0.17 lb). The test stand contained the necessary instrumentation and controls to obtain the data required to characterize the performance of the catalysts and sensitizers tested: flow control and measurement, temperature control and measurement, product and inlet gas analysis, and pressure measurement. A product assurance program was performed implementing the concepts of quality control and safety into the program effort.

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

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

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

Crystal structure of tri­hydrogen bis­{[1,1,1-tris­(2-oxido­ethyl­amino­meth­yl)ethane]­cobalt(III)} trinitrate

PubMed Central

Sethi, Waqas; Johannesen, Heini V.; Morsing, Thorbjørn J.; Piligkos, Stergios; Weihe, Høgni

2015-01-01

The title compound, [Co2(L)2]3+·3NO3 − [where L = CH3C(CH2NHCH2CH2OH1/2)3], has been synthesized from the ligand 1,1,1-tris­(2-hy­droxy­ethyl­amino­meth­yl)ethane. The cobalt(III) dimer has an inter­esting and uncommon O—H⋯O hydrogen-bonding motif with the three bridging hy­droxy H atoms each being equally disordered over two positions. In the dimeric trication, the octa­hedrally coordinated CoIII atoms and the capping C atoms lie on a threefold rotation axis. The N atoms of two crystallographically independent nitrate anions also lie on threefold rotation axes. N—H⋯O hydrogen bonding between the complex cations and nitrate anions leads to the formation of a three-dimensional network structure. The compound is a racemic conglomerate of crystals containing either d or l mol­ecules. The crystal used for this study is a d crystal. PMID:26870462

Syntheses, structures and properties of four organic-inorganic hybrid nicotinate-bridging rare-earth-containing phosphotungstates

NASA Astrophysics Data System (ADS)

Gong, Peijun; Pang, Jingjing; Zhai, Cuiping; Zhao, Junwei

2018-04-01

Four novel organic-inorganic hybrid nicotinate-bridging dimeric rare-earth (RE)-containing phosphotungstates [H2N(CH3)2]8[RE(H2O)(NA)(α-HPW11O39)]2·24H2O (RE = HoIII for 1, ErIII for 2, TbIII for 3, DyIII for 4; HNA = nicotinic acid) have been synthesized from the reaction of trivacant Keggin precursor Na9[α-PW9O34]•16H2O, RE(NO3)3·6H2O, HNA by employing dimethylamine hydrochloride as organic solubilizing agent in the conventional aqueous solution system, which have been further characterized by elemental analyses, IR spectra, thermogravimetric analyses and single-crystal X-ray diffraction. Structural analysis indicates that the hybrid dimeric {[RE(H2O)(NA)(α-HPW11O39)]2}8- polyoxoanion in 1-4 can be considered as two head-to-head mono-RE-containing Keggin [RE(H2O)(NA)(α-HPW11O39)]4- subunits bridged by two (η2,μ-1,1)-nicotinate linkers, which stands for the first organic-inorganic hybrid RE-containing phosphotungstates functionalized by nicotinate ligands. What's more, the solid-state photoluminescence properties and lifetime decay behaviors of 1-4 have been measured at room temperature and their photoluminescence spectra display the characteristic emission bands of corresponding trivalent RE cations.

Feces composition and manure derived methane yield from dairy cows: Influence of diet with focus on fat supplement and roughage type

NASA Astrophysics Data System (ADS)

Møller, Henrik Bjarne; Moset, Verónica; Brask, Maike; Weisbjerg, Martin Riis; Lund, Peter

2014-09-01

The objective of the present study was to evaluate the effect of dairy cow diets on feces composition and methane (CH4) potential from manure with emphasis on fat level and roughage type and compare these results with the corresponding enteric CH4 emission. In experiment 1 six different diets, divided into two fat levels (low and high) and three different roughage types (early cut grass silage, late cut grass silage and maize silage), were used. The high fat level was achieved by adding crushed rapeseed. In experiment 2, the influence of increasing the fat level by using three different types of rapeseed: rapeseed cake, whole seed and rapeseed oil against a low fat ration with no rapeseed fat supplementation was studied. The diet and fat level had a significant influence on feces composition and CH4 yield. In general, ultimate CH4 yields (B0) were 8-9% higher than the present international default values for diets without extra fat and in feces from diets with extra fat supply the yield was 25-31% higher. It was possible to predict the B0 value from feed and feces characteristics; in fact, the best correlation was obtained by including both feed and feces characteristics. Addition of crude fat to diets to dairy cows reduced enteric CH4 emission but at the same time increased CH4 potential from feces both in terms of organic matter in feces and dry matter intake which might lead to increasing emissions unless proper manure handling such as anaerobic digestion is included. Without subsequent anaerobic digestion to produce energy the positive effect achieved at cow level could be counteracted by increasing manure emissions.

Biogas production from vietnamese animal manure, plant residues and organic waste: influence of biomass composition on methane yield.

PubMed

Cu, T T T; Nguyen, T X; Triolo, J M; Pedersen, L; Le, V D; Le, P D; Sommer, S G

2015-02-01

Anaerobic digestion is an efficient and renewable energy technology that can produce biogas from a variety of biomasses such as animal manure, food waste and plant residues. In developing countries this technology is widely used for the production of biogas using local biomasses, but there is little information about the value of these biomasses for energy production. This study was therefore carried out with the objective of estimating the biogas production potential of typical Vietnamese biomasses such as animal manure, slaughterhouse waste and plant residues, and developing a model that relates methane (CH4) production to the chemical characteristics of the biomass. The biochemical methane potential (BMP) and biomass characteristics were measured. Results showed that piglet manure produced the highest CH4 yield of 443 normal litter (NL) CH4 kg(-1) volatile solids (VS) compared to 222 from cows, 177 from sows, 172 from rabbits, 169 from goats and 153 from buffaloes. Methane production from duckweed (Spirodela polyrrhiza) was higher than from lawn grass and water spinach at 340, 220, and 110.6 NL CH4 kg(-1) VS, respectively. The BMP experiment also demonstrated that the CH4 production was inhibited with chicken manure, slaughterhouse waste, cassava residue and shoe-making waste. Statistical analysis showed that lipid and lignin are the most significant predictors of BMP. The model was developed from knowledge that the BMP was related to biomass content of lipid, lignin and protein from manure and plant residues as a percentage of VS with coefficient of determination (R-square) at 0.95. This model was applied to calculate the CH4 yield for a household with 17 fattening pigs in the highlands and lowlands of northern Vietnam.

Biogas Production from Vietnamese Animal Manure, Plant Residues and Organic Waste: Influence of Biomass Composition on Methane Yield

PubMed Central

Cu, T. T. T.; Nguyen, T. X.; Triolo, J. M.; Pedersen, L.; Le, V. D.; Le, P. D.; Sommer, S. G.

2015-01-01

Anaerobic digestion is an efficient and renewable energy technology that can produce biogas from a variety of biomasses such as animal manure, food waste and plant residues. In developing countries this technology is widely used for the production of biogas using local biomasses, but there is little information about the value of these biomasses for energy production. This study was therefore carried out with the objective of estimating the biogas production potential of typical Vietnamese biomasses such as animal manure, slaughterhouse waste and plant residues, and developing a model that relates methane (CH4) production to the chemical characteristics of the biomass. The biochemical methane potential (BMP) and biomass characteristics were measured. Results showed that piglet manure produced the highest CH4 yield of 443 normal litter (NL) CH4 kg−1 volatile solids (VS) compared to 222 from cows, 177 from sows, 172 from rabbits, 169 from goats and 153 from buffaloes. Methane production from duckweed (Spirodela polyrrhiza) was higher than from lawn grass and water spinach at 340, 220, and 110.6 NL CH4 kg−1 VS, respectively. The BMP experiment also demonstrated that the CH4 production was inhibited with chicken manure, slaughterhouse waste, cassava residue and shoe-making waste. Statistical analysis showed that lipid and lignin are the most significant predictors of BMP. The model was developed from knowledge that the BMP was related to biomass content of lipid, lignin and protein from manure and plant residues as a percentage of VS with coefficient of determination (R-square) at 0.95. This model was applied to calculate the CH4 yield for a household with 17 fattening pigs in the highlands and lowlands of northern Vietnam. PMID:25557826

Greenhouse gas emissions from surface flow and subsurface flow constructed wetlands treating dairy wastewater.

PubMed

VanderZaag, A C; Gordon, R J; Burton, D L; Jamieson, R C; Stratton, G W

2010-01-01

Agricultural wastewater treatment is important for protecting water quality in rural ecosystems, and constructed wetlands are an effective treatment option. During treatment, however, some C and N are converted to CH(4), N(2)O, respectively, which are potent greenhouse gases (GHGs). The objective of this study was to assess CH(4), N(2)O, and CO(2) emissions from surface flow (SF) and subsurface flow (SSF) constructed wetlands. Six constructed wetlands (three SF and three SSF; 6.6 m(2) each) were loaded with dairy wastewater in Truro, Nova Scotia, Canada. From August 2005 through September 2006, GHG fluxes were measured continuously using transparent steady-state chambers that encompassed the entire wetlands. Flux densities of all gases were significantly (p < 0.01) different between SF and SSF wetlands changed significantly with time. Overall, SF wetlands had significantly (p < 0.01) higher emissions of CH(4) N(2)O than SSF wetlands and therefore had 180% higher total GHG emissions. The ratio of N(2)O to CH(4) emissions (CO(2)-equivalent) was nearly 1:1 in both wetland types. Emissions of CH(4)-C as a percentage of C removal varied seasonally from 0.2 to 27% were 2 to 3x higher in SF than SSF wetlands. The ratio of N(2)O-N emitted to N removed was between 0.1 and 1.6%, and the difference between wetland types was inconsistent. Thus, N(2)O emissions had a similar contribution to N removal in both wetland types, but SSF wetlands emitted less CH(4) while removing more C from the wastewater than SF wetlands.

The impact of surfactants on Fe(III)-TAML-catalyzed oxidations by peroxides: accelerations, decelerations, and loss of activity.

PubMed

Banerjee, Deboshri; Apollo, Frank M; Ryabov, Alexander D; Collins, Terrence J

2009-10-05

Iron(III) complexes of tetraamidato macrocyclic ligands (TAMLs), [Fe{4-XC(6)H(3)-1,2-(NCOCMe(2)NCO)(2)CR(2)}(OH(2))](-), 1 (1 a: X = H, R = Me; 1 b: X = COOH, R = Me); 1 c: X = CONH(CH(2))(2)COOH, R = Me; 1 d: CONH(CH(2))(2)NMe(2), R = Me; 1 e: X = CONH(CH(2))(2)NMe(3) (+), R = Me; 1 f: X = H, R = F), have been tested as catalysts for the oxidative decolorization of Orange II and Sudan III dyes by hydrogen peroxide and tert-butyl hydroperoxide in the presence of micelles that are neutral (Triton X-100), positively charged (cetyltrimethylammonium bromide, CTAB), and negatively charged (sodium dodecyl sulfate, SDS). The previously reported mechanism of catalysis involves the formation of an oxidized intermediate from 1 and ROOH (k(I)) followed by dye bleaching (k(II)). The micellar effects on k(I) and k(II) have been separately studied and analyzed by using the Berezin pseudophase model of micellar catalysis. The largest micellar acceleration in terms of k(I) occurs for the 1 a-tBuOOH-CTAB system. At pH 9.0-10.5 the rate constant k(I) increased by approximately five times with increasing CTAB concentration and then gradually decreased. There was no acceleration at higher pH, presumably owing to the deprotonation of the axial water ligand of 1 a in this pH range. The k(I) value was only slightly affected by SDS (in the oxidation of Orange II), but was strongly decelerated by Triton X-100. No oxidation of the water-insoluble, hydrophobic dye Sudan III was observed in the presence of the SDS micelles. The k(II) value was accelerated by cationic CTAB micelles when the hydrophobic primary oxidant tert-butyl hydroperoxide was used. It is hypothesized that tBuOOH may affect the CTAB micelles and increase the binding of the oxidized catalysts. The tBuOOH-CTAB combination accelerated both of the catalysis steps k(I) and k(II).

Approaches to the Implementation of Environment Pollution Prevention Technologies at Military Bases (Approches de l’application des techniques de prevention de la pollution sur les bases militaires)

DTIC Science & Technology

2000-04-01

The objective is to support the development and effective use of national defence research and technology and to meet the military needs of the...on materials and energy through developing an effective management system. There are many definitions to describe environmental auditing. I would...anthropogenic increase of CH4 (e.g., from rice fields). Therefore the net effect of aircraft is a negative RF due to the CH4 changes: -0.014 Wm" 2 in 1992

Folic acid causes higher prevalence of detectable unmetabolized folic acid in serum than B-complex: a randomized trial.

PubMed

Obeid, Rima; Kirsch, Susanne H; Dilmann, Sarah; Klein, Cosima; Eckert, Rudolf; Geisel, Jürgen; Herrmann, Wolfgang

2016-04-01

Unmetabolized folic acid (UMFA) is common in serum of elderly individuals receiving folic acid (FA)-fortified foods or supplements. We studied the effect of supplementing FA or B-complex on serum concentrations of (6S)-5-methyltetrahydropteroylglutamate [(6S)-5-CH3-H4Pte] and UMFA in elderly people and explored factors associated with detectable UMFA post-supplementation. This is a randomized single-blind non-controlled trial on 58 elderly people using daily 400 µg FA (n = 31) or 400 µg FA, 10 µg cyanocob(III)alamin and 8 mg pyridoxine (n = 27) for a median of 23 days. Main outcome includes changes in concentrations of serum (6S)-5-CH3-H4Pte and UMFA. Total homocysteine declined by a median of 1.6 (p = 0.074) in the FA and 1.3 µmol/L (p = 0.009) in the B-complex arms (p = 0.66 between the arms). Serum (6S)-5-CH3-H4Pte significantly (p < 0.001 vs. baseline) increased by a median of 9.2 and 6.5 nmol/L in the FA and B-complex groups, respectively (p = 0.152 between the groups). Compared to FA, B-complex reduced cystathionine and caused lower post-intervention serum UMFA, percentage of UMFA to (6S)-5-CH3-H4Pte and prevalence of UMFA ≥ 0.21 nmol/L. Higher serum cystathionine and whole-blood folate predicted higher post-intervention serum UMFA. FA caused higher UMFA as compared to B-complex. Pyridoxine appears to improve folate recycling. Data on serum UMFA should be interpreted in relation to other vitamins involved in folate metabolism. Serum UMFA is suggested to play a sensory role through which the cell recognizes FA available for metabolism via dihydrofolate reductase.

Market Analysis and Consumer Impacts Source Document. Part III. Consumer Behavior and Attitudes Toward Fuel Efficient Vehicles

DOT National Transportation Integrated Search

1980-12-01

This source document on motor vehicle market analysis and consumer impacts consists of three parts. Part III consists of studies and reviews on: consumer awareness of fuel efficiency issues; consumer acceptance of fuel efficient vehicles; car size ch...

Biogeochemical modeling of CO 2 and CH 4 production in anoxic Arctic soil microcosms

DOE PAGES

Tang, Guoping; Zheng, Jianqiu; Xu, Xiaofeng; ...

2016-09-12

Soil organic carbon turnover to CO 2 and CH 4 is sensitive to soil redox potential and pH conditions. But, land surface models do not consider redox and pH in the aqueous phase explicitly, thereby limiting their use for making predictions in anoxic environments. Using recent data from incubations of Arctic soils, we extend the Community Land Model with coupled carbon and nitrogen (CLM-CN) decomposition cascade to include simple organic substrate turnover, fermentation, Fe(III) reduction, and methanogenesis reactions, and assess the efficacy of various temperature and pH response functions. Incorporating the Windermere Humic Aqueous Model (WHAM) enables us to approximatelymore » describe the observed pH evolution without additional parameterization. Though Fe(III) reduction is normally assumed to compete with methanogenesis, the model predicts that Fe(III) reduction raises the pH from acidic to neutral, thereby reducing environmental stress to methanogens and accelerating methane production when substrates are not limiting. Furthermore, the equilibrium speciation predicts a substantial increase in CO 2 solubility as pH increases, and taking into account CO 2 adsorption to surface sites of metal oxides further decreases the predicted headspace gas-phase fraction at low pH. Without adequate representation of these speciation reactions, as well as the impacts of pH, temperature, and pressure, the CO 2 production from closed microcosms can be substantially underestimated based on headspace CO 2 measurements only. Our results demonstrate the efficacy of geochemical models for simulating soil biogeochemistry and provide predictive understanding and mechanistic representations that can be incorporated into land surface models to improve climate predictions.« less

Assigning the Cerium Oxidation State for CH2CeF2 and OCeF2 Based on Multireference Wave Function Analysis.

PubMed

Mooßen, Oliver; Dolg, Michael

2016-06-09

The geometric and electronic structure of the recently experimentally studied molecules ZCeF2 (Z = CH2, O) was investigated by density functional theory (DFT) and wave function-based ab initio methods. Special attention was paid to the Ce-Z metal-ligand bonding, especially to the nature of the interaction between the Ce 4f and the Z 2p orbitals and the possible multiconfigurational character arising from it, as well as to the assignment of an oxidation state of Ce reflecting the electronic structure. Complete active space self-consistent field (CASSCF) calculations were performed, followed by orbital rotations in the active orbital space. The methylene compound CH2CeF2 has an open-shell singlet ground state, which is characterized by a two-configurational wave function in the basis of the strongly mixed natural CASSCF orbitals. The system can also be described in a very compact way by the dominant Ce 4f(1) C 2p(1) configuration, if nearly pure Ce 4f and C 2p orbitals are used. In the basis of these localized orbitals, the molecule is almost monoconfigurational and should be best described as a Ce(III) system. The singlet ground state of the oxygen OCeF2 complex is of closed-shell character when a monoconfigurational wave function with very strongly mixed Ce 4f and O 2p CASSCF natural orbitals is used for the description. The transformation to orbitals localized on the cerium and oxygen atoms leads to a multiconfigurational wave function and reveals characteristics of a mixed valent Ce(IV)/Ce(III) compound. Additionally, the interactions of the localized active orbitals were analyzed by evaluating the expectation values of the charge fluctuation operator and the local spin operator. The Ce 4f and C 2p orbital interaction of the CH2CeF2 compound is weakly covalent and resembles the interaction of the H 1s orbitals in a stretched hydrogen dimer. In contrast, the interaction of the localized active orbitals for OCeF2 shows ionic character. Calculated vibrational Ce-C and Ce-O stretching frequencies at the DFT, CASSCF, second-order Rayleigh-Schrödinger perturbation theory (RS2C), multireference configuration interaction (MRCI), as well as single, doubles, and perturbative triples coupled cluster (CCSD(T)) level are reported and compared to experimental infrared absorption data in a Ne and Ar matrix.

The Regulation of CH4 and N2O fluxes by Wetlands at Landscape Level

NASA Astrophysics Data System (ADS)

Soosaar, K.; Maddison, M.; Salm, J. O.; Järveoja, J.; Hansen, R.; Mander, Ü.

2012-04-01

The world's wetlands, despite being only about 5% of the terrestrial landscape, are currently significant net sinks of more than 1 Pg yr-1 of carbon (Mitsch et al 2012). At landscape level wetlands and riparian zones are important regulators of nutrient transport (Zedler 2003). However, they can be also significant hot spots of greenhouse gas (GHG) emissions (Teiter&Mander 2005). Swedish experience shows that the nationally planned wetland creation (12,000 ha) could make a significant contribution to the targeted reduction of N fluxes (up to 27% of the Swedish environmental objective), at an environmental risk equalling 0.04% of the national anthropogenic GHG emission (Thiere et al 2011). Only few studies consider the potential GHG emission throughout both natural and created wetlands. The main objective of this study was to clarify the potential of various wetland ecosystem and riparian zones of northern rural landscapes in regulation of GHG emissions. Monthly-based measurements of GHG emissions using closed chamber method were performed from October 2007 to October 2011 in 47 study sites in Estonia. The study sites cover various wetlands and riparian forests as well as reference areas on automorphic soils. In general, wetlands' drainage was the most significant disturbance factor influencing GHG fluxes, causing significant increase of N2O emission as well as decreasing CH4 emission. However, we also observed significantly high CH4 flux from drained peatlands. In most of the soils with ground/soil water levels deeper than 30 cm from the surface, a significant decrease of CH4 fluxes were detected. The highest CH4 emissions (up to 5060 kg CH4-C ha-1 yr-1) were detected from drained fen grasslands. In the case of N2O, no clear differences were found between colder and warmer periods. Relatively higher N2O fluxes were measured from the drained fen grassland, the fertilized arable land, the riparian forest on automorphic soil, and the drained transition fen forest: median values 4.2, 1.4, 1.1, and 0.9 kg N2O-N ha-1 y-1, respectively. In peatlands, median values of CH4-C were 85.2, 23.7, 0.07 and 0.12 kg ha-1 yr-1, and N2O-N -0.05, -0.01, 0.18 and 0.19 kg ha-1 yr-1, respectively. There were significantly higher emissions of N2O from abandoned and active peat mining areas, whereas CH4 emissions were significantly higher in natural and drained areas. We also found that the buffering capacity of long-term loaded riparian alder forests in agricultural landscapes will decrease over time, which calls for the careful management of these riparian forests. Mitsch, W.J, Zhang, L., Stefanik, K.C., Nahlik, A.M., Anderson, C.J., Bernal, B., Hernandez, M., Song, K. 2012. Creating wetlands: Primary succession, water quality changes, and self-design over 15 years. BioScience in press Zedler, JB. 2003. Wetlands at your service: reducing impacts of agriculture at the watershed scale. Front. Ecol. Environ., 1, pp. 65-72 Teiter, S., Mander, U. 2005. Emission of N2O, N2, CH4, and CO2 from constructed wetlands for wastewater treatment and from riparian buffer zones. Ecol. Eng., 25, pp. 528-541 Thiere, G., Stadmark, J., Weisner, SEB. 2011. Nitrogen retention versus methane emission: Environmental benefits and risks of large-scale wetland creation. Ecol. Eng., 37, pp. 6-15

Effects of Tillage and Nitrogen Fertilizers on CH4 and CO2 Emissions and Soil Organic Carbon in Paddy Fields of Central China

PubMed Central

Zhi-Kui, Kou; Zhi-Sheng, Zhang; Jin-Ping, Wang; Ming-Li, Cai; Cou-Gui, Cao

2012-01-01

Quantifying carbon (C) sequestration in paddy soils is necessary to help better understand the effect of agricultural practices on the C cycle. The objective of the present study was to assess the effects of tillage practices [conventional tillage (CT) and no-tillage (NT)] and the application of nitrogen (N) fertilizer (0 and 210 kg N ha−1) on fluxes of CH4 and CO2, and soil organic C (SOC) sequestration during the 2009 and 2010 rice growing seasons in central China. Application of N fertilizer significantly increased CH4 emissions by 13%–66% and SOC by 21%–94% irrespective of soil sampling depths, but had no effect on CO2 emissions in either year. Tillage significantly affected CH4 and CO2 emissions, where NT significantly decreased CH4 emissions by 10%–36% but increased CO2 emissions by 22%–40% in both years. The effects of tillage on the SOC varied with the depth of soil sampling. NT significantly increased the SOC by 7%–48% in the 0–5 cm layer compared with CT. However, there was no significant difference in the SOC between NT and CT across the entire 0–20 cm layer. Hence, our results suggest that the potential of SOC sequestration in NT paddy fields may be overestimated in central China if only surface soil samples are considered. PMID:22574109

Greenhouse gases inventory and carbon balance of two dairy systems obtained from two methane-estimation methods.

PubMed

Cunha, C S; Lopes, N L; Veloso, C M; Jacovine, L A G; Tomich, T R; Pereira, L G R; Marcondes, M I

2016-11-15

The adoption of carbon inventories for dairy farms in tropical countries based on models developed from animals and diets of temperate climates is questionable. Thus, the objectives of this study were to estimate enteric methane (CH4) emissions through the SF6 tracer gas technique and through equations proposed by the Intergovernmental Panel on Climate Change (IPCC) Tier 2 and to calculate the inventory of greenhouse gas (GHG) emissions from two dairy systems. In addition, the carbon balance of these properties was estimated using enteric CH4 emissions obtained using both methodologies. In trial 1, the CH4 emissions were estimated from seven Holstein dairy cattle categories based on the SF6 tracer gas technique and on IPCC equations. The categories used in the study were prepubertal heifers (n=6); pubertal heifers (n=4); pregnant heifers (n=5); high-producing (n=6); medium-producing (n=5); low-producing (n=4) and dry cows (n=5). Enteric methane emission was higher for the category comprising prepubertal heifers when estimated by the equations proposed by the IPCC Tier 2. However, higher CH4 emissions were estimated by the SF6 technique in the categories including medium- and high-producing cows and dry cows. Pubertal heifers, pregnant heifers, and low-producing cows had equal CH4 emissions as estimated by both methods. In trial 2, two dairy farms were monitored for one year to identify all activities that contributed in any way to GHG emissions. The total emission from Farm 1 was 3.21t CO2e/animal/yr, of which 1.63t corresponded to enteric CH4. Farm 2 emitted 3.18t CO2e/animal/yr, with 1.70t of enteric CH4. IPCC estimations can underestimate CH4 emissions from some categories while overestimate others. However, considering the whole property, these discrepancies are offset and we would submit that the equations suggested by the IPCC properly estimate the total CH4 emission and carbon balance of the properties. Thus, the IPCC equations should be utilized with caution, and the herd composition should be analysed at the property level. When the carbon stock in pasture and other crops was considered, the carbon balance suggested that both farms are sustainable for GHG, by both methods. On the other hand, carbon balance without carbon stock, by both methods, suggests that farms emit more carbon than the system is capable of stock. Copyright © 2016 Elsevier B.V. All rights reserved.

Basic Concepts and Principles of Marketing.

ERIC Educational Resources Information Center

Beder, Hal

1986-01-01

Presents an overview of marketing concepts and principles. These include (1) organizational objectives, (2) exchange, (3) value, (4) market segmentation, (5) market position, (6) consumer analysis, (7) product, (8) promotion, (9) place, and (10) price. (CH)

Bis(μ-2-{[2-(1,3-benzothia­zol-2-yl)hydrazinyl­idene]meth­yl}-6-meth­oxy­phenolato)bis­[dinitratodysprosium(III)] methanol disolvate

PubMed Central

Xu, Xuebin; Ding, Shuai; Shen, Si; Tang, Jinkui; Liu, Zhiliang

2011-01-01

In the centrosymmetric dinuclear title compound, [Dy2(C15H12N3O2S)2(NO3)4]·2CH3OH, the two DyIII atoms are coordinated by two deprotonated 2-{[2-(1,3-benzothia­zol-2-yl)hydrazinyl­idene]meth­yl}-6-meth­oxy­phenol ligands and four nitrate ions, all of which are chelating. The crystal packing is stabilized by inter­molecular N—H⋯O hydrogen bonds and weak O—H⋯O inter­actions, forming a two-dimensional network parallel to (010). PMID:21754674

AltitudeOmics: exercise-induced supraspinal fatigue is attenuated in healthy humans after acclimatization to high altitude.

PubMed

Goodall, S; Twomey, R; Amann, M; Ross, E Z; Lovering, A T; Romer, L M; Subudhi, A W; Roach, R C

2014-04-01

We asked whether acclimatization to chronic hypoxia (CH) attenuates the level of supraspinal fatigue that is observed after locomotor exercise in acute hypoxia (AH). Seven recreationally active participants performed identical bouts of constant-load cycling (131 ± 39 W, 10.1 ± 1.4 min) on three occasions: (i) in normoxia (N, PI O2 , 147.1 mmHg); (ii) in AH (FI O2 , 0.105; PI O2 , 73.8 mmHg); and (iii) after 14 days in CH (5260 m; PI O2 , 75.7 mmHg). Throughout trials, prefrontal-cortex tissue oxygenation and middle cerebral artery blood velocity (MCAV) were assessed using near-infrared-spectroscopy and transcranial Doppler sonography. Pre- and post-exercise twitch responses to femoral nerve stimulation and transcranial magnetic stimulation were obtained to assess neuromuscular and corticospinal function. In AH, prefrontal oxygenation declined at rest (Δ7 ± 5%) and end-exercise (Δ26 ± 13%) (P < 0.01); the degree of deoxygenation in AH was greater than N and CH (P < 0.05). The cerebral O2 delivery index (MCAV × Ca O2 ) was 19 ± 14% lower during the final minute of exercise in AH compared to N (P = 0.013) and 20 ± 12% lower compared to CH (P = 0.040). Maximum voluntary and potentiated twitch force were decreased below baseline after exercise in AH and CH, but not N. Cortical voluntary activation decreased below baseline after exercise in AH (Δ11%, P = 0.014), but not CH (Δ6%, P = 0.174) or N (Δ4%, P = 0.298). A twofold greater increase in motor-evoked potential amplitude was evident after exercise in CH compared to AH and N. These data indicate that exacerbated supraspinal fatigue after exercise in AH is attenuated after 14 days of acclimatization to altitude. The reduced development of supraspinal fatigue in CH may have been attributable to increased corticospinal excitability, consequent to an increased cerebral O2 delivery. © 2014 Scandinavian Physiological Society. Published by John Wiley & Sons Ltd.

Constraining the sources of CH4 emissions during past abrupt climate change using CH4 triple isotopes mass balance from the ice core records

NASA Astrophysics Data System (ADS)

Dyonisius, M.; Petrenko, V. V.; Smith, A. W.; Hmiel, B.; Beck, J.; Seth, B.; Bock, M.; Hua, Q.; Yang, B.; Harth, C. M.; Beaudette, R.; Lee, J.; Erhardt, T.; Schmitt, J.; Brook, E.; Weiss, R. F.; Fischer, H.; Severinghaus, J. P.

2017-12-01

Methane (CH4) is the third most important greenhouse gas in the atmosphere after water vapor and CO2. Understanding how the natural CH4 budget has changed in response to changing climate in the past can provide insights on the sensitivity of the natural CH4 emissions to the current anthropogenic warming. CH4 isotopes (Δ14CH4, δ13C-CH4, and δD-CH4) from ice cores can be used to fingerprint the sources of CH4 increases in the past. We have successfully extracted 6 large volume (>1000kg) ice core samples from Taylor Glacier, Antarctica spanning the Oldest Dryas-Bølling transition ( 14.7ka) - the first abrupt warming and CH4 rise since the Last Glacial Maximum. Among the CH4 isotopes, our Δ 14CH4 data are unique in their ability to unambiguously distinguish between "old" CH4 sources (e.g. marine clathrate, geologic sources, old permafrost) and "modern" CH4 sources (e.g. tropical and boreal wetlands). Our Δ14CH4 data unambiguously rule out marine clathrate and old permafrost as the sources of the abrupt CH4 rise. Preliminary CH4 stable isotopes box modeling combined with interpolar CH4 concentration gradient from existing ice core records suggest that tropical wetlands were the dominant driver for the Oldest Dryas-Bølling CH4 rise.

Reductive transformation of V(iii) precursors into vanadium(ii) oxide nanowires.

PubMed

Ojelere, Olusola; Graf, David; Ludwig, Tim; Vogt, Nicholas; Klein, Axel; Mathur, Sanjay

2018-05-15

Vanadium(ii) oxide nanostructures are promising materials for supercapacitors and electrocatalysis because of their excellent electrochemical properties and high surface area. In this study, new homoleptic vanadium(iii) complexes with bi-dentate O,N-chelating heteroarylalkenol ligands (DmoxCH[double bond, length as m-dash]COCF3, PyCH[double bond, length as m-dash]COCF3 and PyN[double bond, length as m-dash]COCF3) were synthesized and successfully transformed by reductive conversion into VO nanowires. The chemical identity of V(iii) complexes and their redox behaviour were unambiguously established by single crystal X-ray diffraction studies, cyclic voltammetry, spectrometric studies and DFT calculations. Transformation into the metastable VO phase was verified by powder X-ray diffraction and thermo-gravimetry. Transmission electron microscopy and X-ray photoelectron spectroscopy data confirmed the morphology and chemical composition of VO nanostructures, respectively.

Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe 3Mn-Iodosobenzene Adducts

DOE PAGES

de Ruiter, Graham; Carsch, Kurtis M.; Gul, Sheraz; ...

2017-03-24

In this paper, we report the synthesis, characterization, and reactivity of [LFe 3(PhPz) 3OMn( sPhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene–metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2Fe IIMn II vs. Fe III 3Mn II) influence oxygen atom transfer in tetranuclear Fe 3Mn clusters. Finally, in particular, a one-electron redox change atmore » a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.« less

Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3 Mn-Iodosobenzene Adducts.

PubMed

de Ruiter, Graham; Carsch, Kurtis M; Gul, Sheraz; Chatterjee, Ruchira; Thompson, Niklas B; Takase, Michael K; Yano, Junko; Agapie, Theodor

2017-04-18

We report the synthesis, characterization, and reactivity of [LFe 3 (PhPz) 3 OMn( s PhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene-metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57 Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2 Fe II Mn II vs. Fe III 3 Mn II ) influence oxygen atom transfer in tetranuclear Fe 3 Mn clusters. In particular, a one-electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lanthanide-Connecting and Lone-Electron-Pair Active Trigonal-Pyramidal-AsO3 Inducing Nanosized Poly(polyoxotungstate) Aggregates and Their Anticancer Activities

NASA Astrophysics Data System (ADS)

Zhao, Jun-Wei; Li, Hai-Lou; Ma, Xing; Xie, Zhigang; Chen, Li-Juan; Zhu, Yongsheng

2016-05-01

By virtue of the stereochemical effect of the lone-electron pair located on the trigonal-pyramidal-AsO3 groups and the one-pot self-assembly strategy in the conventional aqueous solution, a series of novel lanthanide-bridging and lone-electron-pair active trigonal-pyramidal-AsO3 inducing nanosized poly(polyoxotungstate) aggregates [H2N(CH3)2]6 Na24H16{[Ln10W16(H2O)30O50](B-α-AsW9O33)8}·97H2O [Ln = EuIII (1), SmIII (2), GdIII (3), TbIII (4), DyIII (5), HoIII (6), ErIII (7), TmIII (8)] were prepared and further characterized by elemental analyses, IR spectra, UV spectra, thermogravimetric (TG) analyses and single-crystal X-ray diffraction. The most remarkable structural feature is that the polyanionic skeleton of {[Ln10W16(H2O)30O50](B-α-AsW9O33)8}46- is constructed from eight trivacant Keggin [B-α-AsW9O33]9- fragments through ten Ln centers and sixteen bridging W atoms in the participation of fifty extraneous oxygen atoms. Notably, 4 and 8 can be stable in the aqueous solution not only for eight days but also in the range of pH = 3.9-7.5. Moreover, the cytotoxicity tests of 4 and 8 toward human cervical cancer (HeLa) cells, human breast cancer (MCF-7) cells and mouse fibroblast (L929) cells were performed by the 3-(4,5-cimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) assay and the cell apoptosis processes were characterized by calcein AM/PI staining experiments, annexin V-FITC/PI staining experiments and morphological changes.

Mechanisms of Polymer Curing and Thermal Degradation

DTIC Science & Technology

1979-12-01

respectively. 29 0)- Fi . J . IR S e t u f i ( - 3 E hy y p e o y Ph n l S f n .30 z Iii 41 rI2P6i4000 3500 3000 42500 §200010 6010 2010 0 0 0 0...Polymer X Obs.6(_pm) Obs.(ppmA H 7.9,8.0 g,h 7.8 g,h 7.5 I ,e 7.5 i ,c,2 7.3 b,e 6.0-7.2 b,d,f,j,=CH 7.2 d 7.0 f,j 3.1 a HC C =- T O" 7.9 g 7.9 g 7.3 b...e 7.4 b,e 7.1 d 6.0-7.1 c,d,f,=CH 7.0 f,c 3.1 a 3.1 a aFor X 0 H, ggh, f= i b Based on first-order analysis of multiplets. 37 t TABLE 4. SUMMARY OF 13C

Development of Novel Decontamination Techniques for Chemical Agents (GB, VX, HD) Contaminated Facilities. Phase I. Identification and Evaluation of Novel Decontamination Concepts. Volume 1

DTIC Science & Technology

1983-02-01

ACTIVITY . . . . . . 4 3.0 PHASE I RESULTS . . . . . . . . . . . . . . . . . . . . . . 5 3.1 RESOURCE REVIEW . . . . . . . . . . . . . 5 ŗ.1.1 Surveys...commonly known as mustard, is a vesicant while VX and GB are organophosphorus compounds which act as anticholinesterases . HD Cl-( CH)-S-(CH- );cI 0...order to satisfy the task objective, work during this phase . consisted of three principal interrelated activities . The goal of the first activity was

Synthesis, characterization and luminescence of europium perchlorate with MABA-Si complex and coating structure SiO2 @Eu(MABA-Si) luminescence nanoparticles.

PubMed

Fu, Zhi-Fang; Li, Wen-Xian; Bai, Juan; Bao, Jin-Rong; Cao, Xiao-Fang; Zheng, Yu-Shan

2017-05-01

This article reports a novel category of coating structure SiO 2 @Eu(MABA-Si) luminescence nanoparticles (NPs) consisting of a unique organic shell, composed of perchlorate europium(III) complex, and an inorganic core, composed of silica. The binary complex Eu(MABA-Si) 3 ·(ClO 4 ) 3 ·5H 2 O was synthesized using HOOCC 6 H 4 N(CONH(CH 2 ) 3 Si(OCH 2 CH 3 ) 3 ) 2 (MABA-Si) and was used as a ligand. Furthermore, the as-prepared silica NPs were successfully coated with the -Si(OCH 2 CH 3 ) 3 group of MABA-Si to form Si-O-Si chemical bonds by means of the hydrolyzation of MABA-Si. The binary complexes were characterized by elemental analysis, molar conductivity and coordination titration analysis. The results indicated that the composition of the binary complex was Eu(MABA-Si) 3 ·(ClO 4 ) 3 ·5H 2 O. Coating structure SiO 2 @Eu(MABA-Si) NPs were characterized using transmission electron microscopy (TEM), scanning electron microscopy (SEM) and infrared (IR) spectra. Based on the SEM and TEM measurements, the diameter of core-SiO 2 particles was ~400 and 600 nm, and the thickness of the cladding layer Eu(MABA-Si) was ~20 nm. In the binary complex Eu(MABA-Si) 3 ·(ClO 4 ) 3 ·5H 2 O, the fluorescence spectra illustrated that the energy of the ligand MABA-Si transferred to the energy level for the excitation state of europium(III) ion. Coating structure SiO 2 @Eu(MABA-Si) NPs exhibited intense red luminescence compared with the binary complex. The fluorescence lifetime and fluorescence quantum efficiency of the binary complex and of the coating structure NPs were also calculated. The way in which the size of core-SiO 2 spheres influences the luminescence was also studied. Moreover, the luminescent mechanisms of the complex were studied and explained. Copyright © 2016 John Wiley & Sons, Ltd.

Generic and Brand-Name l-Thyroxine Are Not Bioequivalent for Children With Severe Congenital Hypothyroidism

PubMed Central

Carswell, Jeremi M.; Gordon, Joshua H.; Popovsky, Erica; Hale, Andrea

2013-01-01

Context: In the United States, generic substitution of levothyroxine (l-T4) by pharmacists is permitted if the formulations are deemed to be bioequivalent by the Federal Drug Administration, but there is widespread concern that the pharmacokinetic standard used is too insensitive. Objective: We aimed to evaluate the bioequivalence of a brand-name l-T4 (Synthroid) and an AB-rated generic formulation (Sandoz, Princeton, NJ) in children with severe hypothyroidism. Design: This was a prospective randomized crossover study in which patients received 8 weeks of one l-T4 formulation followed by 8 weeks of the other. Setting: The setting was an academic medical center. Patients: Of 31 children with an initial serum TSH concentration >100 mU/L, 20 had congenital hypothyroidism (CH), and 11 had autoimmune thyroiditis. Main Outcome Measures: The primary endpoint was the serum TSH concentration. Secondary endpoints were the free T4 and total T3 concentrations. Results: The serum TSH concentration was significantly lower after 8 weeks of Synthroid than after generic drug (P = .002), but thyroid hormone levels did not differ significantly. Subgroup analysis revealed that the difference in TSH was restricted to patients with CH (P = .0005). Patients with CH required a higher l-T4 dose (P < .0004) and were younger (P = .003) but were not resistant to thyroid hormone; 15 of 16 CH patients had severe thyroid dysgenesis or agenesis on imaging. The response to generic vs brand-name preparation remained significant when adjusted for age. Conclusions: Synthroid and an AB-rated generic l-T4 are not bioequivalent for patients with severe hypothyroidism due to CH, probably because of diminished thyroid reserve. It would therefore seem prudent not to substitute l-T4 formulations in patients with severe CH, particularly in those <3 yr of age. Our results may have important implications for other severely hypothyroid patients in whom precise titration of l-T4 is necessary. PMID:23264396

Anaerobic methane oxidation in two tropical freshwater systems

NASA Astrophysics Data System (ADS)

Roland, Fleur; Darchambeau, François; Crowe, Sean A.; Borges, Alberto V.

2014-05-01

Lake Kivu is one of the East African Great Lakes. It is located at the border between Rwanda and the Democratic Republic of the Congo. It is a deep meromictic lake characterized by huge amounts of methane (CH4) (60 km3 at 0° C and 1 atm) dissolved in its deep waters. Two thirds of the CH4 originates from anoxic bacterial reduction of dissolved carbon dioxide and one third from anaerobic degradation of settling organic material. CH4 then diffuses slowly from the monimolimnion to surface waters where many is oxidised by methanotrophic microorganisms. In Lake Kivu, this biological oxidation of CH4 could occur with different final electron acceptors: oxygen (aerobic oxidation) but also nitrate (NO3-), nitrite, sulfate (SO42-), iron (Fe) or manganese (Mn) in anaerobic conditions. If the anaerobic oxidation of CH4 (AOM) is generally coupled to SO42- reduction in marine waters, electron acceptors of the AOM were rarely investigated in freshwater systems. Five field campaigns were conducted from 2011 to 2013 during periods with contrasted ventilations of the upper water column. The dry season is characterized by a deeper mixing of surface waters ended by a steep gradient of physico-chemical conditions at the redox interface, while during the rainy season the mixed layer is shallower and ended at its deeper part by a NO3- accumulation zone. Sampling was conducted in the main basin of Lake Kivu but also in a particular sub-basin located northeast of the lake, the Kabuno Bay. Both systems are meromictic but differ in terms of morphometry and geochemistry with a shallower permanent chemocline and higher concentrations of CH4, Fe and Mn in the anoxic waters in Kabuno Bay compared to the main lake. Samples were collected for the measurements of CH4 concentrations and the various potential electron acceptors of the AOM. CH4 oxidation rates were measured along vertical profiles at 5 m and 0.5 m depth intervals respectively in the main basin and Kabuno bay water columns. Results indicate high rates of AOM in both main basin (up to 7 μmol L-1 d-1) and Kabuno bay (up to 16 μmol L-1 d-1). In the main basin, we observed a co-occurrence of the AOM and the SO42- reduction in the dry season. During the rainy season, higher oxidation rates occurred in the NO3- accumulation zone, which is in favour of a coupling between AOM and NO3- reduction. In Kabuno Bay, the higher AOM rates were observed at depths with highest particulate Fe concentrations. Our results suggest that AOM coupled with SO42-reduction may occur during the dry season in the main basin, whereas this oxidation could be coupled with NO3- reduction during the rainy season. In Kabuno Bay, the co-occurrence of the Fe [III] peak with high AOM suggests a coupling between the AOM and Fe reduction.

Asymmetric synthesis of isoindolones by chiral cyclopentadienyl-rhodium(III)-catalyzed C-H functionalizations.

PubMed

Ye, Baihua; Cramer, Nicolai

2014-07-21

Directed Cp*Rh(III)-catalyzed carbon-hydrogen (C-H) bond functionalizations have evolved as a powerful strategy for the construction of heterocycles. Despite their high value, the development of related asymmetric reactions is largely lagging behind due to a limited availability of robust and tunable chiral cyclopentadienyl ligands. Rhodium complexes comprising a chiral Cp ligand with an atropchiral biaryl backbone enables an asymmetric synthesis of isoindolones from arylhydroxamates and weakly alkyl donor/acceptor diazo derivatives as one-carbon component under mild conditions. The complex guides the substrates with a high double facial selectivity yielding the chiral isoindolones in good yields and excellent enantioselectivities. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dry etching, surface passivation and capping processes for antimonide based photodetectors

NASA Astrophysics Data System (ADS)

Dutta, Partha; Langer, Jeffery; Bhagwat, Vinay; Juneja, Jasbir

2005-05-01

III-V antimonide based devices suffer from leakage currents. Surface passivation and subsequent capping of the surfaces are absolutely essential for any practical applicability of antimonide based devices. The quest for a suitable surface passivation technology is still on. In this paper, we will present some of the promising recent developments in this area based on dry etching of GaSb based homojunction photodiodes structures followed by various passivation and capping schemes. We have developed a damage-free, universal dry etching recipe based on unique ratios of Cl2/BCl3/CH4/Ar/H2 in ECR plasma. This novel dry plasma process etches all III-V compounds at different rates with minimal damage to the side walls. In GaSb based photodiodes, an order of magnitude lower leakage current, improved ideality factor and higher responsivity has been demonstrated using this recipe compared to widely used Cl2/Ar and wet chemical etch recipes. The dynamic zero bias resistance-area product of the Cl2/BCl3/CH4/Ar/H2 etched diodes (830 Ω cm2) is higher than the Cl2/Ar (300 Ω cm2) and wet etched (330 Ω cm2) diodes. Ammonium sulfide has been known to passivate surfaces of III-V compounds. In GaSb photodiodes, the leakage current density reduces by a factor of 3 upon sulfur passivation using ammonium sulfide. However, device performance degrades over a period of time in the absence of any capping or protective layer. Silicon Nitride has been used as a cap layer by various researchers. We have found that by using silicon nitride caps, the devices exhibit higher leakage than unpassivated devices probably due to plasma damage during SiNx deposition. We have experimented with various polymers for capping material. It has been observed that ammonium sulfide passivation when combined with parylene capping layer (150 Å), devices retain their improved performance for over 4 months.

Job Samples as Tank Gunnery Performance Predictors

DTIC Science & Technology

1980-09-01

previously been obtained ( Maitland , Eaton, and Neff, 1980). Table VI-M. The Table VI-M order of firing and engagement techniques used in Phase III were the... Maitland , Eaton, and Neff (1980) *** <.001 22 Sen 21 ’ )a. datz obtained from ch4 sensing cask was quanti:ied. as in Phase It, by Coti.purtirg the vie.i...of four test weighting methods in multiple regression. Educational and Psychological Measure- ment, 1959, 19, 103-114. Maitland , A. J., Eaton, N. K

Refining of Military Jet Fuels from Shale Oil. Part III. Pilot Plant Sample Preparation.

DTIC Science & Technology

1982-07-01

product gas composition, regen- erator flue gas composition, and carbon contents of the spent and regenerated catalysts were also monitored for...product. Gas samples were collected at eight-hour intervals from the reactor product gas and regenerator flue gas streams and analyzed for material balance...Isobutane C4= Butylene C5 Pentane C5s Pentane and Pentenes I+ C5+, >C5 Compounds Heavier than Pentane in Gas .* Streams C6 Hexane C/H Carbon-to

Reaction pathways of producing and losing particles in atmospheric pressure methane nanosecond pulsed needle-plane discharge plasma

NASA Astrophysics Data System (ADS)

Zhao, Yuefeng; Wang, Chao; Li, Li; Wang, Lijuan; Pan, Jie

2018-03-01

In this work, a two-dimensional fluid model is built up to numerically investigate the reaction pathways of producing and losing particles in atmospheric pressure methane nanosecond pulsed needle-plane discharge plasma. The calculation results indicate that the electron collisions with CH4 are the key pathways to produce the neutral particles CH2 and CH as well as the charged particles e and CH3+. CH3, H2, H, C2H2, and C2H4 primarily result from the reactions between the neutral particles and CH4. The charge transfer reactions are the significant pathways to produce CH4+, C2H2+, and C2H4+. As to the neutral species CH and H and the charged species CH3+, the reactions between themselves and CH4 contribute to substantial losses of these particles. The ways responsible for losing CH3, H2, C2H2, and C2H4 are CH3 + H → CH4, H2 + CH → CH2 + H, CH4+ + C2H2 → C2H2+ + CH4, and CH4+ + C2H4 → C2H4+ + CH4, respectively. Both electrons and C2H4+ are consumed by the dissociative electron-ion recombination reactions. The essential reaction pathways of losing CH4+ and C2H2+ are the charge transfer reactions.

Objective Cough Frequency, Airway Inflammation, and Disease Control in Asthma.

PubMed

Marsden, Paul A; Satia, Imran; Ibrahim, Baharudin; Woodcock, Ashley; Yates, Lucy; Donnelly, Iona; Jolly, Lisa; Thomson, Neil C; Fowler, Stephen J; Smith, Jaclyn A

2016-06-01

Cough is recognized as an important troublesome symptom in the diagnosis and monitoring of asthma. Asthma control is thought to be determined by the degree of airway inflammation and hyperresponsiveness but how these factors relate to cough frequency is unclear. The goal of this study was to investigate the relationships between objective cough frequency, disease control, airflow obstruction, and airway inflammation in asthma. Participants with asthma underwent 24-h ambulatory cough monitoring and assessment of exhaled nitric oxide, spirometry, methacholine challenge, and sputum induction (cell counts and inflammatory mediator levels). Asthma control was assessed by using the Global Initiative for Asthma (GINA) classification and the Asthma Control Questionnaire (ACQ). The number of cough sounds was manually counted and expressed as coughs per hour (c/h). Eighty-nine subjects with asthma (mean ± SD age, 57 ± 12 years; 57% female) were recruited. According to GINA criteria, 18 (20.2%) patients were classified as controlled, 39 (43.8%) partly controlled, and 32 (36%) uncontrolled; the median ACQ score was 1 (range, 0.0-4.4). The 6-item ACQ correlated with 24-h cough frequency (r = 0.40; P < .001), and patients with uncontrolled asthma (per GINA criteria) had higher median 24-h cough frequency (4.2 c/h; range, 0.3-27.6) compared with partially controlled asthma (1.8 c/h; range, 0.2-25.3; P = .01) and controlled asthma (1.7 c/h; range, 0.3-6.7; P = .002). Measures of airway inflammation were not significantly different between GINA categories and were not correlated with ACQ. In multivariate analyses, increasing cough frequency and worsening FEV1 independently predicted measures of asthma control. Ambulatory cough frequency monitoring provides an objective assessment of asthma symptoms that correlates with standard measures of asthma control but not airflow obstruction or airway inflammation. Moreover, cough frequency and airflow obstruction represent independent dimensions of asthma control. Copyright © 2016 American College of Chest Physicians. Published by Elsevier Inc. All rights reserved.

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

PubMed

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

2005-06-27

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

Separation of lanthanides and actinides using magnetic silica particles bearing covalently attached tetra-CMPO-calix[4]arenes.

PubMed

Böhmer, Volker; Dozol, Jean-François; Grüttner, Cordula; Liger, Karine; Matthews, Susan E; Rudershausen, Sandra; Saadioui, Mohamed; Wang, Pingshan

2004-08-21

Calix[4]arene tetraethers in the cone conformation bearing four -NH-CO-CH2-P(O)Ph2 (= CMPO) residues on their wide rim and one, two or four omega-amino alkyl residues of various lengths at the narrow rim were synthesized. Reaction with dichlorotriazinyl (DCT) functionalized magnetic particles led to complete coverage of the available surface by covalently linked CMPO-calix[4]arenes in all cases. Magnetically assisted removal of Eu(iii) and Am(iii) from acidic solutions was distinctly more efficient with these particles in comparison to analogous particles bearing the same amount of analogous single-chain CMPO-functions. The best result, an increase of the extraction efficiency by a factor of 140-160, was obtained for attachment via two propyl spacers. The selectivity Am/Eu was in the range of 1.9-2.8. No decrease of the extraction ability was observed, when the particles were repeatedly used, after simple back extraction with water.

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 column density of solid CH_4_ would be 0.3-4% of solid H_2_O, indicating that solid CH_4_ consumes 0.5+/-0.3% of the cosmic carbon abundance. A gaseous origin would imply a column density of at least this amount, being highly dependent on the assumed temperature of the absorbing gas. A second absorption feature is detected toward W 33A and NGC 7538 : IRS1 at 7.58 μm. The peak position and width of this feature are consistent with the ν_3_ mode of solid SO_2_ in a matrix of solid CH_3_OH or pure SO_2_. The derived column density is 0.1-1% of solid H_2_O, indicating that solid SO_2_ locks up 0.6-6% of the cosmic sulfur abundance. This study shows that 7-8μm spectroscopy of dense molecular clouds, using new airborne and space-based platforms, will provide valuable information on the composition of icy grain mantles and molecular cloud chemistry.

Effect of organic-matter type and thermal maturity on methane adsorption in shale-gas systems

USGS Publications Warehouse

Zhang, Tongwei; Ellis, Geoffrey S.; Ruppel, Stephen C.; Milliken, Kitty; Yang, Rongsheng

2012-01-01

A series of methane (CH4) adsorption experiments on bulk organic rich shales and their isolated kerogens were conducted at 35 °C, 50 °C and 65 °C and CH4 pressure of up to 15 MPa under dry conditions. Samples from the Eocene Green River Formation, Devonian–Mississippian Woodford Shale and Upper Cretaceous Cameo coal were studied to examine how differences in organic matter type affect natural gas adsorption. Vitrinite reflectance values of these samples ranged from 0.56–0.58 %Ro. In addition, thermal maturity effects were determined on three Mississippian Barnett Shale samples with measured vitrinite reflectance values of 0.58, 0.81 and 2.01 %Ro. For all bulk and isolated kerogen samples, the total amount of methane adsorbed was directly proportional to the total organic carbon (TOC) content of the sample and the average maximum amount of gas sorption was 1.36 mmol of methane per gram of TOC. These results indicate that sorption on organic matter plays a critical role in shale-gas storage. Under the experimental conditions, differences in thermal maturity showed no significant effect on the total amount of gas sorbed. Experimental sorption isotherms could be fitted with good accuracy by the Langmuir function by adjusting the Langmuir pressure (PL) and maximum sorption capacity (Γmax). The lowest maturity sample (%Ro = 0.56) displayed a Langmuir pressure (PL) of 5.15 MPa, significantly larger than the 2.33 MPa observed for the highest maturity (%Ro > 2.01) sample at 50 °C. The value of the Langmuir pressure (PL) changes with kerogen type in the following sequence: type I > type II > type III. The thermodynamic parameters of CH4 adsorption on organic rich shales were determined based on the experimental CH4 isotherms. For the adsorption of CH4 on organic rich shales and their isolated kerogen, the heat of adsorption (q) and the standard entropy (Δs0) range from 7.3–28.0 kJ/mol and from −36.2 to −92.2 J/mol/K, respectively.

78 FR 27078 - Native American Graves Protection and Repatriation Act Regulations

Federal Register 2010, 2011, 2012, 2013, 2014

2013-05-09

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Temporal variability of methane fluxes in West Siberian taiga bogs and its implications for estimating regional methane emission

NASA Astrophysics Data System (ADS)

Sabrekov, Alexander; Ilyasov, Danil; Terentieva, Irina; Glagolev, Mikhail; Maksyutov, Shamil

2017-04-01

The West Siberia Lowland (WSL) is the biggest peatland area in Eurasia and is situated in the high latitudes experiencing enhanced rate of climate change. During 2015-16 summer periods, seasonal measurements of methane emission were made at the field station «Mukhrino» in the WSL middle taiga zone. The study was made at 3 wetland ecosystem types covering 80% of the taiga wetland area: i) waterlogged hollows or depressed areas with water level above the moss surface, ii) oligotrophic hollows or depressed parts of bogs with water level beneath the moss surface, iii) forested bogs with dwarf shrubs-sphagnum vegetation. Seven series of measurements were made by a static chamber method in 2016 and four series - in 2015. In 2015, we observed non-typical weather conditions including early dry spring and short cold rainy summer. Oppositely, weather conditions in 2016 were closer to average long-term with warmer drier summer. Significant difference between these years allowed analyzing the temporal variability and its sources. Average methane flux rates from forested bogs were 0.57 mgCH4/m2/h in 2016 and 0.33 mgCH4/m2/h in 2015. Seasonal dynamic during both years had similar concave downward shape. The highest fluxes were observed in June and were corresponded to the highest WTL, the main limiting factor of emission from forested bogs. The lowest fluxes in July were related to the low WTL combining with the highest temperature of upper methanotrophy layer. Average methane flux rates from oligotrophic hollows were 7.18 mgCH4/m2/h in 2016 and 4.28 mgCH4/m2/h in 2015. Seasonal dynamic of methane emission was indistinct in 2015. On the contrary, in 2016 it had regular seasonal pattern with peak emissions in July, which were four times higher than in 2015. WTL was not the limiting factor for CH4 emission from oligotrophic hollows, because even in the driest ones it was only 10 cm below the surface. Thus, the difference between peak emissions in 2015 and 2016 was mainly related to the temperature, which was considerably higher in 2016. Average methane flux rates from waterlogged hollows were 2.19 mgCH4/m2/h in 2016 and 4.07 mgCH4/m2/h in 2015. Seasonal dynamic had prominent shape in both years, however, peak emissions were observed in different months. Overall, patterns of emission in these ecosystems had more complicate nature and needs future investigations. Regional methane emission was estimated using new wetland map by Terentieva et al. (2016). Seasonal dynamic data for 2015-16 years gave the regional flux of 161 and 1257 ktCH4/yr for forested bogs and oligotrophic hollows, respectively. Similar values were obtained using not seasonal dynamic but only flux medians for 2015-16 years. However, the usage of old dataset gave only 32 and 841 ktCH4/yr for forested bogs and oligotrophic hollows, respectively. Thus, seasonal dynamics data had lower impact on regional methane emission estimate comparing to interannual variability data. Terentieva, I.E., Glagolev, M.V., Lapshina, E.D., Sabrekov, A.F., Maksyutov, S. Mapping of West Siberian taiga wetland complexes using Landsat imagery: implications for methane emissions // Biogeosciences. 2016. V. 13. № 16. P. 4615-4626.

Ion abundances and implications for photochemistry in Comets Halley (1986 III) and Bradfield (1987 XXIX)

NASA Astrophysics Data System (ADS)

Lutz, B. L.; Womack, M.; Wagner, R. M.

1993-04-01

The Ohio State University Image Dissector Scanner on the Perkins 1.8-m telescope at the Lowell Observatory was used to record spectra of the plasma tails of Comets P/Halley (1986 III) and P/Bradfield (1987 XXIX, also 1987s). The ionic species CO(+), N2(+), CH(+), and H2O(+) were identified in these spectra, and column densities for them were calculated from measured fluxes. The observed N2(+)/H2O(+) ratios are at least an order of magnitude lower and the observed CH(+)/H2O(+) ratios are a factor of 100 higher than theoretical results. The abundance ratio N2/CO was derived in the plasma tail of Bradfield from N2(+) and CO(+) data, and found to be an order of magnitude higher than a value measured in Halley. The relative ion abundances of CH(+), N2(+), CO(+), and H2O(+) in Halley are consistent with in situ measurements obtained from the Giotto spacecraft.

Impact of a new wavelength-dependent representation of methane photolysis branching ratios on the modeling of Titan’s atmospheric photochemistry

NASA Astrophysics Data System (ADS)

Gans, B.; Peng, Z.; Carrasco, N.; Gauyacq, D.; Lebonnois, S.; Pernot, P.

2013-03-01

A new wavelength-dependent model for CH4 photolysis branching ratios is proposed, based on the values measured recently by Gans et al. (Gans, B. et al. [2011]. Phys. Chem. Chem. Phys. 13, 8140-8152). We quantify the impact of this representation on the predictions of a photochemical model of Titan’s atmosphere, on their precision, and compare to earlier representations. Although the observed effects on the mole fraction of the species are small (never larger than 50%), it is possible to draw some recommendations for further studies: (i) the Ly-α branching ratios of Wang et al. (Wang, J.H. et al. [2000]. J. Chem. Phys. 113, 4146-4152) used in recent models overestimate the CH2:CH3 ratio, a factor to which a lot of species are sensitive; (ii) the description of out-of-Ly-α branching ratios by the “100% CH3” scenario has to be avoided, as it can bias significantly the mole fractions of some important species (C3H8); and (iii) complementary experimental data in the 130-140 nm range would be useful to constrain the models in the Ly-α deprived 500-700 km altitude range.

Structure-activity relationships in cytotoxic Au(I)/Au(III) complexes derived from 2-(2'-pyridyl)benzimidazole.

PubMed

Maiore, Laura; Aragoni, Maria Carla; Deiana, Carlo; Cinellu, Maria Agostina; Isaia, Francesco; Lippolis, Vito; Pintus, Anna; Serratrice, Maria; Arca, Massimiliano

2014-04-21

Gold(I) and gold(III) complexes derived from 2-(2'-pyridyl)benzimidazole (pbiH) were proven to be a promising class of in vitro antitumor agents against A2780 human ovarian cancer cells. In this paper, a comparative electrochemical, UV-vis absorption, and emission spectroscopic investigation is reported on pbiH, the two mononuclear Au(III) complexes [(pbi)AuX2] (X = Cl (1), AcO (2)), the four mononuclear Au(I) derivatives [(pbiH)AuCl] (3), [(pbiH)Au(PPh3)]PF6 ((4(+))(PF6(-))), [(pbi)Au(PPh3)] (5), and [(pbi)Au(TPA)] (6), the three mixed-valence Au(III)/Au(I) complexes [(μ-pbi)Au2Cl3] (7), [(Ph3P)Au(μ-pbi)AuX2]PF6 (X = Cl ((8(+))(PF6(-))), AcO ((9(+))(PF6(-)))), and the binuclear Au(I)-Au(I) compound [(μ-pbi)Au2(PPh3)2]PF6 ((10(+))(PF6(-))). All complexes feature irreversible reduction processes related to the Au(III)/Au(I) or Au(I)/Au(0) processes and peculiar luminescent emission at about 360-370 nm in CH2Cl2, with quantum yields that are remarkably lower ((0.7-14.5) × 10(-2)) in comparison to that determined for the free pbiH ligand (31.5 × 10(-2)) in the same solvent. The spectroscopic and electrochemical properties of all complexes were interpreted on the grounds of time-dependent PBE0/DFT calculations carried out both in the gas phase and in CH2Cl2 implicitly considered within the IEF-PCM SCRF approach. The electronic structure of the complexes, and in particular the energy and composition of the Kohn-Sham LUMOs, can be related to the antiproliferative properties against the A2780 ovarian carcinoma cell line, providing sound quantitative structure-activity relationships and shedding a light on the role played by the global charge and nature of ancillary ligands in the effectiveness of Au-based antitumor drugs.

Anaerobic oxidation of methane in sediments of two boreal lakes

NASA Astrophysics Data System (ADS)

Rissanen, Antti J.; Karvinen, Anu; Nykänen, Hannu; Mpamah, Promise; Peura, Sari; Tiirola, Marja; Kankaala, Paula

2014-05-01

Anaerobic oxidation of methane (AOM) is a considerable sink for methane (CH4) in marine systems, but very little is known about the occurrence and importance of the process in freshwater systems. In addition, much about the microbial communities involved in AOM is unclear. AOM coupled with sulfate reduction is the dominant AOM process in marine systems but the scarce existing data suggest that, in freshwater systems, AOM coupled with reduction of alternative electron acceptors (nitrate/nitrite, manganese, iron) is more important. In this study, potential for AOM coupled with metal reduction was studied in boreal lake sediments. Slurries of sediment samples collected from two sites in southeastern Finland, i.e. from Lake Orivesi, Heposelkä, an vegetated littoral site, dominated by Phragmites australis (Sample Sa, sediment layer 0 - 25 cm) and from the profundal zone of a mesotrophic Lake Ätäskö (Aa, 0 - 10 cm; Ab, 10 - 30 cm; Ac, 90 - 130 cm), were incubated in laboratory in anaerobic conditions at in situ temperatures for up to 5 months. The samples were amended either 1) with 13CH4, 2) 13CH4 + manganese(II) oxide (MnO) or 3) 13CH4 + iron(III) hydroxide (Fe(OH)3), and the processes were measured by following the 13C transfer to the carbon dioxide (CO2) pool and by concentration measurements of CH4 and CO2. Changes in microbial communities were studied from DNA extracted from sediment samples before and after incubation period by next-generation sequencing (Ion Torrent) of polymerase chain reaction (PCR) - amplified bacterial and archaeal 16S rRNA and methyl coenzyme-M reductase gene (mcrA) amplicons. Increase in 13C of CO2 gas confirmed that AOM took place in sediments of both study lakes. In general, 13CO2 - production was significant both at the beginning (0 - 21 days) and at the end (84 - 151 days) of incubation period. Potential AOM rates (calculated based on 13CO2 - production) varied considerably and were much lower in deep sediment (Sample Ac), 0.1 - 0.2 nmol CH4 d-1gwetsediment-1, than in surface sediment samples (Samples Aa, Ab and Sa), 0.2 - 12.3 nmol CH4 d-1gwetsediment-1. AOM took place without metal additions in every sample type. Addition of MnO increased potential AOM rates in surface sediment samples but not in deep sediment samples. Addition of Fe(OH)3increased AOM significantly only in Aa samples. Molecular microbiological analyses are currently in progress and the results will be shown in the poster presentation.

Effects of seasonality, transport pathway, and spatial structure on greenhouse gas fluxes in a restored wetland.

PubMed

McNicol, Gavin; Sturtevant, Cove S; Knox, Sara H; Dronova, Iryna; Baldocchi, Dennis D; Silver, Whendee L

2017-07-01

Wetlands can influence global climate via greenhouse gas (GHG) exchange of carbon dioxide (CO 2 ), methane (CH 4 ), and nitrous oxide (N 2 O). Few studies have quantified the full GHG budget of wetlands due to the high spatial and temporal variability of fluxes. We report annual open-water diffusion and ebullition fluxes of CO 2 , CH 4 , and N 2 O from a restored emergent marsh ecosystem. We combined these data with concurrent eddy-covariance measurements of whole-ecosystem CO 2 and CH 4 exchange to estimate GHG fluxes and associated radiative forcing effects for the whole wetland, and separately for open-water and vegetated cover types. Annual open-water CO 2 , CH 4 , and N 2 O emissions were 915 ± 95 g C-CO 2  m -2  yr -1 , 2.9 ± 0.5 g C-CH 4  m -2  yr -1 , and 62 ± 17 mg N-N 2 O m -2  yr -1 , respectively. Diffusion dominated open-water GHG transport, accounting for >99% of CO 2 and N 2 O emissions, and ~71% of CH 4 emissions. Seasonality was minor for CO 2 emissions, whereas CH 4 and N 2 O fluxes displayed strong and asynchronous seasonal dynamics. Notably, the overall radiative forcing of open-water fluxes (3.5 ± 0.3 kg CO 2 -eq m -2  yr -1 ) exceeded that of vegetated zones (1.4 ± 0.4 kg CO 2 -eq m -2  yr -1 ) due to high ecosystem respiration. After scaling results to the entire wetland using object-based cover classification of remote sensing imagery, net uptake of CO 2 (-1.4 ± 0.6 kt CO 2 -eq yr -1 ) did not offset CH 4 emission (3.7 ± 0.03 kt CO 2 -eq yr -1 ), producing an overall positive radiative forcing effect of 2.4 ± 0.3 kt CO 2 -eq yr -1 . These results demonstrate clear effects of seasonality, spatial structure, and transport pathway on the magnitude and composition of wetland GHG emissions, and the efficacy of multiscale flux measurement to overcome challenges of wetland heterogeneity. © 2017 John Wiley & Sons Ltd.

Synthesis, characterization, and reactivity studies of heterodinuclear complexes modeling active sites in purple acid phospatases.

PubMed

Jarenmark, Martin; Haukka, Matti; Demeshko, Serhiy; Tuczek, Felix; Zuppiroli, Luca; Meyer, Franc; Nordlander, Ebbe

2011-05-02

To model the heterodinuclear active sites in plant purple acid phosphatases, a mononuclear synthon, [Fe(III)(H(2)IPCPMP)(Cl(2))][PF(6)] (1), has been generated in situ from the ligand 2-(N-isopropyl-N-((2-pyridyl)methyl)aminomethyl)-6-(N-(carboxylmethyl)-N-((2-pyridyl)methyl)amino methyl)-4-methylphenol (IPCPMP) and used to synthesize heterodinuclear complexes of the formulas [Fe(III)M(II)(IPCPMP)(OAc)(2)(CH(3)OH)][PF(6)] (M = Zn (2), Co (3), Ni (4), Mn (5)), [Fe(III)Zn(II)(IPCPMP)(mpdp)][PF(6)] (6) (mpdp = meta-phenylene-dipropionate), and [Fe(III)Cu(II)(IPCPMP) (OAc)}(2)(μ-O)][PF(6)] (7). Complexes 2-4, 6, and 7 have been crystallographically characterized. The structure of 6 is a solid state coordination polymer with heterodinuclear monomeric units, and 7 is a tetranuclear complex consisting of two heterodinuclear phenolate-bridged Fe(III)Cu(II) units bridged through a μ-oxido group between the two Fe(III) ions. Mössbauer spectra confirm the presence of high spin Fe(III) in an octahedral environment for 1, 3, and 5 while 2 and 4 display relaxation effects. Magnetic susceptibility measurements indicate weak antiferromagnetic coupling for 3, 4, and 5 and confirm the assignment of the metal centers in 2-5 as high spin Fe(III)-M(II) (M = Zn, Co (high spin), Ni (high spin), Mn (high spin)). Complexes 2-5 are intact in acetonitrile solution as indicated by IR spectroscopy (for 2-4) and electrospray ionization mass spectrometry (ESI-MS) but partly dissociate to hydroxide species and a mononuclear complex in water/acetonitrile solutions. UV-vis spectroscopy reveal pH-dependent behavior, and species that form upon increasing the pH have been assigned to μ-hydroxido-bridged Fe(III)M(II) complexes for 2-5 although 2 and 3 is further transformed into what is propsed to be a μ-oxido-bridged tetranuclear complex similar to 7. Complexes 2-5 enhance phosphodiester cleavage of 2-hydroxy-propyl-p-nitrophenyl phosphate (HPNP) and bis(2,4-dinitrophenyl)phosphate (BDNPP), but the reactivities are different for different complexes and generally show strong pH dependence. © 2011 American Chemical Society

Methods for Finding Legacy Wells in Residential and Commercial Areas

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

Hammack, Richard; Veloski, Garret

2016-06-06

The objective of this study was to locate legacy wells in Versailles Borough so that the Pennsylvania Department of Environmental Protection could mitigate dangerous CH 4 concentrations in the community by venting or plugging leaking wells.

Equipment Decisions: Micros, Terminals, or Typewriters.

ERIC Educational Resources Information Center

Swanson, Jean C.

1986-01-01

Discusses factors to be considered when deciding whether to buy typewriters, terminals, or microcomputers for the school typing room. Factors include (1) objectives of the typewriting program, (2) market needs, (3) student learning methods, (4) costs, and (5) instructional materials. (CH)

Multireversible redox processes in pentanuclear bis(triple-helical) manganese complexes featuring an oxo-centered triangular {Mn(II)2Mn(III)(μ3-O)}5+ or {Mn(II)Mn(III)2(μ3-O)}6+ core wrapped by two {Mn(II)2(bpp)3}-.

PubMed

Romain, Sophie; Rich, Jordi; Sens, Cristina; Stoll, Thibaut; Benet-Buchholz, Jordi; Llobet, Antoni; Rodriguez, Montserrat; Romero, Isabel; Clérac, Rodolphe; Mathonière, Corine; Duboc, Carole; Deronzier, Alain; Collomb, Marie-Noëlle

2011-09-05

A new pentanuclear bis(triple-helical) manganese complex has been isolated and characterized by X-ray diffraction in two oxidation states: [{Mn(II)(μ-bpp)(3)}(2)Mn(II)(2)Mn(III)(μ-O)](3+) (1(3+)) and [{Mn(II)(μ-bpp)(3)}(2)Mn(II)Mn(III)(2)(μ-O)](4+) (1(4+)). The structure consists of a central {Mn(3)(μ(3)-O)} core of Mn(II)(2)Mn(III) (1(3+)) or Mn(II)Mn(III)(2) ions (1(4+)) which is connected to two apical Mn(II) ions through six bpp(-) ligands. Both cations have a triple-stranded helicate configuration, and a pair of enantiomers is present in each crystal. The redox properties of 1(3+) have been investigated in CH(3)CN. A series of five distinct and reversible one-electron waves is observed in the -1.0 and +1.50 V potential range, assigned to the Mn(II)(4)Mn(III)/Mn(II)(5), Mn(II)(3)Mn(III)(2)/Mn(II)(4)Mn(III), Mn(II)(2)Mn(III)(3)/Mn(II)(3)Mn(III)(2), Mn(II)Mn(III)(4)/Mn(II)(2)Mn(III)(3), and Mn(III)(5)/Mn(II)Mn(III)(4) redox couples. The two first oxidation processes leading to Mn(II)(3)Mn(III)(2) (1(4+)) and Mn(II)(2)Mn(III)(3) (1(5+)) are related to the oxidation of the Mn(II) ions of the central core and the two higher oxidation waves, close in potential, are thus assigned to the oxidation of the two apical Mn(II) ions. The 1(4+) and 1(5+) oxidized species and the reduced Mn(4)(II) (1(2+)) species are quantitatively generated by bulk electrolyses demonstrating the high stability of the pentanuclear structure in four oxidation states (1(2+) to 1(5+)). The spectroscopic characteristics (X-band electron paramagnetic resonance, EPR, and UV-visible) of these species are also described as well as the magnetic properties of 1(3+) and 1(4+) in solid state. The powder X- and Q-band EPR signature of 1(3+) corresponds to an S = 5/2 spin state characterized by a small zero-field splitting parameter (|D| = 0.071 cm(-1)) attributed to the two apical Mn(II) ions. At 40 K, the magnetic behavior is consistent for 1(3+) with two apical S = 5/2 {Mn(II)(bpp)(3)}(-) and one S = 2 noninteracting spins (11.75 cm(3) K mol(-1)), and for 1(4+) with three S = 5/2 noninteracting spins (13.125 cm(3) K mol(-1)) suggesting that the {Mn(II)(2)Mn(III)(μ(3)-O)}(5+) and {Mn(II)Mn(III)(2)(μ(3)-O)}(6+) cores behave at low temperature like S = 2 and S = 5/2 spin centers, respectively. The thermal behavior below 40 K highlights the presence of intracomplex magnetic interactions between the two apical spins and the central core, which is antiferromagnetic for 1(3+) leading to an S(T) = 3 and ferromagnetic for 1(4+) giving thus an S(T) = 15/2 ground state.

Methane oxidation associated to submerged brown-mosses buffers methane emissions from Siberian polygonal peatlands

NASA Astrophysics Data System (ADS)

Liebner, Susanne; Zeyer, Josef; Knoblauch, Christian

2010-05-01

Circumpolar peatlands store roughly 18 % of the globally stored carbon in soils [based on 1, 2]. Also, northern wetlands and tundra are a net source of methane (CH4), an effective greenhouse gas (GHG), with an estimated annual CH4 release of 7.2% [3] or 8.1% [4] of the global total CH4 emission. Although it is definite that Arctic tundra significantly contributes to the global methane emissions in general, regional variations in GHG fluxes are enormous. CH4 fluxes of polygonal tundra within the Siberian Lena Delta, for example, were reported to be low [5, 6], particularly at open water polygonal ponds and small lakes [7] which make up around 10 % of the delta's surface. Low methane emissions from polygonal ponds oppose that Arctic permafrost thaw ponds are generally known to emit large amounts of CH4 [8]. Combining tools of biogeochemistry and molecular microbiology, we identified sinks of CH4 in polygonal ponds from the Lena Delta that were not considered so far in GHG studies from Arctic wetlands. Pore water CH4 profiling in polygonal ponds on Samoylov, a small island in the central part of the Lena Delta, revealed a pronounced zone of CH4 oxidation near the vegetation surface in submerged layers of brown-mosses. Here, potential CH4 oxidation was an order of magnitude higher than in non-submerged mosses and in adjacent bulk soil. We could additionally show that this moss associated methane oxidation (MAMO) is hampered when exposure of light is prevented. Shading of plots with submerged Scorpidium scorpioides inhibited MAMO leading to higher CH4 concentrations and an increase in CH4 fluxes by a factor of ~13. Compared to non-submerged mosses, the submerged mosses also showed significantly lower δ13C values indicating that they use carbon dioxide derived from methane oxidation for photosynthesis. Applying stable isotope probing of DNA, type II methanotrophs were identified to be responsible for the oxidation of CH4 in the submerged Scorpidium scorpioides. Our study gives first evidence for MAMO in submerged brown-mosses and in the oligotrophic polygonal peatlands of the Lena Delta. It shows that MAMO might effectively reduce methane fluxes to the atmosphere also in Arctic GHG emission hot spots. References: [1] Zhang, T., Barry, R.G., Knowles, K., Heginbottom, J.A., and Brown, J. (1999) Statistics and characteristics of permafrost and ground-ice distribution in the Northern Hemisphere. Polar Geography 23(2): 132-154 [2] Schuur, E.A.G., Bockheim, J., Candell, J.G., Euskirchen, E., Field, C.B., Goryachkin, S.V., Hagemann, S., Kuhry, P., Lafleur, P.M., Lee, H., Mazhitova, G., Nelson, F.E., Rinke, A., Romanovsky, V., Shiklomanov, N., Tarnocai, C., Venevsky, S., Vogel, J., and Zimov, S. (2008) Vulnerability of Permafrost Carbon to Climate Change: Implications for the Global Carbon Cycle. BioScience 58 (8): 701-714 [3] Denman, K.L., Brasseur G., Chidthaisong A., Ciais, P., Cox, P.M., Dickinson, R.E., Hauglustaine, D., Heinze, C., Holland, E., Jacob, D., Lohmann, U., Ramachandran, S., da Silva Dias, P.L., Wofsy, S.C., and Zhang, X. (2007) Couplings Between Changes in the Climate System and Biogeochemistry. In: Climate Change 2007: The Physical Science Basis. Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change [Solomon, S., D. Qin, M. Manning, Z. Chen, M. Marquis, K.B. Averyt, M.Tignor and H.L. Miller (eds.)]. Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA [4] Wuebbles, J., and Hayhoe, K. (2002) Atmospheric methane and global change. Earth-Science Reviews 57: 177-210 [5] Sachs, T., Wille, C., Boike, J., and Kutzbach, L. (2008) Environmental controls on ecosystem-scale CH4 emission from polygonal tundra in the Lena River Delta, Siberia. Journal of Geophysical Research 113: G00A03 [6] Wille, C., Kutzbach, L., Sachs, T., Wagner, D., and Pfeiffer, E.M. (2008) Methane emissions from Siberian arctic polygonal tundra: Eddy covariance measurements and modeling. Global Change Biology 14: 1395-1408 [7] Schneider, J., Grosse, G., and Wagner, D. (2009) Land cover classification of tundra environments in the Arctic Lena Delta based on Landsat 7 ETM+ data and its application for upscaling of methane emissions. Remote Sensing of Environment 113: 380-391 [8] Walter, K.M., Edwards, M.E., Grosse, G., Zimov, S.A., and Chapin III, F.S. (2007) Thermokarst Lakes as a Source of Atmospheric CH4 During the Last Deglaciation. Science 318: 633-636

Low complements and high titre of anti-Sm antibody as predictors of histopathologically proven silent lupus nephritis without abnormal urinalysis in patients with systemic lupus erythematosus.

PubMed

Ishizaki, Jun; Saito, Kazuyoshi; Nawata, Masao; Mizuno, Yasushi; Tokunaga, Mikiko; Sawamukai, Norifumi; Tamura, Masahito; Hirata, Shintaro; Yamaoka, Kunihiro; Hasegawa, Hitoshi; Tanaka, Yoshiya

2015-03-01

The aim of this study was to clarify the clinical characteristics and predictors of silent LN (SLN), a type of LN in SLE without abnormal urinalysis or renal impairment. Of 182 patients who underwent renal biopsy, 48 did not present with abnormal urinalysis or renal impairment at the time of biopsy. The patients with LN (SLN group, n = 36) and those without LN (non-LN group, n = 12) were compared with respect to their baseline characteristics. Bivariate analysis comprised Fisher's exact test and the Mann-Whitney test, whereas multivariate analysis employed binomial logistic regression analysis. LN was histopathologically identified in 36 of 48 patients. According to the International Society of Nephrology/Renal Pathology Society classification, 72% of the SLN patients were classified as having class I/II, with a further 17% having class III/IV. Bivariate analyses indicated that platelet count, serum albumin, complement components (C3 and C4), complement haemolytic activity (CH50), anti-Sm antibody titre and anti-ribonucleoprotein antibody titre were significantly different between groups. Multivariate analysis indicated that CH50 and C3 titres were significantly lower in the SLN group, whereas anti-Sm antibody titre was significantly higher. The cut-off titre, calculated based on the receiver operating characteristic curve for CH50, was 33 U/ml, with a sensitivity and specificity of 89% and 83%, respectively. The cut-off titre for anti-Sm antibodies was 9 U/ml, with a sensitivity and specificity of 74% and 83%, respectively. Low titres of CH50 and C3 and a high titre of anti-Sm antibody were identified as predictors of SLN. © The Author 2014. Published by Oxford University Press on behalf of the British Society for Rheumatology. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Short communication: Use of a portable, automated, open-circuit gas quantification system and the sulfur hexafluoride tracer technique for measuring enteric methane emissions in Holstein cows fed ad libitum or restricted.

PubMed

Dorich, C D; Varner, R K; Pereira, A B D; Martineau, R; Soder, K J; Brito, A F

2015-04-01

The objective of this study was to measure enteric CH4 emissions using a new portable automated open-circuit gas quantification system (GQS) and the sulfur hexafluoride tracer technique (SF6) in midlactation Holstein cows housed in a tiestall barn. Sixteen cows averaging 176 ± 34 d in milk, 40.7 ± 6.1 kg of milk yield, and 685 ± 49 kg of body weight were randomly assigned to 1 out of 2 treatments according to a crossover design. Treatments were (1) ad libitum (adjusted daily to yield 10% orts) and (2) restricted feed intake [set to restrict feed by 10% of baseline dry matter intake (DMI)]. Each experimental period lasted 22d, with 14 d for treatment adaptation and 8d for data and sample collection. A common diet was fed to the cows as a total mixed ration and contained 40.4% corn silage, 11.2% grass-legume haylage, and 48.4% concentrate on a dry matter basis. Spot 5-min measurements using the GQS were taken twice daily with a 12-h interval between sampling and sampling times advanced 2h daily to account for diurnal variation in CH4 emissions. Canisters for the SF6 method were sampled twice daily before milking with 4 local background gas canisters inside the barn analyzed for background gas concentrations. Enteric CH4 emissions were not affected by treatments and averaged 472 and 458 g/d (standard error of the mean = 18 g/d) for ad libitum and restricted intake treatments, respectively (data not shown). The GQS appears to be a reliable method because of the relatively low coefficients of variation (ranging from 14.1 to 22.4%) for CH4 emissions and a moderate relationship (coefficient of determination = 0.42) between CH4 emissions and DMI. The SF6 resulted in large coefficients of variation (ranging from 16.0 to 111%) for CH4 emissions and a poor relationship (coefficient of determination = 0.17) between CH4 emissions and DMI, likely because of limited barn ventilation and high background gas concentration. Research with improved barn ventilation systems or outdoors is warranted to further assess the GQS and SF6 methodologies. Copyright © 2015 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Conventional (CH) vs. stapled hemorrhoidectomy (SH) in surgical treatment of hemorrhoids. Ten years experience.

PubMed

Manfredelli, Simone; Montalto, Gioacchino; Leonetti, Giovanni; Covotta, Marco; Amatucci, Chiara; Covotta, Alfredo; Forte, Angelo

2012-01-01

Interest about hemorrhoids is related to its high incidence and elevated social costs that derive from its treatment. Several comparative studies are reported in Literature to define a standard for ideal treatment of hemorrhoidal disease. Radical surgery is the only therapeutic option in case of III and IV stage haemorrhoids. Hemorrhoids surgical techniques are classified as Open, Closed and Stapled ones. We report our decennial experience on surgical treatment focusing on early, middle and late complications, indications and contraindications, satisfaction level of each surgical procedure for hemorrhoids. Four hundred forty-eight patients have been hospitalized in our department fom 1st January to 31st December 2008. Of these 241 underwent surgery with traditional open or closed technique and 207 with the SH technique according to Longo. This retrospective study includes only patients with symptomatic hemorrhoids at III or IV stage. There were no differences between CH and SH about both pre and post surgery hospitalization and intraoperative length. Pain is the most frequently observed early complication with a statistically significant difference in favour of SH. We obtain good results in CH group using anoderma sparing and perianal anaesthetic infiltration at the end of the surgery. In all cases, pain relief was obtained only with standard analgesic drugs (NSAIDs). We also observed that pain level influences the outcome after surgical treatment. No chronic pain cases were observed in both groups. Bleeding is another relevant early complication in particular after SH: we reported 2 cases of immediate surgical reintenvention and 2 cases treated with blood transfusion. Only in SH group we report also 5 cases of thrombosis of external haemorrhoids and 7 perianal hematoma both solved with medical therapy There were no statistical significant differences between two groups about fever, incontinence to flatus, urinary retention, fecal incontinence, substenosis and anal burning. No cases of anal stenosis were observed. About late complications, most frequently observed were rectal prolapse and hemorrhoidal recurrence, especially after SH. Our experience confirms the validity of both CH and SH. Failure may be related to wrong surgical indication or technical execution. Certainly CH procedure is more invasive and slightly more painfull in immediate postoperative period than SH surgery, which is slightly more expensive and has more complications. In our opinion the high risk of possible early and immediate complications after surgery requires at least a 24 hours hospitalization length. SH is the gold standard for III grade haemorrhoids with mucous prolapse while CH is suggested in IV grade cases. Hemorrhoidal arterial ligation operation (HALO) technique in III and IV degree needs further validations.

Volatile arsenic species released from Escherichia coli expressing the AsIII S-adenosylmethionine methyltransferase gene.

PubMed

Yuan, Chungang; Lu, Xiufen; Qin, Jie; Rosen, Barry P; Le, X Chris

2008-05-01

Biological systems, ranging from bacteria and fungi to humans, can methylate arsenic. Recent studies have suggested that the AsIII S-adenosylmethionine methyltransferase (arsM) gene in bacteria was responsible for the removal of arsenic as the volatile arsines from the bacteria. However, there has been no direct measure of the arsines released from bacteria cultures. We describe here an integrated system incorporating the bacterial incubation and volatile arsenic species analysis, and we demonstrate its application to the identification of the volatile arsines produced in bacterial cultures. The headspace of the bacterial cultures was purged with helium, and the volatile arsenic species were trapped in a chromatographic column immersed in liquid nitrogen. The cryogenically trapped arsines [AsH3, (CH3)AsH2, (CH3)2AsH, and (CH3)3As] were separated by gas chromatography and were detected by inductively coupled plasma mass spectrometry. A hydride generation system was coupled to the bacterial culture system, allowing for spiking standards and for generating calibration arsines necessary for quantitative analysis. Both bacteria containing the arsM gene or its variant arsMC2 gene were able to produce 400-500 ng of trimethylarsine. No trimethylarsine was detectable in bacteria lacking the arsM gene (containing the vector plasmid as negative control). These results confirm that arsM is responsible for releasing arsenic as volatile species from the arsenic-resistant bacteria. Our results also show traces of AsH3, CH3AsH2, and (CH3)2AsH in cultures of bacteria expressing arsM. The method detection limits for AsH3, CH3AsH2, (CH3)2AsH, and (CH3)3As were 0.5, 0.5, 0.7, and 0.6 pg, respectively. The ability to quantify trace levels of these volatile arsenic species makes it possible to study the biotransformation and biochemical roles of the evolution of these volatile arsenic species by biological systems.

Tweezering the core of dendrimers: medium effect on the kinetic and thermodynamic properties.

PubMed

Giansante, Carlo; Mazzanti, Andrea; Baroncini, Massimo; Ceroni, Paola; Venturi, Margherita; Klärner, Frank-Gerrit; Vögtle, Fritz

2009-10-02

We have investigated the complex formation between dendritic guests and a molecular tweezer host by NMR, absorption, and emission spectroscopy as well as electrochemical techniques. The dendrimers are constituted by an electron-acceptor 4,4'-bipyridinium core appended with one (DnB(2+)) or two (Dn(2)B(2+)) polyaryl-ether dendrons. Tweezer T comprises a naphthalene and four benzene components bridged by four methylene groups. Medium effects on molecular recognition phenomena are discussed and provide insight into the conformation of dendrimers: change in solvent polarity from pure CH(2)Cl(2) to CH(2)Cl(2)/CH(3)CN mixtures and addition of tetrabutylammonium hexafluorophosphate (NBu(4)PF(6), up to 0.15 M), the supporting electrolyte used in the electrochemical measurements, have been investigated. The association constants measured in different media show the following trend: (i) they decrease upon increasing polarity of the solvent, as expected for host-guest complexes stabilized by electron donor-acceptor interactions; (ii) no effect of generation and number of dendrons (one for the DnB(2+) family and two for the Dn(2)B(2+) family) appended to the core is observed in higher polarity media; and (iii) in a low-polarity solvent, like CH(2)Cl(2), the stability of the inclusion complexes is higher for DnB(2+) dendrimers than for Dn(2)B(2+) ones, while within each dendrimer family it increases by decreasing dendron generation, and upon addition of NBu(4)PF(6). The last result has been ascribed to a partial dendron unfolding. Kinetic investigations performed in lower polarity media evidence that the rate constants of complex formation are slower for symmetric Dn(2)B(2+) dendrimers than for the nonsymmetric DnB(2+) ones, and that within the Dn(2)B(2+) family, they decrease by increasing dendron generation. The dependence of the rate constants for the formation and dissociation of the complexes upon addition of NBu(4)PF(6) has also been investigated and discussed.

Effects of warming and nitrogen fertilization on GHG flux in an alpine swamp meadow of a permafrost region.

PubMed

Chen, Xiaopeng; Wang, Genxu; Zhang, Tao; Mao, Tianxu; Wei, Da; Song, Chunlin; Hu, Zhaoyong; Huang, Kewei

2017-12-01

Uncertainties in the seasonal changes of greenhouse gases (GHG) fluxes in wetlands limit our accurate understanding of the responses of permafrost ecosystems to future warming and increased nitrogen (N) deposition. Therefore, in an alpine swamp meadow in the hinterland of the Qinghai-Tibet Plateau, a simulated warming with N fertilization experiment was conducted to investigate the key GHG fluxes (ecosystem respiration [Re], CH 4 and N 2 O) in the early (EG), mid (MG) and late (LG) growing seasons. Results showed that warming (6.2 °C) increased the average seasonal Re by 30.9% and transformed the alpine swamp meadow from a N 2 O sink to a source, whereas CH 4 flux was not significantly affected. N fertilization (4 g N m -2 a -1 ) alone had no significant effect on the fluxes of GHGs. The interaction of warming and N fertilization increased CH 4 uptake by 69.6% and N 2 O emissions by 26.2% compared with warming, whereas the Re was not significantly affected. During the EG, although the soil temperature sensitivity of the Re was the highest, the effect of warming on the Re was the weakest. The primary driving factor for Re was soil surface temperature, whereas soil moisture controlled CH 4 flux, and the N 2 O flux was primarily affected by rain events. The results indicated: (i) increasing N deposition has both positive and negative feedbacks on GHG fluxes in response to climate warming; (ii) during soil thawing process at active layer, low temperature of deep frozen soils have a negative contribution to Re in alpine ecosystems; and (iii) although these alpine wetland ecosystems are buffers against increased temperature, their feedbacks on climate change cannot be ignored because of the large soil organic carbon pool and high temperature sensitivity of the Re. Copyright © 2017 Elsevier B.V. All rights reserved.

An Effective-Hamiltonian Approach to CH5+, Using Ideas from Atomic Spectroscopy

NASA Astrophysics Data System (ADS)

Hougen, Jon T.

2016-06-01

In this talk we present the first steps in the design of an effective Hamiltonian for the vibration-rotation energy levels of CH5+. Such a Hamiltonian would allow calculation of energy level patterns anywhere along the path travelled by a hypothetical CH5+ (or CD5+) molecule as it passes through various coupling cases, and might thus provide some hints for assigning the observed high-resolution spectra. The steps discussed here, which have not yet addressed computational problems, focus on mapping the vibration-rotation problem in CH5+ onto the five-electron problem in the boron atom, using ideas and mathematical machinery from Condon and Shortley's book on atomic spectroscopy. The mapping ideas are divided into: (i) a mapping of particles, (ii) a mapping of coordinates (i.e., mathematical degrees of freedom), and (iii) a mapping of quantum mechanical interaction terms. The various coupling cases along the path correspond conceptually to: (i) the analog of a free-rotor limit, where the H atoms see the central C atom but do not see each other, (ii) the low-barrier and high-barrier tunneling regimes, and (iii) the rigid-molecule limit, where the H atoms remain locked in some fixed molecular geometry. Since the mappings considered here often involve significant changes in mathematics, a number of interesting qualitative changes occur in the basic ideas when passing from B to CH5+, particularly in discussions of: (i) antisymmetrization and symmetrization ideas, (ii) n,l,ml,ms or n,l,j,mj quantum numbers, and (iii) Russell-Saunders computations and energy level patterns. Some of the mappings from B to CH5+ to be discussed are as follows. Particles: the atomic nucleus is replaced by the C atom, the electrons are replaced by protons, and the empty space between particles is replaced by an "electron soup." Coordinates: the radial coordinates of the electrons map onto the five local C-H stretching modes, the angular coordinates of the electrons map onto three rotational degrees of freedom and seven bending vibrational degrees of freedom. The half-integral electron spins map onto half-integral proton spins or onto integral deuterium spins (for CD5+). Interactions: the Coulomb attraction between nucleus and electrons maps onto a Morse-oscillator C-H stretching potential, spin-orbit interaction maps onto proton-spin-overall-rotation interaction, and Coulomb repulsion between electrons maps onto some kind of proton repulsion that leads to the equilibrium geometry.

Serpentinization and the Formation of H2 and CH4 on Celestial Bodies (Planets, Moons, Comets).

PubMed

Holm, N G; Oze, C; Mousis, O; Waite, J H; Guilbert-Lepoutre, A

2015-07-01

Serpentinization involves the hydrolysis and transformation of primary ferromagnesian minerals such as olivine ((Mg,Fe)2SiO4) and pyroxenes ((Mg,Fe)SiO3) to produce H2-rich fluids and a variety of secondary minerals over a wide range of environmental conditions. The continual and elevated production of H2 is capable of reducing carbon, thus initiating an inorganic pathway to produce organic compounds. The production of H2 and H2-dependent CH4 in serpentinization systems has received significant interdisciplinary interest, especially with regard to the abiotic synthesis of organic compounds and the origins and maintenance of life in Earth's lithosphere and elsewhere in the Universe. Here, serpentinization with an emphasis on the formation of H2 and CH4 are reviewed within the context of the mineralogy, temperature/pressure, and fluid/gas chemistry present in planetary environments. Whether deep in Earth's interior or in Kuiper Belt Objects in space, serpentinization is a feasible process to invoke as a means of producing astrobiologically indispensable H2 capable of reducing carbon to organic compounds.

Stable carbon isotopic evidence of methane consumption and production in three alpine ecosystems on the Qinghai-Tibetan Plateau

NASA Astrophysics Data System (ADS)

Kato, Tomomichi; Yamada, Keita; Tang, Yanhong; Yoshida, Naohiro; Wada, Eitaro

2013-10-01

To understand the mechanisms of soil CH4 consumption and production in alpine ecosystems, we for the first time examined the stable carbon isotope ratio of CH4 (δ13C-CH4) at three major grassland vegetation types, alpine meadow, alpine shrub, and alpine wetland, on the Qinghai-Tibetan Plateau. The alpine meadow and shrub showed net CH4 absorption in their vertical profiles of CH4 concentration in summer, but a difference in their processes. Whereas the alpine shrub was dominated by CH4 consumption in its soil profile, CH4 production in the alpine meadow could slightly cancel consumed CH4 in shallow soil from -0.3 to -0.1 m. This potential CH4 production can be attributed to the relatively wet soil type of that ecosystem, which might allow methanogenesis to act in moist soil lumps in the shallow layer. The alpine wetland differed in methane production, consumption, and transport pathways between hummock and hollow plots. In summer, both plots were enriched in 13C-CH4 in dissolved CH4 in soil pore water, suggesting that CH4 production was conducted mainly by acetate fermentation. In autumn, CH4 production was shifted toward CO2/H2 reduction. Furthermore, in hummocks, plant-mediated transport of CH4 by vascular plants appeared to perform passive CH4 flow from deep soil to atmosphere, which allowed the produced CH4 to bypass the oxidation zone in shallow soil. In hollows, however, CH4 produced in shallow soil was subject to simultaneous oxidation. The fractional oxidation rate on gross CH4 production in hollows was estimated by simple mass balance model at 7-17% in summer and 35-36% in autumn.

Susceptibility of Permafrost Soil Organic Carbon under Warming Climate

NASA Astrophysics Data System (ADS)

Yang, Z.; Wullschleger, S. D.; Liang, L.; Graham, D. E.; Gu, B.

2015-12-01

Degradation of soil organic carbon (SOC) that has been stored in permafrost is a key concern under warming climate because it could provide a positive feedback. Studies and conceptual models suggest that SOC degradation is largely controlled by the decomposability of SOC, but it is unclear exactly what portions of SOC are susceptible to rapid breakdown and what mechanisms may be involved in SOC degradation. Using a suite of analytical techniques, we examined the dynamic consumption and production of labile SOC compounds, including sugars, alcohols, and small molecular weight organic acids in incubation experiments (up to 240 days at either -2 or 8 °C) with a tundra soil under anoxic conditions, where SOC respiration and iron(III) reduction were monitored. We observe that sugars and alcohols are main components in SOC accounting for initial rapid release of CO2 and CH4 through anaerobic fermentation, whereas the fermentation products such as acetate and formate are subsequently utilized as primary substrates for methanogenesis. Iron(III) reduction is correlated to acetate production and methanogenesis, suggesting its important roles as an electron acceptor in tundra SOC respiration. These observations corroborate strongly with the glucose addition during incubation, in which rapid CO2 and CH4 production is observed concurrently with rapid production and consumption of organics such as acetate. Thus, the biogeochemical processes we document here are pertinent to understanding the accelerated SOC decomposition with temperature and could provide basis for model predicting feedbacks to climate warming in the Arctic.

A highly selective colorimetric and fluorescent chemosensor for Al(III) based-on simple naphthol in aqueous solution

NASA Astrophysics Data System (ADS)

Liu, Zhaodi; Xu, Huajie; Sheng, Liangquan; Chen, Shuisheng; Huang, Deqian; Liu, Jie

2016-03-01

A colorimetric and fluorescent chemosensor (L) for Al(III) was synthesized and fully characterized. L could be both used as a colorimetric and fluorescent chemosensor for the detection of Al3 + ions with low detection limit (8.87 × 10- 7 M) in CH3CN-H2O (1:1, v/v) solution. The binding ratio of L-Al3 + was determined from the Job plot (absorption and fluorescence spectra) and MALDI-TOF MS data to be 1:1. The binding constant (Ka) of Al3 + binding to L was calculated to be 4.8 × 105 M- 1 from a Benesi-Hildebrand plot. Moreover, the binding site of L with Al3 + was determined by 1H NMR titration experiment.

Landscape patterns of CH4 fluxes in an alpine tundra ecosystem

USGS Publications Warehouse

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

1999-01-01

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

Strategic grazing management towards sustainable intensification at tropical pasture-based dairy systems.

PubMed

Congio, Guilhermo F S; Batalha, Camila D A; Chiavegato, Marília B; Berndt, Alexandre; Oliveira, Patrícia P A; Frighetto, Rosa T S; Maxwell, Thomas M R; Gregorini, Pablo; Da Silva, Sila C

2018-05-01

Agricultural systems are responsible for environmental impacts that can be mitigated through the adoption of more sustainable principles. Our objective was to investigate the influence of two pre-grazing targets (95% and maximum canopy light interception during pasture regrowth; LI 95% and LI Max , respectively) on sward structure and herbage nutritive value of elephant grass cv. Cameroon, and dry matter intake (DMI), milk yield, stocking rate, enteric methane (CH 4 ) emissions by Holstein × Jersey dairy cows. We hypothesized that grazing strategies modifying the sward structure of elephant grass (Pennisetum purpureum Schum.) improves nutritive value of herbage, increasing DMI and reducing intensity of enteric CH 4 emissions, providing environmental and productivity benefits to tropical pasture-based dairy systems. Results indicated that pre-sward surface height was greater for LI Max (≈135 cm) than LI 95% (≈100 cm) and can be used as a reliable field guide for monitoring sward structure. Grazing management based on LI 95% criteria improved herbage nutritive value and grazing efficiency, allowing greater DMI, milk yield and stocking rate by dairy cows. Daily enteric CH 4 emission was not affected; however, cows grazing elephant grass at LI 95% were more efficient and emitted 21% less CH 4 /kg of milk yield and 18% less CH 4 /kg of DMI. The 51% increase in milk yield per hectare overcame the 29% increase in enteric CH 4 emissions per hectare in LI 95% grazing management. Thereby the same resource allocation resulted in a 16% mitigation of the main greenhouse gas from pasture-based dairy systems. Overall, strategic grazing management is an environmental friendly practice that improves use efficiency of allocated resources through optimization of processes evolving plant, ruminant and their interface, and enhances milk production efficiency of tropical pasture-based systems. Copyright © 2018 Elsevier B.V. All rights reserved.

Invited review: Large-scale indirect measurements for enteric methane emissions in dairy cattle: A review of proxies and their potential for use in management and breeding decisions.

PubMed

Negussie, E; de Haas, Y; Dehareng, F; Dewhurst, R J; Dijkstra, J; Gengler, N; Morgavi, D P; Soyeurt, H; van Gastelen, S; Yan, T; Biscarini, F

2017-04-01

Efforts to reduce the carbon footprint of milk production through selection and management of low-emitting cows require accurate and large-scale measurements of methane (CH 4 ) emissions from individual cows. Several techniques have been developed to measure CH 4 in a research setting but most are not suitable for large-scale recording on farm. Several groups have explored proxies (i.e., indicators or indirect traits) for CH 4 ; ideally these should be accurate, inexpensive, and amenable to being recorded individually on a large scale. This review (1) systematically describes the biological basis of current potential CH 4 proxies for dairy cattle; (2) assesses the accuracy and predictive power of single proxies and determines the added value of combining proxies; (3) provides a critical evaluation of the relative merit of the main proxies in terms of their simplicity, cost, accuracy, invasiveness, and throughput; and (4) discusses their suitability as selection traits. The proxies range from simple and low-cost measurements such as body weight and high-throughput milk mid-infrared spectroscopy (MIR) to more challenging measures such as rumen morphology, rumen metabolites, or microbiome profiling. Proxies based on rumen samples are generally poor to moderately accurate predictors of CH 4 , and are costly and difficult to measure routinely on-farm. Proxies related to body weight or milk yield and composition, on the other hand, are relatively simple, inexpensive, and high throughput, and are easier to implement in practice. In particular, milk MIR, along with covariates such as lactation stage, are a promising option for prediction of CH 4 emission in dairy cows. No single proxy was found to accurately predict CH 4 , and combinations of 2 or more proxies are likely to be a better solution. Combining proxies can increase the accuracy of predictions by 15 to 35%, mainly because different proxies describe independent sources of variation in CH 4 and one proxy can correct for shortcomings in the other(s). The most important applications of CH 4 proxies are in dairy cattle management and breeding for lower environmental impact. When breeding for traits of lower environmental impact, single or multiple proxies can be used as indirect criteria for the breeding objective, but care should be taken to avoid unfavorable correlated responses. Finally, although combinations of proxies appear to provide the most accurate estimates of CH 4 , the greatest limitation today is the lack of robustness in their general applicability. Future efforts should therefore be directed toward developing combinations of proxies that are robust and applicable across diverse production systems and environments. The Authors. Published by the Federation of Animal Science Societies and Elsevier Inc. on behalf of the American Dairy Science Association®. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).

High quality human immunoglobulin G purified from Cohn fractions by liquid chromatography.

PubMed

Tanaka, K; Sawatani, E; Dias, G A; Shigueoka, E M; Campos, T C; Nakao, H C; Arashiro, F

2000-01-01

In order to obtain intravenous immunoglobulin G (iv IgG) of high quality from F-I+II+III or F-II+III pastes prepared by the Cohn method, we developed a chromatography process using ion exchange gels, Q-Sepharose FF and CM-Sepharose FF, and Sephacryl S-300 gel filtration. Viral inactivation was performed by incubating the preparation with pepsin at pH 4.0 at 35 degrees C for 18 h. The characteristics of 28 batches produced by us were: yield 4.3 +/- 0.2 g/l plasma, i.e., a recovery of 39.1 +/- 1.8%; IgG subclasses distribution: IgG1 = 58.4%, IgG2 = 34.8%, IgG3 = 4.5% and IgG4 = 2. 3%; IgG size distribution was 98.4% monomers, 1.2% dimers and 0.4% polymers and protein aggregates; anticomplement activity was less than 0.5 CH50/mg IgG, and prekallikrein activator activity (PKA) was less than 5 IU/ml. These characteristics satisfied the requirements of the European Pharmacopoea edition, and the regulations of the Brazilian Health Ministry (M.S. Portaria No. 2, 30/10/1998).

Spectroscopic identification of type 2 quasars at z < 1 in SDSS-III/BOSS

NASA Astrophysics Data System (ADS)

Yuan, Sihan; Strauss, Michael A.; Zakamska, Nadia L.

2016-10-01

The physics and demographics of type 2 quasars remain poorly understood, and new samples of such objects selected in a variety of ways can give insight into their physical properties, evolution, and relationship to their host galaxies. We present a sample of 2758 type 2 quasars at z ≲ 1 from the Sloan Digital Sky Survey-III (SDSS-III)/Baryon Oscillation Spectroscopic Survey (BOSS) spectroscopic data base, selected on the basis of their emission-line properties. We probe the luminous end of the population by requiring the rest-frame equivalent width of [O III] to be >100 Å. We distinguish our objects from star-forming galaxies and type 1 quasars using line widths, standard emission line ratio diagnostic diagrams at z < 0.52 and detection of [Ne V]λ3426 Å at z > 0.52. The majority of our objects have [O III] luminosities in the range 1.2 × 1042-3.8 × 1043 erg s-1 and redshifts between 0.4 and 0.65. Our sample includes over 400 type 2 quasars with incorrectly measured redshifts in the BOSS data base; such objects often show kinematic substructure or outflows in the [O III] line. The majority of the sample has counterparts in the Wide-field Infrared Survey Explorer survey, with median infrared luminosity νLν[12 μm] = 4.2 × 1044 erg s- 1. Only 34 per cent of the newly identified type 2 quasars would be selected by infrared colour cuts designed to identify obscured active nuclei, highlighting the difficulty of identifying complete samples of type 2 quasars. We make public the multi-Gaussian decompositions of all [O III] profiles for the new sample and for 568 type 2 quasars from SDSS I/II, together with non-parametric measures of the [O III] line profile shapes. We also identify over 600 candidate double-peaked [O III] profiles.

The geochemistry of methane in Lake Fryxell, an amictic, permanently ice-covered, antarctic lake

USGS Publications Warehouse

Smith, R.L.; Miller, L.G.; Howes, B.L.

1993-01-01

The abundance and distribution of dissolved CH4 were determined from 1987-1990 in Lake Fryxell, Antarctica, an amictic, permanently ice-covered lake in which solute movement is controlled by diffusion. CH4 concentrations were < 1 ??M in the upper oxic waters, but increased below the oxycline to 936 ??M at 18 m. Sediment CH4 was 1100 ??mol (1 sed)-1 in the 0-5 cm zone. Upward flux from the sediment was the source of the CH4, NH4 +, and DOC in the water column; CH4 was 27% of the DOC+CH4 carbon at 18 m. Incubations with surficial sediments indicated that H14CO3 - reduction was 0.4 ??mol (1 sed)-1 day-1 or 4?? the rate of acetate fermentation to CH4. There was no measurable CH4 production in the water column. However, depth profiles of CH4, NH4, and DIC normalized to bottom water concentrations demonstrated that a significant CH4 sink was evident in the anoxic, sulfate-containing zone of the water column (10-18 m). The ??13CH4 in this zone decreased from -72 % at 18 m to -76% at 12 m, indicating that the consumption mechanism did not result in an isotopic enrichment of 13CH4. In contrast, ??13CH4 increased to -55 % at 9 m due to aerobic oxidation, though this was a minor aspect of the CH4 cycle. The water column CH4 profile was modeled by coupling diffusive flux with a first order consumption term; the best-fit rate constant for anaerobic CH4 consumption was 0.012 yr-1. On a total carbon basis, CH4 consumption in the anoxic water column exerted a major effect on the flux of carbonaceous material from the underlying sediments and serves to exemplify the importance of CH4 to carbon cycling in Lake Fryxell. ?? 1993 Kluwer Academic Publishers.

Electron flow in large metallomacromolecules and electronic switch of nanoparticle stabilization: new click ferrocenyl dentromers that reduce Au(III) to Au nanoparticles.

PubMed

Astruc, Didier; Wang, Qi; Fu, Fangyu; Martinez-Villacorta, Angel M; Moya, Sergio; Salmon, Lionel; Ruiz, Jaime; Hunel, Julien; Vax, Amélie

2018-06-04

Click ferrocenyl-terminal dentromers, a family of arene-cored dendrimers with triple branching (9-Fc, 27-Fc, 81-Fc and 243-Fc) reduce Au(III) to ferricinium dentromer-stabilized Au nanoparticles (AuNPs). Cyclic voltammetry studies in CH2Cl2 show reversible CV waves with some adsorption for the 243-Fc dentromer and a number of redox groups found, 255 ± 25, using the Bard-Anson method, close to the theoretical number of 243. The dentromers reduce aqueous HAuCl4 to water-soluble ferricinium chloride dentromer-stabilized gold nanoparticles (AuNPs) with core sizes between 30 and 47 nm. These triazolylferricinium dentromer-stabilized AuNPs are reduced by cobaltocene to cobalticinium chloride and ferrocene dentromer-weakly stabilized AuNPs together with red shift of the AuNP plasmon. The weakness of the AuNP stabilization is characterized by dentromer extraction with CH2Cl2 along with irreversible AuNP agglomeration for the 9, 27 and 81-ferrocenyl dentromer, only the 243-ferrocenyl dentromer-AuNP withstanding this process. Altogether this demonstrates the electronic switch of the dentromer-mediated AuNP stabilization. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Luminescence enhancement of terbium(III) perchlorate by 2,2'-dipyridyl on bis(benzylsulfinyl)methane complex and luminescence mechanism.

PubMed

Feng, Shu-Yan; Li, Wen-Xian; Guo, Feng; Cao, Xiao-Fang

2014-11-01

A novel ternary complex, Tb(2)L4 · L'·(ClO4)6 · 8H2O, has been synthesized using bis(benzylsulfinyl)methane as the first ligand L and 2,2'-dipyridyl as the second ligand L'. The ternary complex was characterized by element analysis, molar conductivity, coordination titration analysis, infrared, thermogravimetric-differential scanning calorimetric and ultraviolet spectra. The results indicated that the composition of the complex was Tb2 L4 · L'·(ClO4)6 · 8H2O (L = C(6)H(5)CH(2) SOCH(2)SOCH(2)C(6)H(5); L' = Dipy). Fourier transform infrared results revealed that the perchlorate group was bonded with the Tb(III) ion by the oxygen atom, and the coordination was bidentate. The fluorescent spectra illustrated that the complex displayed characteristic fluorescence in the solid state. After the introduction of the second ligand, 2,2-dipyridyl, the relative emission intensity and fluorescence lifetime of the ternary complex Tb(2)L(4) · L'·(ClO(4))(6) · 8H2O were enhanced compared to the binary complex TbL(2.5)(ClO4)3 · 3H2O. This indicated that the presence of both organic ligand bis(benzylsulfinyl)methane and the second ligand 2,2-dipyridyl could sensitize the fluorescence intensity of Tb(III) ion, and introduction of the 2,2-dipyridyl group resulted in an enhancement of the fluorescence of the Tb(III) ternary rare earth complex. The strongest characteristic fluorescence emission intensity of the ternary complex was 9.36 times that of the binary complex. The phosphorescence spectra and fluorescence lifetime of the complex were also measured. Copyright © 2014 John Wiley & Sons, Ltd.

Purification and Biochemical Characterization of Mutacin I from the Group I Strain of Streptococcus mutans, CH43, and Genetic Analysis of Mutacin I Biosynthesis Genes

PubMed Central

Qi, Fengxia; Chen, Ping; Caufield, Page W.

2000-01-01

Previously, we reported isolation and characterization of mutacin III and genetic analysis of mutacin III biosynthesis genes from the group III strain of Streptococcus mutans, UA787 (F. Qi, P. Chen, and P. W. Caufield, Appl. Environ. Microbiol. 65:3880–3887, 1999). During the same process of isolating the mutacin III structural gene, we also cloned the structural gene for mutacin I. In this report, we present purification and biochemical characterization of mutacin I from the group I strain CH43 and compare mutacin I and mutacin III biosynthesis genes. The mutacin I biosynthesis gene locus consists of 14 genes in the order mutR, -A, -A′, -B, -C, -D, -P, -T, -F, -E, -G, orfX, orfY, orfZ. mutA is the structural gene for mutacin I, while mutA′ is not required for mutacin I activity. DNA and protein sequence analysis revealed that mutacins I and III are homologous to each other, possibly arising from a common ancestor. The mature mutacin I is 24 amino acids in size and has a molecular mass of 2,364 Da. Ethanethiol modification and peptide sequencing of mutacin I revealed that it contains six dehydrated serines, four of which are probably involved with thioether bridge formation. Comparison of the primary sequence of mutacin I with that of mutacin III and epidermin suggests that mutacin I likely has the same bridging pattern as epidermin. PMID:10919773

Purification and biochemical characterization of mutacin I from the group I strain of Streptococcus mutans, CH43, and genetic analysis of mutacin I biosynthesis genes.

PubMed

Qi, F; Chen, P; Caufield, P W

2000-08-01

Previously, we reported isolation and characterization of mutacin III and genetic analysis of mutacin III biosynthesis genes from the group III strain of Streptococcus mutans, UA787 (F. Qi, P. Chen, and P. W. Caufield, Appl. Environ. Microbiol. 65:3880-3887, 1999). During the same process of isolating the mutacin III structural gene, we also cloned the structural gene for mutacin I. In this report, we present purification and biochemical characterization of mutacin I from the group I strain CH43 and compare mutacin I and mutacin III biosynthesis genes. The mutacin I biosynthesis gene locus consists of 14 genes in the order mutR, -A, -A', -B, -C, -D, -P, -T, -F, -E, -G, orfX, orfY, orfZ. mutA is the structural gene for mutacin I, while mutA' is not required for mutacin I activity. DNA and protein sequence analysis revealed that mutacins I and III are homologous to each other, possibly arising from a common ancestor. The mature mutacin I is 24 amino acids in size and has a molecular mass of 2, 364 Da. Ethanethiol modification and peptide sequencing of mutacin I revealed that it contains six dehydrated serines, four of which are probably involved with thioether bridge formation. Comparison of the primary sequence of mutacin I with that of mutacin III and epidermin suggests that mutacin I likely has the same bridging pattern as epidermin.

A psychometric study of the Test of Everyday Attention for Children in the Chinese setting.

PubMed

Chan, Raymond C K; Wang, Li; Ye, Jiawen; Leung, Winnie W Y; Mok, Monica Y K

2008-07-01

To explore the psychometric properties of the Test of Everyday Attention for Children (TEA-Ch) in the context of a Chinese setting. Confirmatory factor analysis was conducted to examine the construct validity of the Chinese version of the TEA-Ch among a group of 232 children without attention deficit hyperactivity disorder (ADHD). Test-retest reliability was tested on a random sub-sample of 20 children at a 4-week interval. Clinical discrimination was also examined by comparing children with and without ADHD (22 in each group) on the performances of the TEA-Ch. The current Chinese sample demonstrated a three-factor solution for attentional performance among children without ADHD, namely selective attention, executive control/switch, and sustained attention (chi(2)(24)=34.56; RMSEA=.044; p=.075). Moreover, the whole test demonstrated acceptable test-retest reliability at a 4-week interval among a small sub-sample. Children with ADHD performed significantly more poorly than healthy controls in most of the subtests of the TEA-Ch. The results of the present study demonstrate that the test items remain useful in China, a culture very different from that in which the test originated. Finally, the TEA-Ch also presents several advantages when compared to other conventional objective measures of attention.

40 CFR 98.323 - Calculating GHG emissions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... systems (metric tons CH4). CH4V = Quarterly CH4 liberated from each ventilation monitoring point (metric... vent holes are collected, you must calculate the quarterly CH4 liberated from the ventilation system... CH4 liberated from a ventilation monitoring point (metric tons CH4). V = Volumetric flow rate for the...

Gas production, composition and emission at a modern disposal site receiving waste with a low-organic content

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

Scheutz, Charlotte, E-mail: chs@env.dtu.dk; Fredenslund, Anders M., E-mail: amf@env.dtu.dk; Nedenskov, Jonas, E-mail: jne@amfor.dk

2011-05-15

AV Miljo is a modern waste disposal site receiving non-combustible waste with a low-organic content. The objective of the current project was to determine the gas generation, composition, emission, and oxidation in top covers on selected waste cells as well as the total methane (CH{sub 4}) emission from the disposal site. The investigations focused particularly on three waste disposal cells containing shredder waste (cell 1.5.1), mixed industrial waste (cell 2.2.2), and mixed combustible waste (cell 1.3). Laboratory waste incubation experiments as well as gas modeling showed that significant gas generation was occurring in all three cells. Field analysis showed thatmore » the gas generated in the cell with mixed combustible waste consisted of mainly CH{sub 4} (70%) and carbon dioxide (CO{sub 2}) (29%) whereas the gas generated within the shredder waste, primarily consisted of CH{sub 4} (27%) and nitrogen (N{sub 2}) (71%), containing no CO{sub 2}. The results indicated that the gas composition in the shredder waste was governed by chemical reactions as well as microbial reactions. CH{sub 4} mass balances from three individual waste cells showed that a significant part (between 15% and 67%) of the CH{sub 4} generated in cell 1.3 and 2.2.2 was emitted through leachate collection wells, as a result of the relatively impermeable covers in place at these two cells preventing vertical migration of the gas. At cell 1.5.1, which is un-covered, the CH{sub 4} emission through the leachate system was low due to the high gas permeability of the shredder waste. Instead the gas was emitted through the waste resulting in some hotspot observations on the shredder surface with higher emission rates. The remaining gas that was not emitted through surfaces or the leachate collection system could potentially be oxidized as the measured oxidation capacity exceeded the potential emission rate. The whole CH{sub 4} emission from the disposal site was found to be 820 {+-} 202 kg CH{sub 4} d{sup -1}. The total emission rate through the leachate collection system at AV Miljo was found to be 211 kg CH{sub 4} d{sup -1}. This showed that approximately 1/4 of the emitted gas was emitted through the leachate collections system making the leachate collection system an important source controlling the overall gas migration from the site. The emission pathway for the remaining part of the gas was more uncertain, but emission from open cells where waste is being disposed of or being excavated for incineration, or from horizontal leachate drainage pipes placed in permeable gravel layers in the bottom of empty cells was likely.« less

SOFIA + FORCAST Observations of 10 Aqueously Altered Asteroids

NASA Astrophysics Data System (ADS)

McAdam, Margaret; Sunshine, Jessica M.; Kelley, Michael S.; Bus, Schelte J.

2016-10-01

Aqueous alteration, or the reaction of water and minerals to produce hydrated minerals, has affected certain groups of carbonaceous meteorites (e.g., the CM and CI meteorites) and asteroids. In the visible/near-infrared (VNIR), CM/CI meteorites and some dark C-complex asteroids are known to have 0.7-µm absorptions that indicate the presence of hydrated minerals [1, 2, 3]. However, this feature does not provide any information about the amount of hydrated minerals in asteroids or meteorites [1]. In contrast, at mid-infrared (MIR) wavelengths, strong spectral features change continuously with amount of hydrated minerals in a suite of well-characterized CM/CI meteorites [1].Using these results, we analyze the spectra of 10 C-complex asteroids observed by SOFIA + FORCAST. These targets are large objects (>95 km diameter) situated in the mid to outer Main Asteroid Belt (2.4 - 3.4 AU). We present spectra of the following asteroids, spectral types in parentheses: 36 Atalante (C), 38 Leda (Cgh), 62 Erato (Ch), 121 Hermione (Ch), 165 Loreley (Cb), 194 Prokne (C), 203 Pompeja (C), 266 Aline (Ch), 52 Europa (Ch), and 19 Fortuna (Ch). Spectra were obtained in two wavelength regions: 8.5-13.6-μm and 17.6-27.7-μm. In these spectral regions, mineralogical features that are known to change continuously with amount of hydrated minerals appear. Most of these targets are known to have hydrated minerals on their surfaces by the presence of the 0.7-μm feature [e.g. 3, 4] or from observations in the 3-μm region [5]. We interpret the spectral features observed using SOFIA and estimate the abundances of hydrated minerals for each asteroid. Additionally, we compare these observations to Spitzer observations of similar objects. A subset of these asteroids have also been measured in VNIR, which allows us to directly compare the signatures of hydration in both the VNIR and the MIR.[1] McAdam et al., (2015), Icarus, 245, 320-332. [2] Cloutis, et al., (2011), Icarus, 216, 309-346. [3] Vilas and Gaffey (1989), Science, 246, 790-792. [4] Bus and Binzel (2002), Icarus, 158, 146-177. Takir and Emery (2012), Icarus, 219, 641-654.

Health- related quality of life and self-worth in 10-year old children with congenital hypothyroidism diagnosed by neonatal screening

PubMed Central

2012-01-01

Background Much is written about cognitive and motor development; less is known about social and emotional consequences of growing up with congenital hypothyroidism (CH). The objectives of the study were: (1) to compare health related quality of life (HRQoL) and self-worth of 10 year old patients with CH with the general population; (2) to explore associations of disease factors, IQ and motor skills with the outcomes. Methods Children with CH and their parents completed several questionnaires. Patients were classified to ‘severe CH, n = 41’ or ‘moderate/mild CH, n = 41’ based on pre-treatment FT4 concentration. Differences between CH and the general population were tested by analysis of covariance and one sample t-tests (mean scale scores HRQoL and self-worth), chi-square tests and binomial tests (% at risk of impaired HRQoL and self-worth). Linear regression analyses corrected for gender were conducted to explore associations of the outcomes with disease factors, IQ and motor skills. Results Patients with CH reported lower mean HRQoL on motor, cognitive and social functioning, and on autonomy and positive emotions (p < 0.0001). Patients were also more often at risk for impaired HRQoL and self-worth. No differences were found between the severity groups. Lower IQ was only significant associated with worse cognitive HRQoL. Initial FT4 plasma, age at onset of therapy, initial T4 dose and motor skills were not significantly associated with HRQoL and self-worth. Conclusions Negative consequences in terms of HRQoL and self-worth are prevalent in children with CH, independent of disease factors, IQ and motor skills. Physicians should to be attentive to these consequences and provide attention and supportive care. PMID:23034129

The role of forest floor and trees to the ecosystem scale methane budget of boreal forests

NASA Astrophysics Data System (ADS)

Pihlatie, Mari; Halmeenmäki, Elisa; Peltola, Olli; Haikarainen, Iikka; Heinonsalo, Jussi; Santalahti, Minna; Putkinen, Anuliina; Fritze, Hannu; Urban, Otmar; Machacova, Katerina

2016-04-01

Boreal forests are considered as a sink of atmospheric methane (CH4) due to the activity of CH4 oxidizing bacteria (methanotrophs) in the soil. This soil CH4 sink is especially strong for upland forest soils, whereas forests growing on organic soils may act as small sources due to the domination of CH4 production by methanogens in the anaerobic parts of the soil. The role of trees to the ecosystem-scale CH4 fluxes has until recently been neglected due to the perception that trees do not contribute to the CH4 exchange, and also due to difficulties in measuring the CH4 exchange from trees. Findings of aerobic CH4 formation in plants and emissions from tree-stems in temperate and tropical forests during the past decade demonstrate that our understanding of CH4 cycling in forest ecosystems is not complete. Especially the role of forest canopies still remain unresolved, and very little is known of CH4 fluxes from trees in boreal region. We measured the CH4 exchange of tree-stems and tree-canopies from pine (Pinus sylvestris), spruce (Picea abies) and birch (Betula pubescens, Betula pendula) trees growing in Southern Finland (SMEAR II station) on varying soil conditions, from upland mineral soils to paludified soil. We compared the CH4 fluxes from trees to forest-floor CH4 exchange, both measured by static chambers, and to CH4 fluxes measured above the forest canopy by a flux gradient technique. We link the CH4 fluxes from trees and forest floor to physiological activity of the trees, such as transpiration, sap-flow, CO2 net ecosystem exchange (NEE), soil properties such as temperature and moisture, and to the presence of CH4 producing methanogens and CH4 oxidizing methanotrophs in trees or soil. The above canopy CH4 flux measurements show that the whole forest ecosystem was a small source of CH4 over extended periods in the spring and summer 2012, 2014 and 2015. Throughout the 2013-2014 measurements, the forest floor was in total a net sink of CH4, with variation between high CH4 uptake in the dominating dry upland areas and high emissions from the few wet spots of the forest. All the studied tree species emitted small amounts of CH4 from the stems and shoots, with emission rates depending on the season, tree species and soil conditions. Especially, CH4 emissions from birch canopies were high and can therefore contribute significantly to the ecosystem-scale CH4 fluxes. Processes behind the canopy and stem CH4emission remain unresolved, however, ongoing analysis of the methanogens and methanotrophs within the plant-soil systems will reveal whether CH4 production or consumption is of microbial origin. Also, comparison of the CH4 fluxes from trees and forest floor to sap-flow, transpiration, and NEE as well as soil parameters will help to explain the seasonality and mechanisms involved in the CH4 emissions.

Double photoionization of propylene oxide: A coincidence study of the ejection of a pair of valence-shell electrons

NASA Astrophysics Data System (ADS)

Falcinelli, Stefano; Vecchiocattivi, Franco; Alagia, Michele; Schio, Luca; Richter, Robert; Stranges, Stefano; Catone, Daniele; Arruda, Manuela S.; Mendes, Luiz A. V.; Palazzetti, Federico; Aquilanti, Vincenzo; Pirani, Fernando

2018-03-01

Propylene oxide, a favorite target of experimental and theoretical studies of circular dichroism, was recently discovered in interstellar space, further amplifying the attention to its role in the current debate on protobiological homochirality. In the present work, a photoelectron-photoion-photoion coincidence technique, using an ion-imaging detector and tunable synchrotron radiation in the 18.0-37.0 eV energy range, permits us (i) to observe six double ionization fragmentation channels, their relative yields being accounted for about two-thirds by the couple (C2H4+, CH2O+) and one-fifth by (C2H3+, CH3O+); (ii) to measure thresholds for their openings as a function of photon energy; and (iii) to unravel a pronounced bimodality for a kinetic-energy-released distribution, fingerprint of competitive non-adiabatic mechanisms.

Hydrogen and methanol exchange processes for (TMP)Rh-OCH3(CH3OH) in binary solutions of methanol and benzene.

PubMed

Sarkar, Sounak; Li, Shan; Wayland, Bradford B

2011-04-18

Tetramesityl porphinato rhodium(III) methoxide ((TMP)Rh-OCH(3)) binds with methanol in benzene to form a 1:1 methanol complex ((TMP)Rh-OCH(3)(CH(3)OH)) (1). Dynamic processes are observed to occur for the rhodium(III) methoxide methanol complex (1) that involve both hydrogen and methanol exchange. Hydrogen exchange between coordinated methanol and methoxide through methanol in solution results in an interchange of the environments for the non-equivalent porphyrin faces that contain methoxide and methanol ligands. Interchange of the environments of the coordinated methanol and methoxide sites in 1 produces interchange of the inequivalent mesityl o-CH(3) groups, but methanol ligand exchange occurs on one face of the porphyrin and the mesityl o-CH(3) groups remain inequivalent. Rate constants for dynamic processes are evaluated by full line shape analysis for the (1)H NMR of the mesityl o-CH(3) and high field methyl resonances of coordinated methanol and methoxide groups in 1. The rate constant for interchange of the inequivalent porphyrin faces is associated with hydrogen exchange between 1 and methanol in solution and is observed to increase regularly with the increase in the mole fraction of methanol. The rate constant for methanol ligand exchange between 1 and the solution varies with the solution composition and fluctuates in a manner that parallels the change in the activation energy for methanol diffusion which is a consequence of solution non-ideality from hydrogen bonded clusters.

Martian CH(4): sources, flux, and detection.

PubMed

Onstott, T C; McGown, D; Kessler, J; Lollar, B Sherwood; Lehmann, K K; Clifford, S M

2006-04-01

Recent observations have detected trace amounts of CH(4) heterogeneously distributed in the martian atmosphere, which indicated a subsurface CH(4) flux of ~2 x 10(5) to 2 x 10(9) cm(2) s(1). Four different origins for this CH(4) were considered: (1) volcanogenic; (2) sublimation of hydrate- rich ice; (3) diffusive transport through hydrate-saturated cryosphere; and (4) microbial CH(4) generation above the cryosphere. A diffusive flux model of the martian crust for He, H(2), and CH(4) was developed based upon measurements of deep fracture water samples from South Africa. This model distinguishes between abiogenic and microbial CH(4) sources based upon their isotopic composition, and couples microbial CH(4) production to H(2) generation by H(2)O radiolysis. For a He flux of approximately 10(5) cm(2) s(1) this model yields an abiogenic CH(4) flux and a microbial CH(4) flux of approximately 10(6) and approximately 10(9) cm(2) s(1), respectively. This flux will only reach the martian surface if CH(4) hydrate is saturated in the cryosphere; otherwise it will be captured within the cryosphere. The sublimation of a hydrate-rich cryosphere could generate the observed CH(4) flux, whereas microbial CH(4) production in a hypersaline environment above the hydrate stability zone only seems capable of supplying approximately 10(5) cm(2) s(1) of CH(4). The model predicts that He/H(2)/CH(4)/C(2)H(6) abundances and the C and H isotopic values of CH(4) and the C isotopic composition of C(2)H(6) could reveal the different sources. Cavity ring-down spectrometers represent the instrument type that would be most capable of performing the C and H measurements of CH(4) on near future rover missions and pinpointing the cause and source of the CH(4) emissions.

40 CFR 98.326 - Data reporting requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... information for each mine: (a) Quarterly CH4 liberated from each ventilation monitoring point (CH4Vm), (metric tons CH4). (b) Weekly CH4 liberated from each degasification system monitoring point (metric tons CH4... degasification systems (metric tons CH4). (e) Quarterly CO2 emissions from on-site destruction of coal mine gas...

40 CFR 98.326 - Data reporting requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... information for each mine: (a) Quarterly CH4 liberated from each ventilation monitoring point (CH4Vm), (metric tons CH4). (b) Weekly CH4 liberated from each degasification system monitoring point (metric tons CH4... degasification systems (metric tons CH4). (e) Quarterly CO2 emissions from on-site destruction of coal mine gas...

40 CFR 98.326 - Data reporting requirements.

Code of Federal Regulations, 2011 CFR

2011-07-01

... information for each mine: (a) Quarterly CH4 liberated from each ventilation monitoring point (CH4Vm), (metric tons CH4). (b) Weekly CH4 liberated from each degasification system monitoring point (metric tons CH4... degasification systems (metric tons CH4). (e) Quarterly CO2 emissions from on-site destruction of coal mine gas...

Complex organic molecules in strongly UV-irradiated gas.

PubMed

Cuadrado, S; Goicoechea, J R; Cernicharo, J; Fuente, A; Pety, J; Tercero, B

2017-07-01

We investigate the presence of complex organic molecules (COMs) in strongly UV-irradiated interstellar molecular gas. We have carried out a complete millimetre (mm) line survey using the IRAM 30 m telescope towards the edge of the Orion Bar photodissociation region (PDR), close to the H 2 dissociation front, a position irradiated by a very intense far-UV (FUV) radiation field. These observations have been complemented with 8.5″ resolution maps of the H 2 CO J K a , K c = 5 1,5 → 4 1,4 and C 18 O J = 3 → 2 emission at 0.9 mm. Despite being a harsh environment, we detect more than 250 lines from COMs and related precursors: H 2 CO, CH 3 OH, HCO, H 2 CCO, CH 3 CHO, H 2 CS, HCOOH, CH 3 CN, CH 2 NH, HNCO, [Formula: see text] and HC 3 N (in decreasing order of abundance). For each species, the large number of detected lines allowed us to accurately constrain their rotational temperatures ( T rot ) and column densities ( N ). Owing to subthermal excitation and intricate spectroscopy of some COMs (symmetric- and asymmetric-top molecules such as CH 3 CN and H 2 CO, respectively), a correct determination of N and T rot requires building rotational population diagrams of their rotational ladders separately. The inferred column densities are in the 10 11 - 10 13 cm -2 range. We also provide accurate upper limit abundances for chemically related molecules that might have been expected, but are not conclusively detected at the edge of the PDR (HDCO, CH 3 O, CH 3 NC, CH 3 CCH, CH 3 OCH 3 , HCOOCH 3 , CH 3 CH 2 OH, CH 3 CH 2 CN, and CH 2 CHCN). A non-thermodynamic equilibrium excitation analysis for molecules with known collisional rate coefficients suggests that some COMs arise from different PDR layers but we cannot resolve them spatially. In particular, H 2 CO and CH 3 CN survive in the extended gas directly exposed to the strong FUV flux ( T k = 150 - 250 K and T d ≳ 60 K), whereas CH 3 OH only arises from denser and cooler gas clumps in the more shielded PDR interior ( T k = 40 - 50 K). The non-detection of HDCO towards the PDR edge is consistent with the minor role of pure gas-phase deuteration at very high temperatures. We find a HCO/H 2 CO/CH 3 OH ≃ 1/5/3 abundance ratio. These ratios are different from those inferred in hot cores and shocks. Taking into account the elevated gas and dust temperatures at the edge of the Bar (mostly mantle-free grains), we suggest the following scenarios for the formation of COMs: (i) hot gas-phase reactions not included in current models; (ii) warm grain-surface chemistry; or (iii) the PDR dynamics is such that COMs or precursors formed in cold icy grains deeper inside the molecular cloud desorb and advect into the PDR.

Gaia's breath - Global methane exhalations

USGS Publications Warehouse

Kvenvolden, K.A.; Rogers, B.W.

2005-01-01

Methane (CH4) is the most abundant organic compound in the Earth's atmosphere, where it acts as a greenhouse gas and thus has implications for global climate change. The current atmospheric CH4 budget, however, does not take into account geologically-sourced CH4 seepage. Geological sources of CH4 include natural macro- and micro-seeps, mud volcanoes, and other miscellaneous sources such as gas hydrates, magmatic volcanoes, geothermal regions, and mid-ocean ridges. Macro-seeps contribute ???25 Tg (teragrams) CH4/yr to the atmosphere, whereas, micro-seepage contributes perhaps 7 Tg CH4/yr. Mud volcanoes emit ???5 Tg CH4/yr, and miscellaneous sources emit ???8 Tg CH4/yr to the atmosphere. Thus, the total contribution to the atmosphere from geological sources is estimated to be 45 Tg CH4/yr, which is significant to the atmospheric organic carbon cycle and should be included in any global inventory of atmospheric CH4. We argue that the atmospheric CH4 global inventory of the Interplanetary Panel on Climate Change must be adjusted in order to incorporate geologically-sourced CH4 from naturally occurring seepage.

Slow magnetic relaxation in a dimeric Mn2Ca2 complex enabled by the large Mn(iii) rhombicity.

PubMed

Arauzo, Ana; Bartolomé, Elena; Benniston, Andrew C; Melnic, Silvia; Shova, Sergiu; Luzón, Javier; Alonso, Pablo J; Barra, Anne-Laure; Bartolomé, Juan

2017-01-17

In this paper we present the characterization of a complex with the formula [Mn 2 Ca 2 (hmp) 6 (H 2 O) 4 (CH 3 CN) 2 ](ClO 4 ) 4 (1), where hmp-H = 2-(hydroxymethyl)pyridine. Compound 1 crystallizes in the monoclinic space group C2/c with the cation lying on an inversion centre. Static magnetic susceptibility, magnetization and heat capacity measurements reflect a unique Mn(iii) valence state, and single-ion ligand field parameters with remarkable large rhombic distortion (D/k B = -6.4 K, E/k B = -2.1 K), in good agreement with the high-field electron paramagnetic resonance experiments. At low temperature Mn 2 Ca 2 cluster behaves as a system of ferromagnetically coupled (J/k B = 1.1 K) Mn dimers with a S T = 4 and m T = ±4 ground state doublet. Frequency dependent ac susceptibility measurements reveal the slow magnetic relaxation characteristic of a single molecule magnet (SMM) below T = 4 K. At zero magnetic field, an Orbach-type spin relaxation process (τ ∼ 10 -5 s) with an activation energy E a = 5.6 K is observed, enabled by the large E/D rhombicity of the Mn(iii) ions. Upon the application of a magnetic field, a second, very slow process (τ ∼ 0.2 s) is observed, attributed to a direct relaxation mechanism with enhanced relaxation time owing to the phonon bottleneck effect.

A preliminary ab-initio calculation of the spectrum of CH4 and its applications to the spectra of giant planets and brown dwarfs.

NASA Astrophysics Data System (ADS)

Freedman, R. S.; Schwenke, D. W.

2000-12-01

Methane is not only an important opacity source in brown dwarfs and giant planets, but its appearance in the spectrum is often used as an indicator of a low temperature object. Unfortunately, the analysis of the spectrum of this important molecule is far from complete due to its great complexity. In this presentation we will show progress that has been made by David Schwenke and Harry Partridge in developing an ab initio potential surface for CH4. Examples will be given to illustrate the current state of the calculations, and the applications to the interpretation of astronomical spectra. Computational Chemistry Branch - NASA Ames.

Multiheteromacrocycles that Complex Metal Ions. Second Progress Report, 1 May 1975 -- 30 April 1976

DOE R&D Accomplishments Database

Cram, D. J.

1976-01-15

Objective is to develop cyclic and polycyclic host organic compounds to complex and lipophilize metal ions. Macrorings were synthesized: (OCH{sub 2} CH{sub 2} O CH{sub 2}COCH{sub 2} COCH{sub 2}){sub 2} and (OCH{sub 2} CH{sub 2} O CH{sub 2} COCH{sub 2} COCH{sub 2}){sub 3}. The smaller ring complexes divalent metals 10{sup 1+9} times better than the open-chain model CH{sub 3} O CH{sub 2} CO CH{sub 2} COCH{sub 2} O CH{sub 3}, and the order in which metal ions are complexed is Cu{sup 2+}, UO{sub 2}{sup 2+} greater than Ni{sup 2+} greater than Fe{sup 2+}, Co{sup 2+}, Zn{sup 2+}, Cd{sup 2+} greater than Mn{sup 2+}. The UO{sub 2}{sup 2+} and Cu{sup 2+} complexes were isolated and characterized. The larger ring complexes trivalent metals 10{sup 0.9-1.7} times better than the open- chain model compound, and the order is La{sup 3+}, Ce{sup 3+} greater than Cr{sup 3+}. Five other macrocycles were also synthesized, and their binding constants with Na, K, NH{sub 4}, and Cs picrates were measured. Six compounds containing one macroring and two inward-pointing ArOH or ArOCH{sub 3} groups were also prepared and tested for binding of Li, Na, K, Rb, and NH{sub 4} picrates. Racemic compounds containing two binaphthyls and its sulfur analog were prepared. Cage-shaped multiheteromacrocycles containing ten O ligand sites or four S and six O ligand sites were prepared and the binding capability of the first compound for picrates studied. Two ring systems with phosphonate ester groups were also prepared. (DLC)

Investigating CH4 production in an oxic plant-soil system -a new approach combining isotopic labelling (13C) and inhibitors

NASA Astrophysics Data System (ADS)

Lenhart, Katharina; Keppler, Frank

2017-04-01

Typically, aerated soil are net sinks of atmospheric methane (CH4), being highest in native ecosystems (pristine forests > managed forests > grasslands > crop fields). However, this does not exclude a simultaneous endogenic CH4 production in the plant-soil system, which cannot be detected simply via CH4 flux measurements. Methanogenic archaea producing CH4 under anoxic conditions were thought to be the only biotic source of CH4 in the soil. However, until recently a non-archaeal pathway of CH4 formation is known where CH4 is produced under oxic conditions in plants (Keppler et al. 2006) and fungi (Lenhart et al. 2012). Additionally, abiotic formation of CH4 from soil organic matter was reported (Jugold et al. 2012) and may be ubiquitous in terrestrial ecosystems. The major goal of this project was to determine soil endogenic CH4 sources and to estimate their contribution to the endogenic CH4 production. Especially the effect of plants and fungi on soil CH4 production was investigated. Therefore, a series of experiments was carried out on field fresh soil collected in a grassland and a forest ecosystem under controlled laboratory conditions. By combining selective inhibitors and 13C labelling, CH4 production rates of several CH4 sources were quantified. The major difficulty was to detect the comparatively small flux of CH4 production against the background of the high CH4 consumption rates due to methanotrophic bacteria. Therefore, we supplemented bare soil and soil with vegetation with selective inhibitors and 13C labelled substrates in a closed chamber system. In a first step, CH4 production was determined by the inhibition of CH4 oxidizing bacteria with Difluoromethane (DFM, 2ml l-1). In the following, a 13C labelled substrate (either CO2, Acetate, or Methionine -S-CH3 labelled) was added in combination with a specific inhibitor -either for archaeal methanogenesis (Bromoethanesulfonate), bacteria (Streptomycin), or fungi (Captan, Cycloheximide). Gas samples were taken during the incubation for CH4 and CO2 concentration measurements and isotope ratio mass spectrometry (CH4, CO2). Grassland and forest soils showed differences in CO2 and CH4 production rates. Based on the 13C-CH4 signature we found that all substrates were metabolized to CH4, but to a different degree. Inhibitors reduced CH4 production and conversion of certain substrates to a different degree. Using the example of acetate and cycloheximide, in both soils acetate increased respiration, whereas cycloheximide reduced respiration by 56 and 62 %, respectively. For CH4 production, however, no effect was visible for the grassland soil, but in the forest soil CH4 production increased by 69 %. Cycloheximide inhibited the substrate-induced CH4 production by 63 %, indicating that fungi were responsible for this pathway. Moreover, the finding that fungi use the methyl group of acetate to produce CH4 was also verified with a sterile culture. References Lenhart, K. et al. Evidence for methane production by saprotrophic fungi. Nat Commun 3, 1046, (2012). Keppler, F., et al. Methane emissions from terrestrial plants under aerobic conditions. Nature 439, 187-191 (2006). Jugold, A. et al. Non-microbial methane formation in oxic soils. Biogeosciences 9, 5291-5301, (2012).

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Multi-wavelength investigations on feedback of massive star formation

NASA Astrophysics Data System (ADS)

Yuan, Jinghua

2014-05-01

In the course of massive star formation, outflows, ionizing radiation and intense stellar winds could heavily affect their adjacent environs and natal clouds. There are several outstanding open questions related to these processes: i) whether they can drive turbulence in molecular clouds; ii) whether they are able to trigger star formation; iii) whether they can destroy natal clouds to terminate star formation at low efficiencies. This thesis investigates feedback in different stages of massive star formation. Influence of such feedback to the ambient medium has been revealed. A new type of millimeter methanol maser is detected for the first time. An uncommon bipolar outflow prominent in the mid-infrared is discovered. And features of triggered star formation are found on the border of an infrared bubble and in the surroundings of a Herbig Be star. Extended green objects (EGOs) are massive outflow candidates showing prominent shocked features in the mid-infrared. We have carried out a high resolution study of the EGO G22.04+0.22 (hereafter, G22) based on archived SMA data. Continuum and molecular lines at 1.3 mm reveal that G22 is still at a hot molecular core stage. A very young multi-polar outflow system is detected, which is interacting with the adjacent dense gas. Anomalous emission features from CH3OH (8,-1,8 - 7,0,7) and CH3OH (4,2,2 - 3,1,2) are proven to be millimeter masers. It is the first time that maser emission of CH3OH (8,-1,8 - 7,0,7) at 218.440 GHz is detected in a massive star-forming region. Bipolar outflows have been revealed and investigated almost always in the microwave or radio domain. It's sort of rare that hourglass-shaped morphology be discovered in the mid-infrared. Based on GLIMPSE data, we have discovered a bipolar object resembling an hourglass at 8.0 um. It is found to be associated with IRAS 18114-1825. Analysis based on fitted SED, optical spectroscopy, and infrared color indices suggests IRAS 18114-1825 is an uncommon bipolar outflow driven by a massive protostar. Multi-wavelength observations based on classical tracers of outflows are highly necessary. Extensive investigations of IRAS 18114-1825 may contribute to our understanding of massive star formation in early stage.

Synthesis, structures and urease inhibitory activity of cobalt(III) complexes with Schiff bases.

PubMed

Jing, Changling; Wang, Cunfang; Yan, Kai; Zhao, Kedong; Sheng, Guihua; Qu, Dan; Niu, Fang; Zhu, Hailiang; You, Zhonglu

2016-01-15

A series of new cobalt(III) complexes were prepared. They are [CoL(1)(py)3]·NO3 (1), [CoL(2)(bipy)(N3)]·CH3OH (2), [CoL(3)(HL(3))(N3)]·NO3 (3), and [CoL(4)(MeOH)(N3)] (4), where L(1), L(2), L(3) and L(4) are the deprotonated form of N'-(2-hydroxy-5-methoxybenzylidene)-3-methylbenzohydrazide, N'-(2-hydroxybenzylidene)-3-hydroxylbenzohydrazide, 2-[(2-dimethylaminoethylimino)methyl]-4-methylphenol, and N,N'-bis(5-methylsalicylidene)-o-phenylenediamine, respectively, py is pyridine, and bipy is 2,2'-bipyridine. The complexes were characterized by infrared and UV-Vis spectra, and single crystal X-ray diffraction. The Co atoms in the complexes are in octahedral coordination. Complexes 1 and 4 show effective urease inhibitory activities, with IC50 values of 4.27 and 0.35 μmol L(-1), respectively. Complex 2 has medium activity against urease, with IC50 value of 68.7 μmol L(-1). While complex 3 has no activity against urease. Molecular docking study of the complexes with Helicobacter pylori urease was performed. Copyright © 2015 Elsevier Ltd. All rights reserved.

The global methane budget 2000-2012

NASA Astrophysics Data System (ADS)

Saunois, Marielle; Bousquet, Philippe; Poulter, Ben; Peregon, Anna; Ciais, Philippe; Canadell, Josep G.; Dlugokencky, Edward J.; Etiope, Giuseppe; Bastviken, David; Houweling, Sander; Janssens-Maenhout, Greet; Tubiello, Francesco N.; Castaldi, Simona; Jackson, Robert B.; Alexe, Mihai; Arora, Vivek K.; Beerling, David J.; Bergamaschi, Peter; Blake, Donald R.; Brailsford, Gordon; Brovkin, Victor; Bruhwiler, Lori; Crevoisier, Cyril; Crill, Patrick; Covey, Kristofer; Curry, Charles; Frankenberg, Christian; Gedney, Nicola; Höglund-Isaksson, Lena; Ishizawa, Misa; Ito, Akihiko; Joos, Fortunat; Kim, Heon-Sook; Kleinen, Thomas; Krummel, Paul; Lamarque, Jean-François; Langenfelds, Ray; Locatelli, Robin; Machida, Toshinobu; Maksyutov, Shamil; McDonald, Kyle C.; Marshall, Julia; Melton, Joe R.; Morino, Isamu; Naik, Vaishali; O'Doherty, Simon; Parmentier, Frans-Jan W.; Patra, Prabir K.; Peng, Changhui; Peng, Shushi; Peters, Glen P.; Pison, Isabelle; Prigent, Catherine; Prinn, Ronald; Ramonet, Michel; Riley, William J.; Saito, Makoto; Santini, Monia; Schroeder, Ronny; Simpson, Isobel J.; Spahni, Renato; Steele, Paul; Takizawa, Atsushi; Thornton, Brett F.; Tian, Hanqin; Tohjima, Yasunori; Viovy, Nicolas; Voulgarakis, Apostolos; van Weele, Michiel; van der Werf, Guido R.; Weiss, Ray; Wiedinmyer, Christine; Wilton, David J.; Wiltshire, Andy; Worthy, Doug; Wunch, Debra; Xu, Xiyan; Yoshida, Yukio; Zhang, Bowen; Zhang, Zhen; Zhu, Qiuan

2016-12-01

The global methane (CH4) budget is becoming an increasingly important component for managing realistic pathways to mitigate climate change. This relevance, due to a shorter atmospheric lifetime and a stronger warming potential than carbon dioxide, is challenged by the still unexplained changes of atmospheric CH4 over the past decade. Emissions and concentrations of CH4 are continuing to increase, making CH4 the second most important human-induced greenhouse gas after carbon dioxide. Two major difficulties in reducing uncertainties come from the large variety of diffusive CH4 sources that overlap geographically, and from the destruction of CH4 by the very short-lived hydroxyl radical (OH). To address these difficulties, we have established a consortium of multi-disciplinary scientists under the umbrella of the Global Carbon Project to synthesize and stimulate research on the methane cycle, and producing regular (˜ biennial) updates of the global methane budget. This consortium includes atmospheric physicists and chemists, biogeochemists of surface and marine emissions, and socio-economists who study anthropogenic emissions. Following Kirschke et al. (2013), we propose here the first version of a living review paper that integrates results of top-down studies (exploiting atmospheric observations within an atmospheric inverse-modelling framework) and bottom-up models, inventories and data-driven approaches (including process-based models for estimating land surface emissions and atmospheric chemistry, and inventories for anthropogenic emissions, data-driven extrapolations). For the 2003-2012 decade, global methane emissions are estimated by top-down inversions at 558 Tg CH4 yr-1, range 540-568. About 60 % of global emissions are anthropogenic (range 50-65 %). Since 2010, the bottom-up global emission inventories have been closer to methane emissions in the most carbon-intensive Representative Concentrations Pathway (RCP8.5) and higher than all other RCP scenarios. Bottom-up approaches suggest larger global emissions (736 Tg CH4 yr-1, range 596-884) mostly because of larger natural emissions from individual sources such as inland waters, natural wetlands and geological sources. Considering the atmospheric constraints on the top-down budget, it is likely that some of the individual emissions reported by the bottom-up approaches are overestimated, leading to too large global emissions. Latitudinal data from top-down emissions indicate a predominance of tropical emissions (˜ 64 % of the global budget, < 30° N) as compared to mid (˜ 32 %, 30-60° N) and high northern latitudes (˜ 4 %, 60-90° N). Top-down inversions consistently infer lower emissions in China (˜ 58 Tg CH4 yr-1, range 51-72, -14 %) and higher emissions in Africa (86 Tg CH4 yr-1, range 73-108, +19 %) than bottom-up values used as prior estimates. Overall, uncertainties for anthropogenic emissions appear smaller than those from natural sources, and the uncertainties on source categories appear larger for top-down inversions than for bottom-up inventories and models. The most important source of uncertainty on the methane budget is attributable to emissions from wetland and other inland waters. We show that the wetland extent could contribute 30-40 % on the estimated range for wetland emissions. Other priorities for improving the methane budget include the following: (i) the development of process-based models for inland-water emissions, (ii) the intensification of methane observations at local scale (flux measurements) to constrain bottom-up land surface models, and at regional scale (surface networks and satellites) to constrain top-down inversions, (iii) improvements in the estimation of atmospheric loss by OH, and (iv) improvements of the transport models integrated in top-down inversions. The data presented here can be downloaded from the Carbon Dioxide Information Analysis Center (http://doi.org/10.3334/CDIAC/GLOBAL_METHANE_BUDGET_2016_V1.1) and the Global Carbon Project.

The Global Methane Budget 2000-2012

NASA Technical Reports Server (NTRS)

Saunois, Marielle; Bousquet, Philippe; Poulter, Benjamin; Peregon, Anna; Ciais, Philippe; Canadell, Josep G.; Dlugokencky, Edward J.; Etiope, Giuseppe; Bastviken, David; Houweling, Sander;

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

PubMed Central

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

2017-01-01

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

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

PubMed

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

2017-01-01

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

Extensive hydrothermal activity revealed by multi-tracer survey in the Wallis and Futuna region (SW Pacific)

NASA Astrophysics Data System (ADS)

Konn, C.; Fourré, E.; Jean-Baptiste, P.; Donval, J. P.; Guyader, V.; Birot, D.; Alix, A. S.; Gaillot, A.; Perez, F.; Dapoigny, A.; Pelleter, E.; Resing, J. A.; Charlou, J. L.; Fouquet, Y.

2016-10-01

The study area is close to the Wallis and Futuna Islands in the French EEZ. It exists on the western boundary of the fastest tectonic area in the world at the junction of the Lau and North-Fiji basins. At this place, the unstable back-arc accommodates the plate motion in three ways: (i) the north Fiji transform fault, (ii) numerous unstable spreading ridges, and (iii) large areas of recent volcanic activity. This instability creates bountiful opportunity for hydrothermal discharge to occur. Based on geochemical (CH4, TDM, 3He) and geophysical (nephelometry) tracer surveys: (1) no hydrothermal activity could be found on the Futuna Spreading Centre (FSC) which sets the western limit of hydrothermal activity; (2) four distinct hydrothermal active areas were identified: Kulo Lasi Caldera, Amanaki Volcano, Fatu Kapa and Tasi Tulo areas; (3) extensive and diverse hydrothermal manifestations were observed and especially a 2D distribution of the sources. At Kulo Lasi, our data and especially tracer ratios (CH4/3He 50×106 and CH4/TDM 4.5) reveal a transient CH4 input, with elevated levels of CH4 measured in 2010, that had vanished in 2011, most likely caused by an eruptive magmatic event. By contrast at Amanaki, vertical tracer profiles and tracer ratios point to typical seawater/basalt interactions. Fatu Kapa is characterised by a substantial spatial variability of the hydrothermal water column anomalies, most likely due to widespread focused and diffuse hydrothermal discharge in the area. In the Tasi Tulo zone, the hydrothermal signal is characterised by a total lack of turbidity, although other tracer anomalies are in the same range as in nearby Fatu Kapa. The background data set revealed the presence of a Mn and 3He chronic plume due to the extensive and cumulative venting over the entire area. To that respect, we believe that the joined domain composed of our active area and the nearby active area discovered in the East by Lupton et al. (2012) highly contribute to the extensive Tonga-Fiji plume and which thus may not originate from a sole source near the Samoa. Our results also emphasize and support the idea that back-arc hydrothermal systems have a significant input to the regional and global ocean and maybe more important than their MOR analogues.

CH5424802 (RO5424802) for patients with ALK-rearranged advanced non-small-cell lung cancer (AF-001JP study): a single-arm, open-label, phase 1-2 study.

PubMed

Seto, Takashi; Kiura, Katsuyuki; Nishio, Makoto; Nakagawa, Kazuhiko; Maemondo, Makoto; Inoue, Akira; Hida, Toyoaki; Yamamoto, Nobuyuki; Yoshioka, Hiroshige; Harada, Masao; Ohe, Yuichiro; Nogami, Naoyuki; Takeuchi, Kengo; Shimada, Tadashi; Tanaka, Tomohiro; Tamura, Tomohide

2013-06-01

Currently, crizotinib is the only drug that has been approved for treatment of ALK-rearranged non-small-cell lung cancer (NSCLC). We aimed to study the activity and safety of CH5424802, a potent, selective, and orally available ALK inhibitor. In this multicentre, single-arm, open-label, phase 1-2 study of CH5424802, we recruited ALK inhibitor-naive patients with ALK-rearranged advanced NSCLC from 13 hospitals in Japan. In the phase 1 portion of the study, patients received CH5424802 orally twice daily by dose escalation. The primary endpoints of the phase 1 were dose limiting toxicity (DLT), maximum tolerated dose (MTD), and pharmacokinetic parameters. In the phase 2 portion of the study, patients received CH5424802 at the recommended dose identified in the phase 1 portion of the study orally twice a day. The primary endpoint of the phase 2 was the proportion of patients who had an objective response. Treatment was continued in 21-day cycles until disease progression, intolerable adverse events, or withdrawal of consent. The analysis was done by intent to treat. This study is registered with the Japan Pharmaceutical Information Center, number JapicCTI-101264. Patients were enrolled between Sept 10, 2010, and April 18, 2012. The data cutoff date was July 31, 2012. In the phase 1 portion, 24 patients were treated at doses of 20-300 mg twice daily. No DLTs or adverse events of grade 4 were noted up to the highest dose; thus 300 mg twice daily was the recommended phase 2 dose. In the phase 2 portion of the study, 46 patients were treated with the recommended dose, of whom 43 achieved an objective response (93.5%, 95% CI 82.1-98.6) including two complete responses (4.3%, 0.5-14.8) and 41 partial responses (89.1%, 76.4-96.4). Treatment-related adverse events of grade 3 were recorded in 12 (26%) of 46 patients, including two patients each experiencing decreased neutrophil count and increased blood creatine phosphokinase. Serious adverse events occurred in five patients (11%). No grade 4 adverse events or deaths were reported. The study is still ongoing, since 40 of the 46 patients in the phase 2 portion remain on treatment. CH5424802 is well tolerated and highly active in patients with advanced ALK-rearranged NSCLC. Chugai Pharmaceutical Co, Ltd. Copyright © 2013 Elsevier Ltd. All rights reserved.

Hexavalent chromium removal in contaminated water using reticulated chitosan micro/nanoparticles from seafood processing wastes.

PubMed

Dima, Jimena Bernadette; Sequeiros, Cynthia; Zaritzky, Noemi E

2015-12-01

Chitosan particles (CH) were obtained from seafood processing wastes (shrimp shells) and physicochemically characterized; deacetylation degree of CH was measured by Infrared Spectroscopy (FTIR) and potentiometric titration; polymer molecular weight was determined by intrinsic viscosity measurements. Reticulated micro/nanoparticles of chitosan (MCH) with an average diameter close to 100nm were synthesized by ionic gelation of chitosan using tripolyphosphate (TPP), and characterized by SEM, size distribution and Zeta-potential. Detoxification capacities of CH and MCH were tested analyzing the removal of hexavalent chromium Cr(VI) from contaminated water, at different initial chromium concentrations. The effect of pH on adsorption capacity of CH and MCH was experimentally determined and analyzed considering the Cr(VI) stable complexes (anions) formed, the presence of protonated groups in chitosan particles and the addition of the reticulating agent (TPP). Chitosan crosslinking was necessary to adsorb Cr(VI) at pH<2 due to the instability of CH particles in acid media. Langmuir isotherm described better than Freundlich and Temkin equations the equilibrium adsorption data. Pseudo-second order rate provided the best fitting to the kinetic data in comparison to pseudo-first order and Elovich equations. Chemical analysis to determine the oxidation state of the adsorbed Cr, showed that Cr(VI) was adsorbed on CH particles without further reduction; in contrast Cr(VI) removed from the solution was reduced and bound to the MCH as Cr(III). The reduction of toxic Cr(VI) to the less or nontoxic Cr(III) by the reticulated chitosan micro/nanoparticles can be considered a very efficient detoxification technique for the treatment of Cr(VI) contaminated water. Copyright © 2015 Elsevier Ltd. All rights reserved.

Adding stable carbon isotopes improves model representation of the role of microbial communities in peatland methane cycling

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

Deng, Jia; McCalley, Carmody K.; Frolking, Steve

Climate change is expected to have significant and uncertain impacts on methane (CH 4) emissions from northern peatlands. Biogeochemical models can extrapolate site-specific CH 4 measurements to larger scales and predict responses of CH 4 emissions to environmental changes. However, these models include considerable uncertainties and limitations in representing CH4 production, consumption, and transport processes. To improve predictions of CH 4 transformations, we incorporated acetate and stable carbon (C) isotopic dynamics associated with CH 4 cycling into a biogeochemistry model, DNDC. By including these new features, DNDC explicitly simulates acetate dynamics and the relative contribution of acetotrophic and hydrogenotrophic methanogenesismore » (AM and HM) to CH 4 production, and predicts the C isotopic signature (δ 13C) in soil C pools and emitted gases. When tested against biogeochemical and microbial community observations at two sites in a zone of thawing permafrost in a subarctic peatland in Sweden, the new formulation substantially improved agreement with CH 4 production pathways and δ 13C in emitted CH 4 (δ 13C-CH 4), a measure of the integrated effects of microbial production and consumption, and of physical transport. We also investigated the sensitivity of simulated δ 13C-CH 4 to C isotopic composition of substrates and, to fractionation factors for CH4 production (α AM and α HM), CH 4 oxidation (α MO), and plant-mediated CH 4 transport (α TP). The sensitivity analysis indicated that the δ13C-CH 4 is highly sensitive to the factors associated with microbial metabolism (α AM, α HM, and α MO). The model framework simulating stable C isotopic dynamics provides a robust basis for better constraining and testing microbial mechanisms in predicting CH 4 cycling in peatlands.« less

Adding stable carbon isotopes improves model representation of the role of microbial communities in peatland methane cycling

DOE PAGES

Deng, Jia; McCalley, Carmody K.; Frolking, Steve; ...

2017-06-13

Climate change is expected to have significant and uncertain impacts on methane (CH 4) emissions from northern peatlands. Biogeochemical models can extrapolate site-specific CH 4 measurements to larger scales and predict responses of CH 4 emissions to environmental changes. However, these models include considerable uncertainties and limitations in representing CH4 production, consumption, and transport processes. To improve predictions of CH 4 transformations, we incorporated acetate and stable carbon (C) isotopic dynamics associated with CH 4 cycling into a biogeochemistry model, DNDC. By including these new features, DNDC explicitly simulates acetate dynamics and the relative contribution of acetotrophic and hydrogenotrophic methanogenesismore » (AM and HM) to CH 4 production, and predicts the C isotopic signature (δ 13C) in soil C pools and emitted gases. When tested against biogeochemical and microbial community observations at two sites in a zone of thawing permafrost in a subarctic peatland in Sweden, the new formulation substantially improved agreement with CH 4 production pathways and δ 13C in emitted CH 4 (δ 13C-CH 4), a measure of the integrated effects of microbial production and consumption, and of physical transport. We also investigated the sensitivity of simulated δ 13C-CH 4 to C isotopic composition of substrates and, to fractionation factors for CH4 production (α AM and α HM), CH 4 oxidation (α MO), and plant-mediated CH 4 transport (α TP). The sensitivity analysis indicated that the δ13C-CH 4 is highly sensitive to the factors associated with microbial metabolism (α AM, α HM, and α MO). The model framework simulating stable C isotopic dynamics provides a robust basis for better constraining and testing microbial mechanisms in predicting CH 4 cycling in peatlands.« less

Aerial photography based census of Adélie Penguin and its application in CH4 and N2O budget estimation in Victoria Land, Antarctic.

PubMed

He, Hong; Cheng, Xiao; Li, Xianglan; Zhu, Renbin; Hui, Fengming; Wu, Wenhui; Zhao, Tiancheng; Kang, Jing; Tang, Jianwu

2017-10-11

Penguin guano provides favorable conditions for production and emission of greenhouse gases (GHGs). Many studies have been conducted to determine the GHG fluxes from penguin colonies, however, at regional scale, there is still no accurate estimation of total GHG emissions. We used object-based image analysis (OBIA) method to estimate the Adélie penguin (Pygoscelis adeliae) population based on aerial photography data. A model was developed to estimate total GHG emission potential from Adélie penguin colonies during breeding seasons in 1983 and 2012, respectively. Results indicated that OBIA method was effective for extracting penguin information from aerial photographs. There were 17,120 and 21,183 Adélie penguin breeding pairs on Inexpressible Island in 1983 and 2012, respectively, with overall accuracy of the estimation of 76.8%. The main reasons for the increase in Adélie penguin populations were attributed to increase in temperature, sea ice and phytoplankton. The average estimated CH 4 and N 2 O emissions tended to be increasing during the period from 1983 to 2012 and CH 4 was the main GHG emitted from penguin colonies. Total global warming potential (GWP) of CH 4 and N 2 O emissions was 5303 kg CO 2 -eq in 1983 and 6561 kg CO 2 -eq in 2012, respectively.

Isotopic signatures of anthropogenic CH4 sources in Alberta, Canada

NASA Astrophysics Data System (ADS)

Lopez, M.; Sherwood, O. A.; Dlugokencky, E. J.; Kessler, R.; Giroux, L.; Worthy, D. E. J.

2017-09-01

A mobile system was used for continuous ambient measurements of stable CH4 isotopes (12CH4 and 13CH4) and ethane (C2H6). This system was used during a winter mobile campaign to investigate the CH4 isotopic signatures and the C2H6/CH4 ratios of the main anthropogenic sources of CH4 in the Canadian province of Alberta. Individual signatures were derived from δ13CH4 and C2H6 measurements in plumes arriving from identifiable single sources. Methane emissions from beef cattle feedlots (n = 2) and landfill (n = 1) had δ13CH4 signatures of -66.7 ± 2.4‰ and -55.3 ± 0.2‰, respectively. The CH4 emissions associated with the oil or gas industry had distinct δ13CH4 signatures, depending on the formation process. Emissions from oil storage tanks (n = 5) had δ13CH4 signatures ranging from -54.9 ± 2.9‰ to -60.6 ± 0.6‰ and non-detectable C2H6, characteristic of secondary microbial methanogenesis in oil-bearing reservoirs. In contrast, CH4 emissions associated with natural gas facilities (n = 8) had δ13CH4 signatures ranging from -41.7 ± 0.7‰ to -49.7 ± 0.7‰ and C2H6/CH4 molar ratios of 0.10 for raw natural gas to 0.04 for processed/refined natural gas, consistent with thermogenic origins. These isotopic signatures and C2H6/CH4 ratios have been used for source discrimination in the weekly atmospheric measurements of stable CH4 isotopes over a two-month winter period at the Lac La Biche (LLB) measurement station, located in Alberta, approximately 200 km northeast of Edmonton. The average signature of -59.5 ± 1.4‰ observed at LLB is likely associated with transport of air after passing over oil industry sources located south of the station.

Methane production potential and emission at different water levels in the restored reed wetland of Hangzhou Bay

PubMed Central

Sheng, Xuancai; Wu, Ming; Wu, Hao; Ning, Xiao

2017-01-01

Changes in the hydrological conditions of coastal wetlands may potentially affect the role of wetlands in the methane (CH4) cycle. In this study, the CH4 production potential and emissions from restored coastal reed wetlands at different water levels were examined in eastern China at a field scale in two phenological seasons. Results showed that the total CH4 flux from reeds at various water levels were positive, indicating that they were “sources” of CH4. During the peak growing season, CH4 flux from reeds was greater than that during the spring thaw. CH4 flux from reeds in inundated conditions was greater than that in non-inundated conditions. The CH4 production potential during the peak growing season was far greater than that during the spring thaw. However, the effect of water level on wetland CH4 production potential differed among seasons. The correlations among CH4 production potential, soil properties and CH4 flux change at different water level. These results demonstrate that water level was related to CH4 production and CH4 flux. The growing season also plays a role in CH4 fluxes. Controlling the hydrological environment in restored wetlands has important implications for the maintenance of their function as carbon sinks. PMID:28968419

C-H activation in Ir(III) and N-demethylation in Pt(II) complexes with mesoionic carbene ligands: examples of monometallic, homobimetallic and heterobimetallic complexes.

PubMed

Maity, Ramananda; Tichter, Tim; van der Meer, Margarethe; Sarkar, Biprajit

2015-11-14

Mononuclear Pt(II) and the first dinuclear Pt(II) complexes along with a cyclometalated heterobimetallic Ir(III)/Pd(II) complex bearing mesoionic carbene donor ligands are presented starting from the same bis-triazolium salt. The mononuclear Pt(II) complex possesses a free triazole moiety which is generated from the corresponding triazolium salt through an N-demethylation reaction, whereas the mononuclear Ir(III) complex features an unreacted triazolium unit.

Effects on enteric methane production and bacterial and archaeal communities by the addition of cashew nut shell extract or glycerol-an in vitro evaluation.

PubMed

Danielsson, Rebecca; Werner-Omazic, Anna; Ramin, Mohammad; Schnürer, Anna; Griinari, Mikko; Dicksved, Johan; Bertilsson, Jan

2014-09-01

The objective of the study was to evaluate the effect of cashew nut shell extract (CNSE) and glycerol (purity >99%) on enteric methane (CH4) production and microbial communities in an automated gas in vitro system. Microbial communities from the in vitro system were compared with samples from the donor cows, in vivo. Inoculated rumen fluid was mixed with a diet with a 60:40 forage:concentrate ratio and, in total, 5 different treatments were set up: 5mg of CNSE (CNSE-L), 10mg of CNSE (CNSE-H), 15mmol of glycerol/L (glycerol-L), and 30mmol of glycerol/L (glycerol-H), and a control without feed additive. Gas samples were taken at 2, 4, 8, 24, 32, and 48h of incubation, and the CH4 concentration was measured. Samples of rumen fluid were taken for volatile fatty acid analysis and for microbial sequence analyses after 8, 24, and 48h of incubation. In vivo rumen samples from the cows were taken 2h after the morning feeding at 3 consecutive days to compare the in vitro system with in vivo conditions. The gas data and data from microbial sequence analysis (454 sequencing) were analyzed using a mixed model and principal components analysis. These analyses illustrated that CH4 production was reduced with the CNSE treatment, by 8 and 18%, respectively, for the L and H concentration. Glycerol instead increased CH4 production by 8 and 12%, respectively, for the L and H concentration. The inhibition with CNSE could be due to the observed shift in bacterial population, possibly resulting in decreased production of hydrogen or formate, the methanogenic substrates. Alternatively the response could be explained by a shift in the methanogenic community. In the glycerol treatments, no main differences in bacterial or archaeal population were detected compared with the in vivo control. Thus, the increase in CH4 production may be explained by the increase in substrate in the in vitro system. The reduced CH4 production in vitro with CNSE suggests that CNSE can be a promising inhibitor of CH4 formation in the rumen of dairy cows. Copyright © 2014 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Study of the daily and seasonal atmospheric CH4 mixing ratio variability in a rural Spanish region using 222Rn tracer

NASA Astrophysics Data System (ADS)

Grossi, Claudia; Vogel, Felix R.; Curcoll, Roger; Àgueda, Alba; Vargas, Arturo; Rodó, Xavier; Morguí, Josep-Anton

2018-04-01

The ClimaDat station at Gredos (GIC3) has been continuously measuring atmospheric (dry air) mixing ratios of carbon dioxide (CO2) and methane (CH4), as well as meteorological parameters, since November 2012. In this study we investigate the atmospheric variability of CH4 mixing ratios between 2013 and 2015 at GIC3 with the help of co-located observations of 222Rn concentrations, modelled 222Rn fluxes and modelled planetary boundary layer heights (PBLHs). Both daily and seasonal changes in atmospheric CH4 can be better understood with the help of atmospheric concentrations of 222Rn (and the corresponding fluxes). On a daily timescale, the variation in the PBLH is the main driver for 222Rn and CH4 variability while, on monthly timescales, their atmospheric variability seems to depend on emission changes. To understand (changing) CH4 emissions, nocturnal fluxes of CH4 were estimated using two methods: the radon tracer method (RTM) and a method based on the EDGARv4.2 bottom-up emission inventory, both using FLEXPARTv9.0.2 footprints. The mean value of RTM-based methane fluxes (FR_CH4) is 0.11 mg CH4 m-2 h-1 with a standard deviation of 0.09 or 0.29 mg CH4 m-2 h-1 with a standard deviation of 0.23 mg CH4 m-2 h-1 when using a rescaled 222Rn map (FR_CH4_rescale). For our observational period, the mean value of methane fluxes based on the bottom-up inventory (FE_CH4) is 0.33 mg CH4 m-2 h-1 with a standard deviation of 0.08 mg CH4 m-2 h-1. Monthly CH4 fluxes based on RTM (both FR_CH4 and FR_CH4_rescale) show a seasonality which is not observed for monthly FE_CH4 fluxes. During January-May, RTM-based CH4 fluxes present mean values 25 % lower than during June-December. This seasonal increase in methane fluxes calculated by RTM for the GIC3 area appears to coincide with the arrival of transhumant livestock at GIC3 in the second half of the year.

A multi-scale comparison of modeled and observed seasonal methane emissions in northern wetlands

DOE PAGES

Xu, Xiyan; Riley, William J.; Koven, Charles D.; ...

2016-09-13

Wetlands are the largest global natural methane (CH 4) source, and emissions between 50 and 70° N latitude contribute 10-30 % to this source. Predictive capability of land models for northern wetland CH 4 emissions is still low due to limited site measurements, strong spatial and temporal variability in emissions, and complex hydrological and biogeochemical dynamics. To explore this issue, we compare wetland CH 4 emission predictions from the Community Land Model 4.5 (CLM4.5-BGC) with site- to regional-scale observations. A comparison of the CH 4 fluxes with eddy flux data highlighted needed changes to the model's estimate of aerenchyma area,more » which we implemented and tested. The model modification substantially reduced biases in CH 4 emissions when compared with CarbonTracker CH 4 predictions. CLM4.5 CH 4 emission predictions agree well with growing season (May–September) CarbonTracker Alaskan regional-level CH 4 predictions and site-level observations. However, CLM4.5 underestimated CH 4 emissions in the cold season (October–April). The monthly atmospheric CH 4 mole fraction enhancements due to wetland emissions are also assessed using the Weather Research and Forecasting-Stochastic Time-Inverted Lagrangian Transport (WRF-STILT) model coupled with daily emissions from CLM4.5 and compared with aircraft CH 4 mole fraction measurements from the Carbon in Arctic Reservoirs Vulnerability Experiment (CARVE) campaign. Both the tower and aircraft analyses confirm the underestimate of cold-season CH 4 emissions by CLM4.5. The greatest uncertainties in predicting the seasonal CH 4 cycle are from the wetland extent, cold-season CH 4 production and CH 4 transport processes. We recommend more cold-season experimental studies in high-latitude systems, which could improve the understanding and parameterization of ecosystem structure and function during this period. Predicted CH 4 emissions remain uncertain, but we show here that benchmarking against observations across spatial scales can inform model structural and parameter improvements.« less

A multi-scale comparison of modeled and observed seasonal methane emissions in northern wetlands

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

Xu, Xiyan; Riley, William J.; Koven, Charles D.

Wetlands are the largest global natural methane (CH 4) source, and emissions between 50 and 70° N latitude contribute 10-30 % to this source. Predictive capability of land models for northern wetland CH 4 emissions is still low due to limited site measurements, strong spatial and temporal variability in emissions, and complex hydrological and biogeochemical dynamics. To explore this issue, we compare wetland CH 4 emission predictions from the Community Land Model 4.5 (CLM4.5-BGC) with site- to regional-scale observations. A comparison of the CH 4 fluxes with eddy flux data highlighted needed changes to the model's estimate of aerenchyma area,more » which we implemented and tested. The model modification substantially reduced biases in CH 4 emissions when compared with CarbonTracker CH 4 predictions. CLM4.5 CH 4 emission predictions agree well with growing season (May–September) CarbonTracker Alaskan regional-level CH 4 predictions and site-level observations. However, CLM4.5 underestimated CH 4 emissions in the cold season (October–April). The monthly atmospheric CH 4 mole fraction enhancements due to wetland emissions are also assessed using the Weather Research and Forecasting-Stochastic Time-Inverted Lagrangian Transport (WRF-STILT) model coupled with daily emissions from CLM4.5 and compared with aircraft CH 4 mole fraction measurements from the Carbon in Arctic Reservoirs Vulnerability Experiment (CARVE) campaign. Both the tower and aircraft analyses confirm the underestimate of cold-season CH 4 emissions by CLM4.5. The greatest uncertainties in predicting the seasonal CH 4 cycle are from the wetland extent, cold-season CH 4 production and CH 4 transport processes. We recommend more cold-season experimental studies in high-latitude systems, which could improve the understanding and parameterization of ecosystem structure and function during this period. Predicted CH 4 emissions remain uncertain, but we show here that benchmarking against observations across spatial scales can inform model structural and parameter improvements.« less

Interlaboratory comparison of δ13C and δD measurements of atmospheric CH4 for combined use of data sets from different laboratories

NASA Astrophysics Data System (ADS)

Umezawa, Taku; Brenninkmeijer, Carl A. M.; Röckmann, Thomas; van der Veen, Carina; Tyler, Stanley C.; Fujita, Ryo; Morimoto, Shinji; Aoki, Shuji; Sowers, Todd; Schmitt, Jochen; Bock, Michael; Beck, Jonas; Fischer, Hubertus; Michel, Sylvia E.; Vaughn, Bruce H.; Miller, John B.; White, James W. C.; Brailsford, Gordon; Schaefer, Hinrich; Sperlich, Peter; Brand, Willi A.; Rothe, Michael; Blunier, Thomas; Lowry, David; Fisher, Rebecca E.; Nisbet, Euan G.; Rice, Andrew L.; Bergamaschi, Peter; Veidt, Cordelia; Levin, Ingeborg

2018-03-01

We report results from a worldwide interlaboratory comparison of samples among laboratories that measure (or measured) stable carbon and hydrogen isotope ratios of atmospheric CH4 (δ13C-CH4 and δD-CH4). The offsets among the laboratories are larger than the measurement reproducibility of individual laboratories. To disentangle plausible measurement offsets, we evaluated and critically assessed a large number of intercomparison results, some of which have been documented previously in the literature. The results indicate significant offsets of δ13C-CH4 and δD-CH4 measurements among data sets reported from different laboratories; the differences among laboratories at modern atmospheric CH4 level spread over ranges of 0.5 ‰ for δ13C-CH4 and 13 ‰ for δD-CH4. The intercomparison results summarized in this study may be of help in future attempts to harmonize δ13C-CH4 and δD-CH4 data sets from different laboratories in order to jointly incorporate them into modelling studies. However, establishing a merged data set, which includes δ13C-CH4 and δD-CH4 data from multiple laboratories with desirable compatibility, is still challenging due to differences among laboratories in instrument settings, correction methods, traceability to reference materials and long-term data management. Further efforts are needed to identify causes of the interlaboratory measurement offsets and to decrease those to move towards the best use of available δ13C-CH4 and δD-CH4 data sets.

Evaluation of methane oxidation activity in waste biocover soil during landfill stabilization.

PubMed

He, Ruo; Wang, Jing; Xia, Fang-Fang; Mao, Li-Juan; Shen, Dong-Sheng

2012-10-01

Biocover soil has been demonstrated to have high CH(4) oxidation capacity and is considered as a good alternative cover material to mitigate CH(4) emission from landfills, yet the response of CH(4) oxidation activity of biocover soils to the variation of CH(4) loading during landfill stabilization is poorly understood. Compared with a landfill cover soil (LCS) collected from Hangzhou Tianziling landfill cell, the development of CH(4) oxidation activity of waste biocover soil (WBS) was investigated using simulated landfill systems in this study. Although a fluctuation of influent CH(4) flux occurred during landfill stabilization, the WBS covers showed a high CH(4) removal efficiency of 94-96% during the entire experiment. In the LCS covers, the CH(4) removal efficiencies varied with the fluctuation of CH(4) influent flux, even negative ones occurred due to the storage of CH(4) in the soil porosities after the high CH(4) influent flux of ~137 gm(-2) d(-1). The lower concentrations of O(2) and CH(4) as well as the higher concentration of CO(2) were observed in the WBS covers than those in the LCS covers. The highest CH(4) oxidation rates of the two types of soil covers both occurred in the bottom layer (20-30 cm). Compared to the LCS, the WBS showed higher CH(4) oxidation activity and methane monooxygenase activity over the course of the experiment. Overall, this study indicated the WBS worked well for the fluctuation of CH(4) influent flux during landfill stabilization. Copyright © 2012 Elsevier Ltd. All rights reserved.

Temperate Forest Methane Sink Diminished by Tree Emissions

NASA Astrophysics Data System (ADS)

Megonigal, P.; Pitz, S.

2015-12-01

Global budgets ascribe 4-10% of atmospheric CH4 sinks to upland soils and assume that soils are the sole surface for CH4 exchange between upland forests and the atmosphere. The prevailing dogma that upland forests are sinks of atmospheric CH4 was challenged a decade ago by large discrepancies in bottom-up versus top-down models of CH4 concentrations over upland forests that are still unexplained. Evidence of a novel abiotic mechanism for CH4 production from plant tissue is too small to explain the discrepancy. Alternative hypotheses for this observation have been proposed, but not tested. Here we demonstrate that CH4 is emitted from the stems of dominant tree species in an upland forest. Tree emissions occur throughout the growing season while soils adjacent to the trees are consuming CH4, challenging the concept that forests are uniform sinks of CH4. Scaling by stem surface area showed the forest to be a net CH4 source during a wet sample in June and a reduced CH4 sink by 5% annually. High frequency measurements revealed diurnal cycling in the rate of CH4 emissions, pointing to soils as the CH4 source and transpiration as the most likely pathway for CH4 transport. We propose the forests are smaller CH4 sinks than previously estimated due to stem emissions. Stem emissions may be particularly important in upland tropical forests characterized by high rainfall and transpiration, resolving differences between models and measurements.

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

White, Travis A.; Witt, Suzanne E.; Li, Zhanyong

Formamidinate-bridged Rh 2 II,II complexes containing diimine ligands of the formula cis-[Rh 2 II,II(μ-DTolF) 2(NN) 2] 2+ (Rh 2-NN 2), where DTolF = p-ditolylformamidinate and NN = dppn (benzo[i]dipyrido[3,2-a:2',3'-h]quinoxaline), dppz (dipyrido[3,2-a:2',3'-c]phenazine), and phen (1,10-phenanthroline), electrocatalytically reduce H + to H 2 in DMF solutions containing CH 3COOH at a glassy carbon electrode. Cathodic scans in the absence of acid display a Rh III,II/II,II reduction at -0.90 V vs Fc +/Fc followed by NN 0/– reduction at -1.13, -1.36, and -1.65 V for Rh 2-dppn 2, Rh 2-dppz 2, and Rh 2-phen 2, respectively. Upon the addition of acid, Rh 2-dppnmore » 2 and Rh 2-dppz 2 undergo reduction–protonation–reduction at each pyrazine-containing NN ligand prior to the Rh 2 II,II/II,I reduction. The Rh 2 II,I species is thus protonated at one of the metal centers, resulting in the formation of the corresponding Rh 2 II,III-hydride. In the case of Rh 2-phen 2, the reduction of the phen ligand is followed by intramolecular electron transfer to the Rh 2 II,II core in the presence of protons to form a Rh 2 II,III-hydride species. Further reduction and protonation at the Rh 2 core for all three complexes rapidly catalyzes H 2 formation with varied calculated turnover frequencies (TOF) and overpotential values (η): 2.6 × 10 4 s –1 and 0.56 V for Rh 2-dppn, 2.8 × 10 4 s –1 and 0.50 V for Rh 2-dppz 2, and 5.9 × 10 4 s –1 and 0.64 V for Rh 2-phen 2. Bulk electrolysis confirmed H 2 formation, and further CH 3COOH addition regenerates H 2 production, attesting to the robust nature of the architecture. The cis-[Rh 2 II,II(μ-DTolF) 2(NN) 2] 2+ architecture benefits by combining electron-rich formamidinate bridges, a redox-active Rh 2 II,II core, and electron-accepting NN diimine ligands to allow for the electrocatalysis of H + substrate to H 2 fuel.« less

New Rh 2 (II,II) Architecture for the Catalytic Reduction of H +

DOE PAGES

White, Travis A.; Witt, Suzanne E.; Li, Zhanyong; ...

2015-09-25

Formamidinate-bridged Rh 2 II,II complexes containing diimine ligands of the formula cis-[Rh 2 II,II(μ-DTolF) 2(NN) 2] 2+ (Rh 2-NN 2), where DTolF = p-ditolylformamidinate and NN = dppn (benzo[i]dipyrido[3,2-a:2',3'-h]quinoxaline), dppz (dipyrido[3,2-a:2',3'-c]phenazine), and phen (1,10-phenanthroline), electrocatalytically reduce H + to H 2 in DMF solutions containing CH 3COOH at a glassy carbon electrode. Cathodic scans in the absence of acid display a Rh III,II/II,II reduction at -0.90 V vs Fc +/Fc followed by NN 0/– reduction at -1.13, -1.36, and -1.65 V for Rh 2-dppn 2, Rh 2-dppz 2, and Rh 2-phen 2, respectively. Upon the addition of acid, Rh 2-dppnmore » 2 and Rh 2-dppz 2 undergo reduction–protonation–reduction at each pyrazine-containing NN ligand prior to the Rh 2 II,II/II,I reduction. The Rh 2 II,I species is thus protonated at one of the metal centers, resulting in the formation of the corresponding Rh 2 II,III-hydride. In the case of Rh 2-phen 2, the reduction of the phen ligand is followed by intramolecular electron transfer to the Rh 2 II,II core in the presence of protons to form a Rh 2 II,III-hydride species. Further reduction and protonation at the Rh 2 core for all three complexes rapidly catalyzes H 2 formation with varied calculated turnover frequencies (TOF) and overpotential values (η): 2.6 × 10 4 s –1 and 0.56 V for Rh 2-dppn, 2.8 × 10 4 s –1 and 0.50 V for Rh 2-dppz 2, and 5.9 × 10 4 s –1 and 0.64 V for Rh 2-phen 2. Bulk electrolysis confirmed H 2 formation, and further CH 3COOH addition regenerates H 2 production, attesting to the robust nature of the architecture. The cis-[Rh 2 II,II(μ-DTolF) 2(NN) 2] 2+ architecture benefits by combining electron-rich formamidinate bridges, a redox-active Rh 2 II,II core, and electron-accepting NN diimine ligands to allow for the electrocatalysis of H + substrate to H 2 fuel.« less

Alkaline hydrolysis of the cyclic nitramine explosives RDX, HMX, and CL-20: new insights into degradation pathways obtained by the observation of novel intermediates.

PubMed

Balakrishnan, Vimal K; Halasz, Annamaria; Hawari, Jalal

2003-05-01

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX, I) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) hydrolyze at pH > 10 to form end products including NO2-, HCHO, HCOOH, NH3, and N2O, but little information is available on intermediates, apart from the tentatively identified pentahydro-3,5-dinitro-1,3,5-triazacyclohex-1-ene (II). Despite suggestions that RDX and HMX contaminated groundwater could be economically treated via alkaline hydrolysis, the optimization of such a process requires more detailed knowledge of intermediates and degradation pathways. In this study, we hydrolyzed the monocyclic nitramines RDX, MNX (hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine), and HMX in aqueous solution (pH 10-12.3) and found that nitramine removal was accompanied by formation of 1 molar equiv of nitrite and the accumulation of the key ring cleavage product 4-nitro-2,4-diazabutanal (4-NDAB, O2NNHCH2NHCHO). Most of the remaining C and N content of RDX, MNX, and HMX was found in HCHO, N2O, HCOOH, and NH3. Consequently, we selected RDX as a model compound and hydrolyzed it in aqueous acetonitrile solutions (pH 12.3) in the presence and absence of hydroxypropyl-beta-cyclodextrin (HP-beta-CD) to explore other early intermediates in more detail. We observed a transient LC-MS peak with a [M-H] at 192 Da that was tentatively identified as 4,6-dinitro-2,4,6-triaza-hexanal (O2NNHCH2NNO2CH2NHCHO, III) considered as the hydrolyzed product of II. In addition, we detected another novel intermediate with a [M-H] at 148 Da that was tentatively identified as a hydrolyzed product of III, namely, 5-hydroxy-4-nitro-2,4-diaza-pentanal (HOCH2NNO2CH2NHCHO, IV). Both III and IV can act as precursors to 4-NDAB. In the case of the polycyclic nitramine 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20), denitration (two NO2-) also led to the formation of HCOOH, NH3, and N2O, but neither HCHO nor 4-NDAB were detected. The results provide strong evidence that initial denitration of cyclic nitramines in water is sufficient to cause ring cleavage followed by spontaneous decomposition to form the final products.

An algorithm to generate input data from meteorological and space shuttle observations to validate a CH4-CO model

NASA Technical Reports Server (NTRS)

Peters, L. K.; Yamanis, J.

1981-01-01

Objective procedures to analyze data from meteorological and space shuttle observations to validate a three dimensional model were investigated. The transport and chemistry of carbon monoxide and methane in the troposphere were studied. Four aspects were examined: (1) detailed evaluation of the variational calculus procedure, with the equation of continuity as a strong constraint, for adjustment of global tropospheric wind fields; (2) reduction of the National Meteorological Center (NMC) data tapes for data input to the OSTA-1/MAPS Experiment; (3) interpolation of the NMC Data for input to the CH4-CO model; and (4) temporal and spatial interpolation procedures of the CO measurements from the OSTA-1/MAPS Experiment to generate usable contours of the data.

Macroscopic and Microscopic Investigation of U(VI) and Eu(III) Adsorption on Carbonaceous Nanofibers.

PubMed

Sun, Yubing; Wu, Zhen-Yu; Wang, Xiangxue; Ding, Congcong; Cheng, Wencai; Yu, Shu-Hong; Wang, Xiangke

2016-04-19

The adsorption mechanism of U(VI) and Eu(III) on carbonaceous nanofibers (CNFs) was investigated using batch, IR, XPS, XANES, and EXAFS techniques. The pH-dependent adsorption indicated that the adsorption of U(VI) on the CNFs was significantly higher than the adsorption of Eu(III) at pH < 7.0. The maximum adsorption capacity of the CNFs calculated from the Langmuir model at pH 4.5 and 298 K for U(VI) and Eu(III) were 125 and 91 mg/g, respectively. The CNFs displayed good recyclability and recoverability by regeneration experiments. Based on XPS and XANES analyses, the enrichment of U(VI) and Eu(III) was attributed to the abundant adsorption sites (e.g., -OH and -COOH groups) of the CNFs. IR analysis further demonstrated that -COOH groups were more responsible for U(VI) adsorption. In addition, the remarkable reducing agents of the R-CH2OH groups were responsible for the highly efficient adsorption of U(VI) on the CNFs. The adsorption mechanism of U(VI) on the CNFs at pH 4.5 was shifted from inner- to outer-sphere surface complexation with increasing initial concentration, whereas the surface (co)precipitate (i.e., schoepite) was observed at pH 7.0 by EXAFS spectra. The findings presented herein play an important role in the removal of radionuclides on inexpensive and available carbon-based nanoparticles in environmental cleanup applications.

A serials of sandwich-like trinuclear and one-dimensional chain cyanide-bridged iron(III)-copper(II) complexes: Syntheses, crystal structures and magnetic properties

NASA Astrophysics Data System (ADS)

Shi, Jingwen; Lan, Wenlong; Ren, Yanjie; Liu, Qingyun; Liu, Hui; Dong, Yunhui; Zhang, Daopeng

2018-04-01

Four pyridinecarboxamide trans-dicyanideiron(III) building blocks and one macrocyclic copper(II) compound have been employed to assemble cyanide-bridged heterometallic complexes, resulting in a serials of cyanide-bridged FeIII-CuII complexes with different structure types. The series of complexes can be formulated as: {[Cu(Cyclam)][Fe(bpb)(CN)2]2}·4H2O (1), {{[Cu(Cyclam)][Fe(bpb)(CN)2]}ClO4}n·nH2O (2), and {[Cu(Cyclam)][Fe(bpmb)(CN)2]2}·4H2O (3), {[Cu(Cyclam)][Fe(bpClb)(CN)2]2}·4H2O (4) and {{[Cu(Cyclam)][Fe(bpdmb)(CN)2]}ClO4}n·2nCH3OH (5) (bpb2- = 1,2-bis(pyridine-2-carboxamido)benzenate, bpmb2- = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate, bpClb2- = 1,2-bis(pyridine-2-carboxamido)-4-chloro-benzenate, bpdmb2- = 1,2-bis(pyridine-2-carboxamido)-4,5-dimethyl-benzenate, Cyclam = 1,4,8,11-tetraazacyclotetradecane). All the complexes have been characterized by elemental analysis, IR spectra and structural determination. Single X-ray diffraction analysis shows the similar neutral sandwich-like structures for complexes 1, 3 and 4, in which the two cyano precursors acting as monodentate ligand through one of their two cyanide groups were coordinated face to face to central Cu(II) ion. The complexes 2 and 5 can be structurally characterized as one-dimensional cationic single chain consisting of alternating units of [Cu(Cyclam)]2+ and [Fe(bpb/bpdmb)(CN)2]- with free ClO4- as balanced anion. Investigation over magnetic properties of the whole serials of complexes reveals the antiferromagnetic magnetic coupling between the neighboring cyanide-bridged Fe(III) and Cu(II) ions in complexes 3 and 4 and the ferromagnetic interaction in complexes 1, 2 and 5, respectively.

Environmental and vegetation controls on the spatial variability of CH4 emission from wet-sedge and tussock tundra ecosystems in the Arctic.

PubMed

McEwing, Katherine Rose; Fisher, James Paul; Zona, Donatella

Despite multiple studies investigating the environmental controls on CH 4 fluxes from arctic tundra ecosystems, the high spatial variability of CH 4 emissions is not fully understood. This makes the upscaling of CH 4 fluxes from plot to regional scale, particularly challenging. The goal of this study is to refine our knowledge of the spatial variability and controls on CH 4 emission from tundra ecosystems. CH 4 fluxes were measured in four sites across a variety of wet-sedge and tussock tundra ecosystems in Alaska using chambers and a Los Gatos CO 2 and CH 4 gas analyser. All sites were found to be sources of CH 4 , with northern sites (in Barrow) showing similar CH 4 emission rates to the southernmost site (ca. 300 km south, Ivotuk). Gross primary productivity (GPP), water level and soil temperature were the most important environmental controls on CH 4 emission. Greater vascular plant cover was linked with higher CH 4 emission, but this increased emission with increased vascular plant cover was much higher (86 %) in the drier sites, than the wettest sites (30 %), suggesting that transport and/or substrate availability were crucial limiting factors for CH 4 emission in these tundra ecosystems. Overall, this study provides an increased understanding of the fine scale spatial controls on CH 4 flux, in particular the key role that plant cover and GPP play in enhancing CH 4 emissions from tundra soils.

Tree CH4 fluxes in forestry drained peatland in southern Finland

NASA Astrophysics Data System (ADS)

Haikarainen, Iikka; Putkinen, Anuliina; Pyykkö, Petteri; Halmeenmäki, Elisa; Pihlatie, Mari

2017-04-01

Methane (CH4) is among the most important greenhouse gases and its atmospheric concentration is increasing. Boreal forests are commonly considered a net sink of atmospheric CH4 due to CH4 consuming bacteria in aerated soil layers. Recent studies have, however, demonstrated that trees are capable of emitting CH4 from their stems and shoots by transporting anaerobically produced CH4 from deeper soil layers to the atmosphere. Furthermore, trees may act as independent sources of CH4. We have measured tree stem CH4 exchange of boreal tree species at Lettosuo, a nutrient rich peatland forest in Tammela, southern Finland (60˚ 38' N, 23˚ 57' E), using the static chamber technique. Three species, downy birch (Betula pubescens), Norway spruce (Picea abies) and Scots pine (Pinus sylvestris), were selected under investigation as they represent common boreal tree species. Fluxes of CH4 were measured during 7.6.2016 - 17.10.2016 from in total 25 sample trees growing on two different plots: a treatment plot where all the pines were removed to raise the water table level (WTL) and a control plot. Three birches from the treatment plot were selected to measure CH4 flux variation within vertical profile of the trees. Characterization of microbial communities, quantification of methanogenic and methanotrophic functional genes, and measurements of potential CH4 production and consumption from peat profile and forest floor moss samples were also carried out to obtain insight to the CH4 flux dynamics at the studied sites. The pine removal treatment did not markedly change the average WTL, but it made the WTL more variable with frequently 10-15 cm closer to soil surface compared to the WTL on the control plot. We found small and variable CH4 emissions from the stems of trees on both of the plots, while occasional consumption of CH4 was also present. Generally the CH4 emissions were higher and more dominant at the treatment plot compared to the control plot, and the fluxes were significantly different between the plots (p < 0.001). The CH4 emission rates from the birches at the treatment plot decreased exponentially in the stem vertical profile. Clear seasonal flux dynamics or significant differences in the CH4 flux between the species were not found at either of the plots. Microbial experiments showed that anaerobic CH4 production, CH4 oxidation potential (under 1000 ppm CH4) and the amount of methanogens were higher in the peat of the treatment site. The difference in the CH4 flux rates between the plots indicates that the WTL is a major regulator of tree CH4 emissions on forestry drained peatlands, supporting our hypothesis that the stem emitted CH4 originates from anaerobic soil conditions. This hypothesis is further supported by the results of the microbial analysis and by the observation that more CH4 is emitting from the lower parts of the stems compared to the upper stem.

Effect of cross-linked chitosan iron (III) on vascular calcification in uremic rats.

PubMed

de Castro, Barbara Bruna Abreu; do Carmo, Wander Barros; de Albuquerque Suassuna, Paulo Giovani; Carminatti, Moises; Brito, Julia Bianchi; Dominguez, Wagner Vasques; de Oliveira, Ivone Braga; Jorgetti, Vanda; Custodio, Melani Ribeiro; Sanders-Pinheiro, Helady

2018-05-01

Cross-linked chitosan iron (III) is a chitin-derived polymer with a chelating effect on phosphorus, but it is untested in vascular calcification. We evaluated this compound's ability to reduce hyperphosphatemia and its effect on vascular calcification in uremic rats using an adenine-based, phosphorus-rich diet for seven weeks. We used a control group to characterize the uremia. Uremic rats were divided according the treatment into chronic kidney disease, CKD-Ch-Fe(III)CL (CKD-Ch), CKD-calcium carbonate, or CKD-sevelamer groups. We measured creatinine, phosphorus, calcium, alkaline phosphatase, phosphorus excretion fraction, parathyroid hormone, and fibroblast growth factor 23. Vascular calcification was assessed using the aortic calcium content, and a semi-quantitative analysis was performed using Von Kossa and hematoxylin-eosin staining. At week seven, rats in the chronic kidney disease group had higher creatinine, phosphorus, phosphorus excretion fraction, calcium, alkaline phosphatase, fibroblast growth factor 23, and aortic calcium content than those in the Control group. Treatments with cross-linked chitosan iron (III) and calcium carbonate prevented phosphorus increase (20%-30% reduction). The aortic calcium content was lowered by 88% and 85% in the CKD-Ch and CKD-sevelamer groups, respectively. The prevalence of vascular changes was higher in the chronic kidney disease and CKD-calcium carbonate (62.5%) groups than in the CKD-Ch group (37.5%). In conclusion, cross-linked chitosan iron (III) had a phosphorus chelating effect similar to calcium carbonate already available for clinical use, and prevented calcium accumulation in the aorta. Impact statement Vascular calcification (VC) is a common complication due to CKD-related bone and mineral disorder (BMD) and is characterized by deposition of calcium in vessels. Effective therapies are not yet available but new phosphorus chelators can prevent complications from CV. We tested the effect of chitosan, a new phosphorus chelator, on the VC of uremic animals. It has recently been proposed that chitosan treatment may be effective in the treatment of hyperphosphataemia. However, its action on vascular calcification has not been investigated yet. In this study, we demonstrated that chitosan reduced the calcium content in the aorta, suggesting that this may be a therapeutic approach in the treatment of hyperphosphatemia by preventing CV.

Anaerobic Oxidation of Methane in Sediments of Two Boreal Lakes

NASA Astrophysics Data System (ADS)

Tiirola, M. A.; Rissanen, A. J.; Karvinen, A.; Nykänen, H.; Mpamah, P.; Peura, S.; Kankaala, P.

2014-12-01

In this study, potential for Anaerobic oxidation of methane (AOM) coupled with metal reduction was studied in boreal lake sediments. Slurries of sediment samples collected from two sites in southeastern Finland, i.e. from Lake Orivesi, Heposelkä, an vegetated littoral site, dominated by Phragmites australis (Sample Sa, sediment layer 0 - 25 cm) and from the profundal zone of a mesotrophic Lake Ätäskö (Aa, 0 - 10 cm; Ab, 10 - 30 cm; Ac, 90 - 130 cm), were incubated in laboratory in anaerobic conditions at in situ temperatures for up to 5 months. The samples were amended either 1) with 13CH4, 2) 13CH4 + manganese(IV) oxide (MnO2) or 3) 13CH4 + iron(III) hydroxide (Fe(OH)3), and the processes were measured by following the 13C transfer to the carbon dioxide (CO2) pool and by concentration measurements of CH4 and CO2. Changes in microbial communities were studied from DNA extracted from sediment samples before and after incubation period by next-generation sequencing (Ion Torrent) of polymerase chain reaction (PCR) - amplified bacterial and archaeal 16S rRNA and methyl coenzyme-M reductase gene (mcrA) amplicons. AOM took place in every sample except in deepest sample (Ac) with potential rates up to 2.1 nmol CH4 d-1 g-1wetsedim (~2 nmol d-1 cm-3) which are considerably lower than previously reported metal-driven AOM in marine sediments (10-40 nmol d-1 cm-3) but within a range of NO3- -driven AOM in an oligotrophic lake (0.6-3.6 nmol d-1 cm-3). AOM took place without metal additions but addition of Mn4+ increased the potential rates and this increase was especially high in 10-30 cm layer (Ab) of the profundal site (5-fold increase). The structure of the bacterial and archaeal communities changed considerably during incubation. Communities incubated with Mn4+ were especially different from those incubated with Fe3+ or without metals which were more similar with each other. Surprisingly, anaerobic methanotrophic archaea detected, ANME-2D and AOM-associated archaea (AAA), were almost absent in the littoral site and constituted only up to 3.5% and 5% of archaeal 16S rRNA and mcrA gene sequences, respectively, in the profundal site. Mn4+ induced an increase in the abundance of ANME-2D and AAA in the profundal site which indicates that they are involved in Mn4+ - dependent AOM.

Career Development: A Systems Approach.

ERIC Educational Resources Information Center

Slavenski, Lynn

1987-01-01

The author describes a comprehensive career development system implemented by Coca-Cola USA. The system's objectives are (1) to promote from within, (2) to develop talent for the future, (3) to make managers responsible for development efforts, and (4) to make individuals ultimately responsible for their development. (CH)

Simulation of comprehensive chemistry and atmospheric methane lifetime in the LGM with EMAC

NASA Astrophysics Data System (ADS)

Gromov, Sergey; Steil, Benedikt

2017-04-01

Past records of atmospheric methane (CH4) abundance/isotope composition may provide a substantial insight on C exchanges in the Earth System (ES). When simulated in the climate models, CH4 helps to identify climate parameters transitions via triggering of its different (natural) sources, with a proviso that its sinks are adequately represented in the model. The latter are still a matter of large uncertainty in the studies focussing on the interpretation of CH4 evolution throughout Last Glacial Maximum (LGM), judging the conferred span of tropospheric CH4 lifetime (λ) of 3-16 yr [1-4]. In this study, we attempt to: (i) deliver the most adequate estimate of the LGM atmospheric sink of CH4 in the EMAC AC-GCM [5] equipped with the comprehensive representation of atmospheric chemistry [6], (ii) reveal the ES and CH4 emission parameters that are most influential for λ and (iii) based on these findings, suggest a parameterisation for λ that may be consistently used in climate models. In pursuing (i) we have tuned the EMAC model for simulating LGM atmospheric chemistry state, including careful revisiting of the trace gases emissions from the biosphere, biomass burning/lightning source, etc. The latter affect the key simulated component bound with λ, viz. the abundance and distribution of the hydroxyl radicals (OH) which, upon reacting with CH4, constitute its main tropospheric sink. Our preliminary findings suggest that OH is buffered in the atmosphere in a similar fashion to preindustrial climate, which in line with the recent studies employing comprehensive chemistry mechanisms (e.g., [3]). The analysis in (ii) suggests that tropospheric λ values may be qualitatively described as a convolution of values typical for zonal domain with high and low photolytic recycling rates (i.e. tropics and extra-tropics), as in the latter a dependence of the zonal average λ value on the CH4 emission strength exists. We further use the extensive diagnostic in EMAC to infer the sensitivity of zonal OH to changes in various component of the ES, e.g. in stratospheric O3 input and dynamics. Finally, we discuss the potential set of parameters required for efficient λ and/or OH parameterisation implementation in models dealing with (transient) climate simulations. References 1. Fischer, H., et al.: Changing boreal methane sources and constant biomass burning during the last termination, Nature, 452, 864-867, doi: 10.1038/nature06825, 2008. 2. Kaplan, J. O., Folberth, G.,and Hauglustaine, D. A.: Role of methane and biogenic volatile organic compound sources in late glacial and Holocene fluctuations of atmospheric methane concentrations, Global Biogeochemical Cycles, 20, n/a-n/a, doi: 10.1029/2005GB002590, 2006. 3. Murray, L. T., et al.: Factors controlling variability in the oxidative capacity of the troposphere since the Last Glacial Maximum, Atmos. Chem. Phys., 14, 3589-3622, doi: 10.5194/acp-14-3589-2014, 2014. 4. Valdes, P. J., Beerling, D. J.,and Johnson, C. E.: The ice age methane budget, Geophysical Research Letters, 32, n/a-n/a, doi: 10.1029/2004GL021004, 2005. 5. Jöckel, P., et al.: Development cycle 2 of the Modular Earth Submodel System (MESSy2), Geosci. Model Dev., 3, 717-752, doi: 10.5194/gmd-3-717-2010, 2010. 6. Lelieveld, J., et al.: Global tropospheric hydroxyl distribution, budget and reactivity, Atmos. Chem. Phys., 16, 12477-12493, doi: 10.5194/acp-16-12477-2016, 2016.

Balanced design for the feasible super rocket fuels: A first-principle study on gauche CHN7 and CHN3.

PubMed

Yu, Tao; Lin, Maohua; Wu, Bo; Wang, Jintian; Tsai, Chi-Tay

2018-05-16

On the basis of the framework of cubic gauche nitrogen (cg-N), six one-eighth methanetriyl groups (>CH-) substitutes and fifteen one-fourth >CH- substitutes were optimized using the first-principle calculations based on density functional theory (DFT). Both one-eighth and one-fourth substitutes still keep the gauche structures with the simple formula CHN 7 and CHN 3 , respectively. The most thermodynamic stable gauche CHN 7 and CHN 3 are P2 1 qtg-C 2 H 2 N 14 I and P2 1 qtg-C 4 H 4 N 12 III, respectively. No probability density of C-C single bonds and high probability densities of C-N-C structures were found in the two substitutes. Although gauche CHN 7 and CHN 3 lose energy density in contrast to cg-N, they win kinetic stability and combustion temperature (T c ). Thus, they are more feasible than cg-N, and more effective than the traditional rocket fuels. Copyright © 2018 Elsevier Inc. All rights reserved.

Biotinylated Rh(III) complexes in engineered streptavidin for accelerated asymmetric C-H activation.

PubMed

Hyster, Todd K; Knörr, Livia; Ward, Thomas R; Rovis, Tomislav

2012-10-26

Enzymes provide an exquisitely tailored chiral environment to foster high catalytic activities and selectivities, but their native structures are optimized for very specific biochemical transformations. Designing a protein to accommodate a non-native transition metal complex can broaden the scope of enzymatic transformations while raising the activity and selectivity of small-molecule catalysis. Here, we report the creation of a bifunctional artificial metalloenzyme in which a glutamic acid or aspartic acid residue engineered into streptavidin acts in concert with a docked biotinylated rhodium(III) complex to enable catalytic asymmetric carbon-hydrogen (C-H) activation. The coupling of benzamides and alkenes to access dihydroisoquinolones proceeds with up to nearly a 100-fold rate acceleration compared with the activity of the isolated rhodium complex and enantiomeric ratios as high as 93:7.

Trichlorido[(meth­yl{2-[meth­yl(2-pyridyl­meth­yl)amino]eth­yl}amino)acetonitrile]iron(III) methanol hemisolvate

PubMed Central

Nielsen, Anne; McKenzie, Christine J.; Bond, Andrew D.

2009-01-01

The title compound, [FeCl3(C12H18N4)]·0.5CH3OH, contains an FeIII ion in a distorted octa­hedral coordination environment. The neutral N,N′,N′′-tridentate ligand adopts a fac coordination mode, and chloride ligands lie trans to each of the three coordinated N atoms. In the crystal, the complexes form columns extending parallel to the approximate local threefold axes of the FeN3Cl3 octa­hedra, and the columns are arranged so that the uncoordinated nitrile groups align in an anti­parallel manner and the pyridyl rings form offset face-to-face arrangements [inter­planar separations = 2.95 (1) and 3.11 (1) Å; centroid–centroid distances = 5.31 (1) and 4.92 (1) Å]. The methanol solvent mol­ecule is disordered about a twofold rotation axis. PMID:21578169

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.

Infrared polar brightening on Jupiter. III - Spectrometry from the Voyager 1 IRIS experiment

NASA Technical Reports Server (NTRS)

Kim, S. J.; Caldwell, J.; Rivolo, A. R.; Wagener, R.; Orton, G. S.

1985-01-01

Spectra from the Voyager 1 IRIS experiment confirm the existence of enhanced infrared emission near Jupiter's north magnetic pole in March 1979. The spectral characteristics of the enhanced emission are consistent with a Planck source function. A temperature-pressure profile is derived for the region near the north magnetic pole, from which quantitative abundance estimates of minor species are made. Some species previously detected on Jupiter, including CH3D, C2H2, and C2H6, have been observed again near the pole. Newly discovered species, not previously observed on Jupiter, include C2H4, C3H4, and C6H6. All of these species except CH3D appear to have enhanced abundances at the north polar region with respect to midlatitudes. Upper limits are determined for C4H2 and C3H8. The quantitative results are compared with model calculations based on ultraviolet results from the IUE satellite. The plausibility of the C6H6 identification is discussed in terms of the literature on C2H2 polymerization. The relation of C6H6 to cuprene is also discussed.

NASA Astrophysics Data System (ADS)

2018-05-01

The main reactions considered in OM mineralization during early diagenesis of sediment are listed in Table 1. Under oxidant-depleted conditions, fermentation of metabolizable OM of general formula CxHyOz can yield acetate, CO2 and H2 (r1). Note that reaction r1 takes into account any source of CO2 during fermentation including the partial degradation of high molecular weight OM (HMW OM) into lower molecular weight OM (LMW OM; Corbett et al., 2013; Corbett et al., 2015). The products of this reaction yield CH4 via either acetate fermentation (r2) or hydrogenotrophy (r3). In addition, when electron acceptors (EAs), i.e., Fe(III), SO42-, and partially oxidized HS, are present, CH4 (r4) and OM (r5) can be oxidized to produce CO2. Here, nitrate and Mn oxyhydroxides were not considered as oxidants, owing to the very low concentration of the former (<2 μmol L-1) over the whole sampling interval and because Mn oxyhydroxides do not form under the slightly acidic conditions prevailing in these porewaters (Chappaz et al., 2008). In addition, we neglected precipitation and dissolution of carbonate minerals except for siderite precipitation (r6) due to its positive SI values (SI ≥ 0.5).

Feasibility of biogas production from anaerobic co-digestion of herbal-extraction residues with swine manure.

PubMed

Li, Yan; Yan, Xi-Luan; Fan, Jie-Ping; Zhu, Jian-Hang; Zhou, Wen-Bin

2011-06-01

The objective of this work was to examine the feasibility of biogas production from the anaerobic co-digestion of herbal-extraction residues with swine manure. Batch and semi-continuous experiments were carried out under mesophilic anaerobic conditions. Batch experiments revealed that the highest specific biogas yield was 294 mL CH(4) g(-1) volatile solids added, obtained at 50% of herbal-extraction residues and 3.50 g volatile solids g(-1) mixed liquor suspended solids. Specific methane yield from swine manure alone was 207 mL CH(4) g(-1) volatile solid added d(-1) at 3.50 g volatile solids g(-1) mixed liquor suspended solids. Furthermore, specific methane yields were 162, 180 and 220 mL CH(4) g (-1) volatile solids added d(-1) for the reactors co-digesting mixtures with 10%, 25% and 50% herbal-extraction residues, respectively. These results suggested that biogas production could be enhanced efficiently by the anaerobic co-digestion of herbal-extraction residues with swine manure. Copyright © 2011 Elsevier Ltd. All rights reserved.

Anion exchange polymer electrolytes

DOEpatents

Kim, Yu Seung; Kim, Dae Sik; Lee, Kwan-Soo

2013-07-23

Solid anion exchange polymer electrolytes and compositions comprising chemical compounds comprising a polymeric core, a spacer A, and a guanidine base, wherein said chemical compound is uniformly dispersed in a suitable solvent and has the structure: ##STR00001## wherein: i) A is a spacer having the structure O, S, SO.sub.2, --NH--, --N(CH.sub.2).sub.n, wherein n=1-10, --(CH.sub.2).sub.n--CH.sub.3--, wherein n=1-10, SO.sub.2-Ph, CO-Ph, ##STR00002## wherein R.sub.5, R.sub.6, R.sub.7 and R.sub.8 each are independently --H, --NH.sub.2, F, Cl, Br, CN, or a C.sub.1-C.sub.6 alkyl group, or any combination of thereof; ii) R.sub.9, R.sub.10, R.sub.11, R.sub.12, or R.sub.13 each independently are --H, --CH.sub.3, --NH.sub.2, --NO, --CH.sub.nCH.sub.3 where n=1-6, HC.dbd.O--, NH.sub.2C.dbd.O--, --CH.sub.nCOOH where n=1-6, --(CH.sub.2).sub.n--C(NH.sub.2)--COOH where n=1-6, --CH--(COOH)--CH.sub.2--COOH, --CH.sub.2--CH(O--CH.sub.2CH.sub.3).sub.2, --(C.dbd.S)--NH.sub.2, --(C.dbd.NH)--N--(CH.sub.2).sub.nCH.sub.3, where n=0-6, --NH--(C.dbd.S)--SH, --CH.sub.2--(C.dbd.O)--O--C(CH.sub.3).sub.3, --O--(CH.sub.2).sub.n--CH--(NH.sub.2)--COOH, where n=1-6, --(CH.sub.2).sub.n--CH.dbd.CH wherein n=1-6, --(CH.sub.2).sub.n--CH--CN wherein n=1-6, an aromatic group such as a phenyl, benzyl, phenoxy, methylbenzyl, nitrogen-substituted benzyl or phenyl groups, a halide, or halide-substituted methyl groups; and iii) wherein the composition is suitable for use in a membrane electrode assembly.

Investigation of Biogenic and Non-biogenic Methane Sources in Texas

NASA Astrophysics Data System (ADS)

Yang, S.; Talbot, R. W.; Liu, L.; Lan, X.

2016-12-01

Methane (CH4) is a potent greenhouse gas with its mixing ratio increasing in the global atmosphere. Texas is one of the significant areas where underestimation of CH4 emissions by the U.S. inventories are pronounced. This study focused on two areas of Texas: Houston, the energy capital of the world, and the Barnett Shale area which is one of the largest onshore natural gas fields in the United States. The investigation of background CH4 and the fingerprints of CH4 emissions are critical to understanding potential impacts of extensive nature gas operations in these two areas. One-year of stationary CH4 measurements were studied to deduce the regional background CH4 characteristics and to identify the principle CH4 sources in Houston. Key information concerning CH4 sources can be obtained through the stable carbon isotope δ13CH4 during two field campaigns using a state-of-the-art mobile laboratory. CH4 mixing ratio and δ13C in CH4 were sampled by two cavity ring-down spectrometers (CRDS), one of which is coupled to a custom air core 13C sampling device which can supply more than 600 measurements for each plume analysis. Here, we report results of the overall δ13CH4 values and CH4 emission signatures derived from thirty-three sources in the two studied areas, ranging from oil production and processing, waste managements and landfills, to livestock. δ13CH4 signatures of these sources vary from -76‰ to -23‰. Several repeated measurements were sampled to investigate the variability of source signatures. We investigated a case of unexpected massive CH4 leaking detected near the San Jacinto River Fleet site. At the regional scale, the comparison of background δ13CH4 signatures were conducted to obtain the difference of dominate CH4 sources in two study areas. At the local scale, the combination of tower and mobile lab measurements were used to estimate and characterize CH4 emissions in Houston. The results and findings can supply valuable references for the local emission inventory and atmospheric model inputs.

Field-scale simulation of methane emissions from coastal wetlands in China using an improved version of CH4MODwetland.

PubMed

Li, Tingting; Xie, Baohua; Wang, Guocheng; Zhang, Wen; Zhang, Qing; Vesala, Timo; Raivonen, Maarit

2016-07-15

Coastal wetlands are important CH4 sources to the atmosphere. Coastal wetlands account for ~10% of the total area of natural wetlands in China, but the size of this potential CH4 source remains highly uncertain. We introduced the influence of salinity on CH4 production and CH4 diffusion into a biogeophysical model named CH4MODwetland so that it can be used in coastal wetlands. The improved model can generally simulate seasonal CH4 variations from tidal marshes dominated by Phragmites and Scirpus. However, the model underestimated winter CH4 fluxes from tidal marshes in the Yellow River Delta and YanCheng Estuary. It also failed to capture the accurate timing of the CH4 peaks in YanCheng Estuary and ChongMing Island in 2012. The improved model could generally simulate the difference between the annual mean CH4 fluxes from mangrove sites in GuangZhou and HaiKou city under different salinity and water table depth conditions, although fluxes were systematically underestimated in the mangrove site of HaiKou city. Using the improved model, the seasonal CH4 emissions simulated across all of the coastal wetlands ranged from 0.1 to 44.90gm(-2), with an average value of 7.89gm(-2), which is in good agreement with the observed values. The improved model significantly decreased the RMSE and RMD from 424% to 14% and 314% to -2%, respectively, and improved the EF from -18.30 to 0.99. Model sensitivity analysis showed that CH4 emissions were most sensitive to Pox in the tidal marshes and salinity in the mangroves. The results show that previous studies may have overestimated CH4 emissions on a regional or global scale by neglecting the influence of salinity. In general, the CH4MODwetland model can simulate seasonal CH4 emissions from different types of coastal wetlands under various conditions. Further improvements of CH4MODwetland should include the specific characteristics of CH4 processes in mangroves to decrease the uncertainty in estimating regional or global CH4 emissions from natural wetlands. Copyright © 2016 Elsevier B.V. All rights reserved.

Observing and modeling links between soil moisture, microbes and CH4 fluxes from forest soils

NASA Astrophysics Data System (ADS)

Christiansen, Jesper; Levy-Booth, David; Barker, Jason; Prescott, Cindy; Grayston, Sue

2017-04-01

Soil moisture is a key driver of methane (CH4) fluxes in forest soils, both of the net uptake of atmospheric CH4 and emission from the soil. Climate and land use change will alter spatial patterns of soil moisture as well as temporal variability impacting the net CH4 exchange. The impact on the resultant net CH4 exchange however is linked to the underlying spatial and temporal distribution of the soil microbial communities involved in CH4 cycling as well as the response of the soil microbial community to environmental changes. Significant progress has been made to target specific CH4 consuming and producing soil organisms, which is invaluable in order to understand the microbial regulation of the CH4 cycle in forest soils. However, it is not clear as to which extent soil moisture shapes the structure, function and abundance of CH4 specific microorganisms and how this is linked to observed net CH4 exchange under contrasting soil moisture regimes. Here we report on the results from a research project aiming to understand how the CH4 net exchange is shaped by the interactive effects soil moisture and the spatial distribution CH4 consuming (methanotrophs) and producing (methanogens). We studied the growing season variations of in situ CH4 fluxes, microbial gene abundances of methanotrophs and methanogens, soil hydrology, and nutrient availability in three typical forest types across a soil moisture gradient in a temperate rainforest on the Canadian Pacific coast. Furthermore, we conducted laboratory experiments to determine whether the net CH4 exchange from hydrologically contrasting forest soils responded differently to changes in soil moisture. Lastly, we modelled the microbial mediation of net CH4 exchange along the soil moisture gradient using structural equation modeling. Our study shows that it is possible to link spatial patterns of in situ net exchange of CH4 to microbial abundance of CH4 consuming and producing organisms. We also show that the microbial community responds different to environmental change dependent on the soil moisture regime. These results are important to include in future modeling efforts to predict changes in soil-atmosphere exchange of CH4 under global change.

Windrow composting mitigated CH4 emissions: characterization of methanogenic and methanotrophic communities in manure management.

PubMed

Chen, Ruirui; Wang, Yiming; Wei, Shiping; Wang, Wei; Lin, Xiangui

2014-12-01

With increasing livestock breeding, methane (CH4 ) emissions from manure management will increasingly contribute more to atmospheric CH4 concentration. The dynamics of methanogens and methanotrophs have not yet been studied in the manure environment. The current study combines surface CH4 emissions with methanogenic and methanotrophic community analyses from two management practices, windrow composting (WCOM) and solid storage (SSTO). Our results showed that there was an c. 50% reduction of CH4 emissions with WCOM compared with SSTO over a 50-day period. A sharp decrease in the quantities of both methanogens and methanotrophs in WCOM suggested that CH4 mitigation was mainly due to decreased CH4 production rather than increased CH4 oxidation. Pyrosequencing analysis demonstrated that aeration caused a clear shift of dominant methanogens in the manure, with specifically a significant decrease in Methanosarcina and increase in Methanobrevibacter. The composition of methanogenic community was influenced by manure management and regulated CH4 production. A sharp increase in the quantity of methanotrophs in SSTO suggested that microbial CH4 oxidation is an important sink for the CH4 produced. The increased abundance of Methylococcaceae in SSTO suggested that Type I methanotrophs have an advantage in CH4 oxidation in occupying niches under low CH4 and high O2 conditions. © 2014 Federation of European Microbiological Societies. Published by John Wiley & Sons Ltd. All rights reserved.

Seasonal and spatial variation in soil chemistry and anaerobic processes in an Arctic ecosystem

NASA Astrophysics Data System (ADS)

Lipson, D.; Mauritz, M.; Bozzolo, F.; Raab, T. K.; Santos, M. J.; Friedman, E. F.; Rosenbaum, M.; Angenent, L.

2009-12-01

Drained thaw lake basins (DTLB) are the dominant landform in the Arctic coastal plain near Barrow, Alaska. Our previous work in a DTLB showed that Fe(III) and humic substances are important electron acceptors in anaerobic respiration, and play a significant role in the C cycle of these organic-rich soils. In the current study, we investigated seasonal and spatial patterns of availability of electron acceptors and labile substrate, redox conditions and microbial activity. Landscapes within DTLB contain complex, fine-scale topography arising from ice wedge polygons, which produce raised and lowered areas. One goal of our study was to determine the effects of microtopographic variation on the potential for Fe(III) reduction and other anaerobic processes. Additionally, the soil in the study site has a complex vertical structure, with an organic peat layer overlying a mineral layer, overlying permafrost. We described variations in soil chemistry across depth profiles into the permafrost. Finally, we installed an integrated electrode/potentiostat system to electrochemically monitor microbial activity in the soil. Topographically low areas differed from high areas in most of the measured variables: low areas had lower oxidation-reduction potential, higher pH and electrical conductivity. Soil pore water from low areas had higher concentrations of Fe(III), Fe(II), dissolved organic C (DOC), and aromaticity (UV absorbance at 260nm, “A260”). Low areas also had higher concentrations of dissolve CO2 and CH4 in soil pore water. Laboratory incubations of soil showed a trend toward higher potentials for Fe(III) reduction in topographically low areas. Clearly, ice wedge-induced microtopography exerts a strong control on microbial processes in this DTLB landscape, with increased anaerobic activity occurring in the wetter, depressed areas. Soil water extracted from 5-15 cm depth had higher concentrations of Fe(III), Fe(II), A260, and DOC compared to soil water sampled from 0-5cm. The soil depth profile showed highest concentrations of acid-extractable Fe in the mineral layer and permafrost, though Fe(III) was highest in the surface layer. Total and soluble C increased with depth, as did the potential for CO2 and CH4 production in anaerobic incubations. Thus, the mineral layer may be a significant source of Fe for oxidation-reduction reactions that occur at shallower depths, though methanogenesis dominates in the mineral layer, while Fe(III) reduction dominates in the organic layer. Most of the ions measured in the soil pore water (Fe(III), DOC, A260) showed the same general seasonal pattern: high concentrations soon after soils thawed, declining over time until mid-August. Concentrations of Fe(II) in soil pore water were fairly stable over time. There was a significant positive relationship between A260 and Fe(III) concentrations, possibly indicating the presence of microbially-produced aromatic chelating molecules. Potentiostat measurements confirmed the presence of an electrochemically active microbial community in the soil.

Annual methane budgets of sheep grazing systems were regulated by grazing intensities in the temperate continental steppe: A two-year case study

NASA Astrophysics Data System (ADS)

Ma, Lei; Zhong, Mengying; Zhu, Yuhao; Yang, Helong; Johnson, Douglas A.; Rong, Yuping

2018-02-01

Methane (CH4) emission from animal husbandry accounts for a large percentage of anthropogenic contributions to CH4 emissions. Fully understanding of grazing management effects on the CH4 budget is essential for mitigating CH4 emissions in the temperate grazing steppe systems. Annual CH4 budgets for the sheep grazed steppes at various grazing intensities, un-grazing (UG, 0 sheep ha-1year-1), defer grazing (DG, 1.0 sheep ha-1 year-1), moderate grazing (MG, 1.43 sheep ha-1year-1), and heavy grazing (HG, 2.43 sheep ha-1year-1) were assessed across 2012-2014 in the agro-pastoral region of northern China. Annual soil CH4 uptake averaged across 2012-2014 were 1.1 ± 0.1, 2.4 ± 0.2, 2.2 ± 0.2, and 1.3 ± 0.1 kg CH4-C ha-1 for UG, DG (only 2013-2014), MG and HG sites. Non-growing season CH4 uptake comprised 50.0 ± 4.3% of annual CH4 uptake in 2012-2013 and 37.7 ± 2.0% in 2013-2014. DG and MG significantly promoted annual soil CH4 uptake (P < 0.05), while there was no difference between HG and UG (P > 0.05). Bell-shaped relationship was presented between stocking rates and soil CH4 uptake (r2 = 0.59, P < 0.05). Annual soil CH4 uptake significant linearly and positively correlated with root biomass (r2 = 0.30, P < 0.05). Annual CH4 budgets for the grazed grasslands were -1.1 ± 0.1, 5.7 ± 0.6, 11.5 ± 1.5 and 15.5 ± 1.3 kg CH4-C ha-1 year-1 in UG, DG (only 2013-2014), MG and HG across 2012-2014. Soil CH4 uptake could offset 29.7 ± 5.6, 15.9 ± 4.3 and 6.8 ± 1.0% of total annual CH4 emissions from sheep, sheepfold and faeces in DG, MG, and HG. All grazed steppes are sources for atmospheric CH4 and the magnitude is regulated by grazing intensities. Sheep CH4 emissions for 1-g liveweight gain were 0.21, 0.32 and 0.37 g CH4-C in DG, MG and HG, respectively. DG is the recommended grazing management in this region to achieve greater herbage mass, higher sheep performance and lower CH4 emissions simultaneously.

Effects of grass silage quality and level of feed intake on enteric methane production in lactating dairy cows.

PubMed

Warner, D; Bannink, A; Hatew, B; van Laar, H; Dijkstra, J

2017-08-01

The objective of this study was to determine the effect of level of feed intake and quality of ryegrass silage as well as their interaction on enteric methane (CH) emission from dairy cows. In a randomized block design, 56 lactating dairy cows received a diet of grass silage, corn silage, and a compound feed meal (70:10:20 on DM basis). Treatments consisted of 4 grass silage qualities prepared from grass harvested from leafy through late heading stage, and offered to dairy cows at 96 ± 2.4 (mean ± SEM) days in milk (namely, high intake) and 217 ± 2.4 d in milk (namely, low intake). Grass silage CP content varied between 124 and 286 g/kg of DM, and NDF content between 365 and 546 g/kg of DM. After 12 d of adaptation, enteric CH production of cows was measured in open-circuit climate-controlled respiration chambers for 5 d. No interaction between DMI and grass quality on CH emission, or on milk production, diet digestibility, and energy, and N retention was found ( ≥ 0.17). Cows had a greater DMI (16.6 vs. 15.5 kg/d; SEM 0.46) and greater fat- and protein-corrected milk (FPCM) yield (29.9 vs. 25.4 kg/d; SEM 1.24) at high than low intake (both ≤ 0.001). Apparent total-tract nutrient digestibility was not affected ( ≥ 0.08) by DMI level. Total enteric CH production (346 ± 10.9 g/d) was not affected ( = 0.15) by DMI level. A small, significant ( = 0.025) decrease at high compared with low intake occurred for CH yield (21.8 ± 0.59 g/kg of DMI; -4%). Methane emission intensity (12.8 ± 0.56 g/kg of FPCM; -12%) was considerably smaller ( ≤ 0.001) at high intake as a result of greater milk yields realized in early lactation. As grass quality decreased from leafy through late heading stage, FPCM yield and apparent total-tract OM digestibility declined (-12%; ≤ 0.015), whereas total CH production (+13%), CH yield (+21%), and CH emission intensity (+28%) increased ( ≤ 0.001). Our results suggest that improving grass silage quality by cutting grass at an earlier stage considerably reduces enteric CH emissions from dairy cows, independent of DMI. In contrast, losses of N in manure increased for the earlier cut grass silage treatments. The small increase in DMI at high intake was associated with a small to moderate reduction in CH emission per unit of DMI and GE intake. This study confirmed that enteric CH emissions from dairy cows at distinct levels of feed intake depend on the nutritive value and chemical composition of the grass silage.

The etiologies and incidences of congenital hypothyroidism before and after neonatal TSH screening program implementation: a study in southern Thailand.

PubMed

Jaruratanasirikul, Somchit; Piriyaphan, Jutarat; Saengkaew, Tansit; Janjindamai, Waricha; Sriplung, Hutcha

2018-06-27

Congenital hypothyroidism (CH) is one of the common causes of intellectual disability which can be prevented by early detection of an elevated thyroid stimulating hormone (TSH) level in the newborn and by treatment with thyroxine. In Thailand, neonatal TSH screening was implemented nationwide in 2005. The objective of the study was to determine the etiologies and the estimated incidences of CH in southern Thailand before and after the implementation of a neonatal TSH screening program in 2005. The medical records of pediatric patients who were diagnosed with primary CH at Songklanagarind Hospital during 1995-2013 were retrospectively reviewed. The study was divided into two time periods: study period 1 (SP1) (1995-2004) and study period 2 (SP2) (2005-2013), the time before and after TSH program implementation. The most common form of CH during SP1 was overt permanent CH (66%), mostly caused by athyreosis or ectopic thyroid. In SP2, the most common form of CH was mild permanent CH (39%) (mostly due to dyshormonogenesis), followed by overt CH (32%) and transient CH (29%). The overall annual estimated incidence of CH per 10,000 live births in Songkhla Province was 1.69 (1:5021) in SP1, increasing to 4.77 (1:2238) in SP2; in all 14 provinces in southern Thailand, the estimated incidence was 1.24 (1:8094) in SP1 and 2.33 (1:4274) in SP2. Neonatal TSH screening has a significant impact on the increased detection of the mild form of permanent and transient CH cases, which may be important for the prevention of brain damage from less severe CH although this remains to be documented.

Progression from Mild Cognitive Impairment to Alzheimer's disease: effects of gender, butyrylcholinesterase genotype and rivastigmine treatment

PubMed Central

Ferris, Steven; Nordberg, Agneta; Soininen, Hilkka; Darreh-Shori, Taher; Lane, Roger

2014-01-01

Objective Evaluate the influence of gender and butyrylcholinesterase (BuChE) genotype on incidence of progression to AD, rate of cognitive and functional decline, and response to rivastigmine treatment in mild cognitive impairment (MCI) subjects. Methods This retrospective exploratory analysis from a 3–4 year, randomized, placebo-controlled study of rivastigmine in MCI subjects included participants who consented to pharmacogenetic testing. Results Of 1018 total patients, 490 (253 [52%] female) were successfully genotyped for BuChE. In subjects receiving placebo, the BuChE wt/wt genotype was associated with a statistically significantly higher rate of progression to AD and functional decline in women, compared with men with the BuChE wt/wt genotype. In subjects with a BuChE-K allele receiving placebo, incidence of progression to AD and rate of functional decline were not significantly different by gender, however cognitive decline was significantly faster in men. Statistically significant benefits of rivastigmine treatment on progression to AD, functional decline, ventricular volume expansion, whole brain atrophy and white matter loss were evident in female BuChE wt/wt. Conclusion Gender appears to differentially influence the type of decline in MCI subjects according to BuChE genotype, with more rapid progression of cognitive decline in male BuChE-K, and more rapid progression to AD and functional decline in female BuChE wt/wt. Cognitive decline in male BuChE-K and functional decline and progression to AD in female BuChE wt/wt were significantly attenuated by rivastigmine. Rivastigmine treatment also significantly reduced ventricular expansion, whole brain atrophy rate and white matter loss in female BuChE wt/wt, suggesting a possible disease-modifying effect. PMID:19617863

Two Different Bacterial Community Types Are Linked with the Low-Methane Emission Trait in Sheep

PubMed Central

Kittelmann, Sandra; Pinares-Patiño, Cesar S.; Seedorf, Henning; Kirk, Michelle R.; Ganesh, Siva; McEwan, John C.; Janssen, Peter H.

2014-01-01

The potent greenhouse gas methane (CH4) is produced in the rumens of ruminant animals from hydrogen produced during microbial degradation of ingested feed. The natural animal-to-animal variation in the amount of CH4 emitted and the heritability of this trait offer a means for reducing CH4 emissions by selecting low-CH4 emitting animals for breeding. We demonstrate that differences in rumen microbial community structure are linked to high and low CH4 emissions in sheep. Bacterial community structures in 236 rumen samples from 118 high- and low-CH4 emitting sheep formed gradual transitions between three ruminotypes. Two of these (Q and S) were linked to significantly lower CH4 yields (14.4 and 13.6 g CH4/kg dry matter intake [DMI], respectively) than the third type (H; 15.9 g CH4/kg DMI; p<0.001). Low-CH4 ruminotype Q was associated with a significantly lower ruminal acetate to propionate ratio (3.7±0.4) than S (4.4±0.7; p<0.001) and H (4.3±0.5; p<0.001), and harbored high relative abundances of the propionate-producing Quinella ovalis. Low-CH4 ruminotype S was characterized by lactate- and succinate-producing Fibrobacter spp., Kandleria vitulina, Olsenella spp., Prevotella bryantii, and Sharpea azabuensis. High-CH4 ruminotype H had higher relative abundances of species belonging to Ruminococcus, other Ruminococcaceae, Lachnospiraceae, Catabacteriaceae, Coprococcus, other Clostridiales, Prevotella, other Bacteroidales, and Alphaproteobacteria, many of which are known to form significant amounts of hydrogen. We hypothesize that lower CH4 yields are the result of bacterial communities that ferment ingested feed to relatively less hydrogen, which results in less CH4 being formed. PMID:25078564

Reservoir water level drawdown as a novel, substantial, and manageable control on methane release to the atmosphere

NASA Astrophysics Data System (ADS)

Harrison, J.; Deemer, B. R.; Birchfield, M. K.

2014-12-01

Reservoirs constitute a globally important source of atmospheric methane (CH4). Although it is reasonably well-established that hydrostatic and barometric pressure can influence rates of CH4 release from lake and tidal sediments, the relationship between water-level manipulation and CH4 release from man-made impoundments has not been quantified or characterized. Furthermore, cross-system controls on CH4 production and release to the atmosphere have not been established. We collected CH4 emission (diffusion and ebullition) data for 8 reservoirs in the U.S. Pacific Northwest that are subject to a range of trophic conditions and water level management regimes. Our aim was to: (1) characterize CH4 emissions from these systems, and (2) quantify effects of water level management and eutrophication on CH4 fluxes. Results indicate very high fluxes, in some cases the highest reported reservoir emission rates, and a strong correspondence between lake level reduction and CH4 emissions, including quantitatively important bursts of CH4 bubbling. In one reservoir, drawdown-associated CH4 fluxes accounted for over 25% of annual CH4 emissions in a period of just 16 days (4% of the year). Average CH4 ebullition rates in a reservoir managed for hydropower peaking were nearly three-fold higher than in a paired upstream reservoir managed to maintain a constant water level (528 mg CH4 m-2 d-1 and 187 mg CH4 m-2 d-1 respectively). Highest gas fluxes were observed during the water level drawdown component of the hydropower peaking cycle (14.3 g CH4 m-2 d-1). In addition we observe a strong, positive relationship between eutrophication (as indicated by surface Chl a concentrations) and CH4 production (r2 = 0.88; P<0.001) and between eutrophication and the sensitivity of CH4 emissions to drawdown (r2 = 0.84; P<0.001). This work suggests that manipulation of water levels can significantly affect CH4 emissions from reservoirs to the atmosphere, and that sampling programs that miss drawdown periods may substantially underestimate CH4 fluxes. It also suggests that controlling nutrient loading may reduce greenhouse gas fluxes from surface waters to the atmosphere.

Association of aqueous hydrogen concentration with methane production in continuous cultures modulated to vary pH and solids passage rate.

PubMed

Wenner, B A; de Souza, J; Batistel, F; Hackmann, T J; Yu, Z; Firkins, J L

2017-07-01

The objective of this study was to evaluate the effects of altering pH and solids passage rate (k p ) on concentration of aqueous H 2 [H 2 (aq)], CH 4 production, volatile fatty acids (VFA) production, and fiber digestibility in a continuous culture fermentation system. The present study was conducted as a 2 × 2 factorial treatment arrangement in a Latin square design using continuous culture fermentors (n = 4). Our continuous culture system was converted to a closed system to measure CH 4 and H 2 emission while measuring H 2 (aq) concentration and VFA production for complete stoichiometric assessment of fermentation pattern. Treatments were control pH (CpH; ranging from 6.3 to 6.9) or low pH (LpH; 5.8 to 6.4) factorialized with solids k p that was adjusted to be either low (Lk p ; 2.5%/h) or high (Hk p ; 5.0%/h); liquid dilution was maintained at 7.0%/h. Fermentors were fed once daily (40 g of dry matter; 50:50 concentrate:forage diet). Four periods lasted 10 d each, with 3 d of sample collection. The main effect of LpH increased nonammonia nitrogen flow, and both LpH and Hk p increased nonammonia nonbacterial N flow. We observed a tendency for Hk p to increase bacterial N flow per unit of nonstructural carbohydrates and neutral detergent fiber degraded. The main effect of LpH decreased H 2 (aq) by 4.33 µM compared with CpH. The main effect of LpH decreased CH 4 production rate from 5 to 9 h postfeeding, and Hk p decreased CH 4 production rate from 3 to 9 h postfeeding. We found no effect of LpH on daily CH 4 production or CH 4 produced per gram of neutral detergent fiber degraded, but Hk p decreased daily CH 4 production by 33.2%. Both the main effects of LpH and Hk p decreased acetate molar percentage compared with CpH and Lk p , respectively. The main effect of both LpH and Hk p increased propionate molar percentage, decreasing acetate-to-propionate ratio from 2.62 to 2.34. We noted no treatment effects on butyrate molar percentage or total VFA production. The results indicate increasing k p and decreasing pH decreased acetate-to-propionate ratio, but only increasing k p decreased CH 4 production; lack of differences for LpH might be a result of compensatory methanogenesis during the second half of the day postfeeding. Copyright © 2017 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Carbonato-bridged Ni(II)2Ln(III)2 (Ln(III) = Gd(III), Tb(III), Dy(III)) complexes generated by atmospheric CO2 fixation and their single-molecule-magnet behavior: [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(MeOH or H2O)Ln(III)(NO3)}2]·solvent [3-MeOsaltn = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato].

PubMed

Sakamoto, Soichiro; Fujinami, Takeshi; Nishi, Koshiro; Matsumoto, Naohide; Mochida, Naotaka; Ishida, Takayuki; Sunatsuki, Yukinari; Re, Nazzareno

2013-06-17

Atmospheric CO2 fixation of [Ni(II)(3-MeOsaltn)(H2O)2]·2.5H2O [3-MeOsaltn = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato], Ln(III)(NO3)3·6H2O, and triethylamine occurred in methanol/acetone, giving a first series of carbonato-bridged Ni(II)2Ln(III)2 complexes [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(MeOH)Ln(III)(NO3)}2] (1Gd, 1Tb, and 1Dy). When the reaction was carried out in acetonitrile/water, it gave a second series of complexes [(μ4-CO3)2{Ni(II)(3-MeOsaltn)(H2O)Ln(III)(NO3)}2]·2CH3CN·2H2O (2Gd, 2Tb, and 2Dy). For both series, each Ni(II)2Ln(III)2 structure can be described as two di-μ-phenoxo-bridged Ni(II)Ln(III) binuclear units bridged by two carbonato CO3(2-) units to form a carbonato-bridged (μ4-CO3)2{Ni(II)2Ln(III)2} structure. The high-spin Ni(II) ion has octahedral coordination geometry, and the Ln(III) ion is coordinated by O9 donor atoms from Ni(II)(3-MeOsaltn), bidentate NO3(-), and one and two oxygen atoms of two CO3(2-) ions. The NO3(-) ion for the first series roughly lie on Ln-O(methoxy) bonds and are tilted toward the outside, while for the second series, the two oxygen atoms roughly lie on one of the Ln-O(phenoxy) bonds due to the intramolecular hydrogen bond. The temperature-dependent magnetic susceptibilities indicated a ferromagnetic interaction between the Ni(II) and Ln(III) ions (Ln(III) = Gd(III), Tb(III), Dy(III)) for all of the complexes, with a distinctly different magnetic behavior between the two series in the lowest-temperature region due to the Ln(III)-Ln(III) magnetic interaction and/or different magnetic anisotropies of the Tb(III) or Dy(III) ion. Alternating-current susceptibility measurements under the 0 and 1000 Oe direct-current (dc) bias fields showed no magnetic relaxation for the Ni(II)2Gd(III)2 complexes but exhibited an out-of-phase signal for Ni(II)2Tb(III)2 and Ni(II)2Dy(III)2, indicative of slow relaxation of magnetization. The energy barriers, Δ/kB, for the spin flipping were estimated from the Arrhenius plot to be 12.2(7) and 6.1(3) K for 1Tb and 2Tb, respectively, and 18.1(6) and 14.5(4) K for 1Dy and 2Dy, respectively, under a dc bias field of 1000 Oe. Compound 1Dy showed relatively slow relaxation of magnetization reorientation even at zero dc applied field with Δ/kB = 6.6(4) K.

Structural and energetic properties of acetonitrile-Group IV (A & B) halide complexes.

PubMed

Helminiak, Heather M; Knauf, Robin R; Danforth, Samuel J; Phillips, James A

2014-06-19

We have conducted an extensive computational study of the structural and energetic properties of select acetonitrile-Group IV (A & B) tetrahalide complexes, both CH3CN-MX4 and (CH3CN)2-MX4 (M = Si, Ge, Ti; X = F, Cl). We have also examined the reactivity of CH3CN with SiF4, SiCl4, GeCl4, and TiCl4, and measured low-temperature IR spectra of thin films containing CH3CN with SiF4, GeCl4, or TiCl4. The six 1:1 complexes fall into two general structural classes. CH3CN-TiCl4, CH3CN-TiF4, and CH3CN-GeF4, exhibit relatively short M-N bonds (~2.3 Å), an intermediate degree of distortion in the MX4 subunit, and binding energies ranging from 11.0 to 13.0 kcal/mol. Conversely, CH3CN-GeCl4, CH3CN-SiF4, and CH3CN-SiCl4, are weakly bonded systems, with long M-N distances (>3.0 Å), little distortion in the MX4 subunit, and binding energies ranging from 3.0 to 4.4 kcal/mol. The structural features of analogous 2:1 systems resemble those of their 1:1 counterparts, whereas the binding energies (relative to three isolated fragments) are roughly twice as large. Calculated M-N potential curves in the gas phase and bulk, dielectric media are reported for all 1:1 complexes, and for two systems, CH3CN-GeF4 and CH3CN-SiF4, these data predict significant condensed-phase structural changes. The effect on the CH3CN-SiF4 potential is extreme; the curve becomes quite flat over a broad range in dielectric media, and at higher ε values, the global minimum shifts inward by about 1.0 Å. In bulk reactivity experiments, no reaction was observed between CH3CN and SiF4, SiCl4, or GeCl4, whereas CH3CN and TiCl4 were found to react immediately upon contact. Also, thin-film IR spectra indicate a strong interaction between CH3CN and TiCl4, yet only weak interactions between CH3CN and GeCl4 or SiF4 in the solid state.

Protonation of a lanthanum phosphide-alkyl occurs at the P-La not the C-La bond: isolation of a cationic lanthanum alkyl complex.

PubMed

Izod, Keith; Liddle, Stephen T; Clegg, William

2004-08-07

Protonation of the heteroleptic, cyclometalated lanthanum phosphide complex [((Me3Si)2CH)(C6H4-2-CH2NMe2)P]La(THF)[P(C6H4-2-CH2NMe2)(CH(SiMe3)(SiMe2CH2))] with [Et3NH][BPh4] yields the cationic alkyllanthanum complex [(THF)4La[P(C6H4-2-CH2NMe2)(CH(SiMe3)(SiMe2CH2))

Water in star-forming regions with Herschel (WISH). VI. Constraints on UV and X-ray irradiation from a survey of hydrides in low- to high-mass young stellar objects

NASA Astrophysics Data System (ADS)

Benz, A. O.; Bruderer, S.; van Dishoeck, E. F.; Melchior, M.; Wampfler, S. F.; van der Tak, F.; Goicoechea, J. R.; Indriolo, N.; Kristensen, L. E.; Lis, D. C.; Mottram, J. C.; Bergin, E. A.; Caselli, P.; Herpin, F.; Hogerheijde, M. R.; Johnstone, D.; Liseau, R.; Nisini, B.; Tafalla, M.; Visser, R.; Wyrowski, F.

2016-05-01

Context. Hydrides are simple compounds containing one or a few hydrogen atoms bonded to a heavier atom. They are fundamental precursor molecules in cosmic chemistry and many hydride ions have become observable in high quality for the first time thanks to the Herschel Space Observatory. Ionized hydrides such as CH+ and OH+ (and also HCO+), which affect the chemistry of molecules such as water, provide complementary information on irradiation by far-UV (FUV) or X-rays and gas temperature. Aims: We explore hydrides of the most abundant heavier elements in an observational survey covering young stellar objects (YSOs) with different mass and evolutionary state. The focus is on hydrides associated with the dense protostellar envelope and outflows, contrary to previous work that focused on hydrides in diffuse foreground clouds. Methods: Twelve YSOs were observed with HIFI on Herschel in six spectral settings providing fully velocity-resolved line profiles as part of the Water in star-forming regions with Herschel (WISH) program. The YSOs include objects of low (Class 0 and I), intermediate, and high mass, with luminosities ranging from 4 L⊙ to 2 × 105 L⊙. Results: The targeted lines of CH+, OH+, H2O+, C+, and CH are detected mostly in blue-shifted absorption. H3O+ and SH+ are detected in emission and only toward some high-mass objects. The observed line parameters and correlations suggest two different origins related to gas entrained by the outflows and to the circumstellar envelope. The derived column densities correlate with bolometric luminosity and envelope mass for all molecules, best for CH, CH+, and HCO+. The column density ratios of CH+/OH+ are estimated from chemical slab models, assuming that the H2 density is given by the specific density model of each object at the beam radius. For the low-mass YSOs the observed ratio can be reproduced for an FUV flux of 2-400 times the interstellar radiation field (ISRF) at the location of the molecules. In two high-mass objects, the UV flux is 20-200 times the ISRF derived from absorption lines, and 300-600 ISRF using emission lines. Upper limits for the X-ray luminosity can be derived from H3O+ observations for some low-mass objects. Conclusions: If the FUV flux required for low-mass objects originates at the central protostar, a substantial FUV luminosity, up to 1.5 L⊙, is required. There is no molecular evidence for X-ray induced chemistry in the low-mass objects on the observed scales of a few 1000 AU. For high-mass regions, the FUV flux required to produce the observed molecular ratios is smaller than the unattenuated flux expected from the central object(s) at the Herschel beam radius. This is consistent with an FUV flux reduced by circumstellar extinction or by bloating of the protostar. Herschel is an ESA space observatory with science instruments provided by a European-led Principal Investigator consortia and with important participation from NASA.

Characterization of the Solid-Phase Behavior of n-Nonylammonium Tetrachlorocuprate by Fourier Transform Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Ning, Guo

1995-06-01

The solid-phase behavior of [n-C9H19NH3]2CuCl4 was investigated by infrared spectroscopy. The nature of the three solid phases (phase I, phase II, and phase III) is discussed. A temperature-dependent study of infrared spectra provides evidence for the occurrence of structural phase transitions related to the dynamics of the alkyl chains and -NH3 polar heads. The phase transition at Tc1 (22°C) arises from variation in the interaction and packing structure of the chain. The phase transition at Tc2 (34°C) is related to variation in partial conformational order-disorder at the intramolecular level. The GTG or GTG‧ and small concentration of TG structures near the CH3 group are generated in phase III (above 38°C).

Using carbon isotope fractionation for an improved quantification of CH4 oxidation efficiency in Arctic peatlands

NASA Astrophysics Data System (ADS)

Preuss, I.; Knoblauch, C.; Gebert, J.; Pfeiffer, E.-M.

2012-04-01

Much research effort is focused on identifying global CH4 sources and sinks to estimate their current and potential strength in response to land-use change and global warming. Aerobic CH4 oxidation is regarded as the key process reducing the strength of CH4 emissions in wetlands, but is hitherto difficult to quantify. Recent studies quantify the efficiency of CH4 oxidation based on CH4 stable isotope signatures. The approach utilizes the fact that a significant isotope fractionation occurs when CH4 is oxidized. Moreover, it also considers isotope fractionation by diffusion. For field applications the 'open-system equation' is applied to determine the CH4 oxidation efficiency: fox = (δE - δP)/ (αox - αtrans) where fox is the fraction of CH4 oxidized; δE is δ13C of emitted CH4; δP is δ13C of produced CH4; αox is the isotopic fractionation factor of oxidation; αtrans is the isotopic fractionation factor of transport. We quantified CH4 oxidation in polygonal tundra soils of Russia's Lena River Delta analyzing depth profiles of CH4 concentrations and stable isotope signatures. Therefore, both fractionation factors αox and αtrans were determined for three polygon centers with differing water table positions and a polygon rim. While most previous studies on landfill cover soils have assumed a gas transport dominated by advection (αtrans = 1), other CH4 transport mechanisms as diffusion have to be considered in peatlands and αtrans exceeds a value of 1. At our study we determined αtrans = 1.013 ± 0.003 for CH4 when diffusion is the predominant transport mechanism. Furthermore, results showed that αox differs widely between sites and horizons (αox = 1.013 ± 0.012) and has to be determined for each case. The impact of both fractionation factors on the quantification of CH4 oxidation was estimated by considering both the potential diffusion rate at different water contents and potential oxidation rates. Calculations for a water saturated tundra soil indicated a CH4 oxidation efficiency of 88% in the upper horizon. Using carbon isotope fractionation improves the in situ quantification of CH4 oxidation in wetlands and thus the assessment of current and potential CH4 sources and sinks in these ecosystems.

Hydrocarbon ices in extra-red TNOs and Centaurs

NASA Astrophysics Data System (ADS)

Dalle Ore, C. M.; Barucci, M.; Emery, J. P.; Cruikshank, D. P.; Merlin, F.; Perna, D.

2012-12-01

We present an analysis of the reddest trans-neptunian objects (TNOs) and Centaurs - those belonging to the RR taxon. The RR class contains more than ¼ of the population of TNOs for which photometric colors are available, including a variety of dynamically different objects. The available data cover the spectral range from 0.3 to 2.2 μm. Previous work investigated possible relations between spectral characteristics and other physical and dynamical parameters. The distribution of ices on TNOs has been analyzed as a function of the object absolute magnitude, taxonomy and dynamical class. In a sample of 76 objects for which visible and near-IR spectroscopic measurements are available, CH3OH ice was detected only on three objects belonging to the RR taxonomic class (5145 Pholus, 55638 2002 VE95 and 90377 Sedna). These three objects are among the reddest, they belong to different dynamical classes, and they have different dimensions. However, all three have similar compositions with Sedna showing a more significant heterogeneity in the kind of hydrocarbon ices found on its surface than the others. To further investigate the presence of hydrocarbon ices, and in particular CH3OH, as part of the composition of the RR taxon we used Spitzer IRAC data available for a subgroup of nine objects. Both methanol and methane have a strong absorption at 3.6 μm, the first of the Spitzer IRAC channels, and a much higher albedo at the following channel at 4.5 μm. This albedo pattern is characteristic of some hydrocarbon ices and is very different from H2O ice that shows instead very low albedos at both channels. Our technique makes use of a large database of models including H2O, CH3OH, CH4, and N 2 ices combined with tholins, amorphous carbon, hydrogenated amorphous carbon, serpentine and olivine in different combinations of relative abundances and grain sizes. We automatically extract the models that match the observations at all color wavelengths therefore obtaining for each object a set of compositions that are consistent with its colors. We detect hydrocarbon ices on most objects in our sample. The presence of methanol, or more generally hydrocarbons, on these extra red objects could imply that they exhibit an almost primordial surface. In fact, laboratory experiments of irradiation of compounds rich in methanol show strong reddening. The reddening effect on a Centaur or TNO depends on the composition of the object and on the irradiation history while the thickness of the organic crust depends on the irradiation dose. These objects, following the hypothesis of Brown et al (2011) that objects that formed farther away might be able to retain their methanol ice, have the surface composition and colors set by formation-location-dependent volatile loss in the early solar system. The results of the current work also support the hypothesis that a substantial mixing has occurred after the TNOs formation but cannot exclude the hypothesis of initial heterogeneity.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

An Ecosystem Simulation Model for Methane Production and Emission from Wetlands

NASA Technical Reports Server (NTRS)

Potter, C. S.; Peterson, David L. (Technical Monitor)

1997-01-01

Previous experimental studies suggest that methane emission from wetland is influenced by multiple interactive pathways of gas production and transport through soil and sediment layers to the atmosphere. The objective of this study is to evaluate a new simulation model of methane production and emission in wetland soils that was developed initially to help identify key processes that regulate methanogenesis and net flux of CH4 to the air, but which is designed ultimately for regional simulation using remotely sensed inputs for land cover characteristics. The foundation for these computer simulations is based on a well-documented model (CASA) of ecosystem production and carbon cycling in the terrestrial blaspheme. Modifications to represent flooded wetland soils and anaerobic decomposition include three new sub-models for: (1) layered soil temperature and water table depth (WTD) as a function of daily climate drivers, (2) CH4 production within the anoxic soil layer as a function of WTD and CO2 production under poorly drained conditions, and (3) CH4 gaseous transport pathways (molecular diffusion, ebullition, and plant vascular transport) as a function of WTD and ecosystem type. The model was applied and tested using climate and ecological data to characterize tundra wetland sites near Fairbanks, Alaska studied previously by Whalen and Reeburgh. Comparison of model predictions to measurements of soil temperature and thaw depth, water-table depth, and CH4 emissions over a two year period suggest that inter-site differences in soil physical conditions and methane fluxes could be reproduced accurately for selected periods. Day-to-day comparison of predicted emissions to measured CH4 flux rates reveals good agreement during the early part of the thaw season, but the model tends to underestimate production of CH4 during the months of July and August in both test years. Important seasonal effects, including that of falling WTD during these periods, are apparently overlooked in the model formulation. Nevertheless, reasonably close agreement was achieved between the model's mean daily and seasonal estimates of CH4 flux and observed emission rates for northern wetland ecosystems. Several features of the model are identified as crucial to more accurate prediction of wetland methane emission, including the capacity to incorporate influences of localized topographic and hydrologic features on site-specific soil temperature and WTD dynamics, and mechanistic simulation of methane emission transport pathways from within the soil profile.

Response of Carbon Fluxes to Soil Moisture Variability across an Alaskan Tundra Landscape

NASA Astrophysics Data System (ADS)

Melton, S.; Natali, S.; Schade, J. D.; Holmes, R. M.; Mann, P. J.; Fiske, G. J.

2017-12-01

Soils in arctic and sub-arctic permafrost regions store large amounts of carbon (C), which is becoming more biologically available as soils warm and permafrost thaws. Microbial decay of organic forms of C can result in the production and emission of carbon dioxide (CO2) and methane (CH4), and the amount and form of C released into the atmosphere depend on organic matter composition and soil conditions. Soil moisture, which is a strong driver of microbial processes, varies spatially and temporally across tundra landscapes and may change dramatically as a result of permafrost thaw. The Yukon-Kuskokwim Delta (YKD) of Alaska is underlain by discontinuous permafrost and is particularly vulnerable to permafrost thaw and soil moisture changes associated with thaw. As permafrost thaws, some areas may dry as drainage increases with increasing thaw depth. Alternatively, permafrost thaw may lead to ground subsidence and saturation of previously dry soils. Our objective was to investigate patterns in C storage and processing across the landscape and in response to changes in soil moisture in the YKD. We analyzed soil C pools (0-30 cm) and CO2 and CH4 concentrations in soils from sites of different land cover and landscape position, including moist and dry peat plateaus, high and low intensity burned plateaus, fens, and drained lakes. We also conducted aerobic and anaerobic soil incubations to determine changes in CO2 and CH4 production under a range of soil moisture conditions. Soils from burned plateaus, which were drier and had lower C content than unburned soils, had higher CO2 production (per g soil) than unburned soils during aerobic incubations. Both increased and decreased moisture reduced CO2 production from soils. Soil drying increased net CH4 uptake in all aerobically-incubated burned soils, and wetting resulted in CH4 emissions from low intensity burn soils. CO2 and CH4 production from fen soils were higher than from the other landscape positions analyzed here. Our results suggest that soil drying could lead to decreased microbial respiration, whereas subsidence may result in increased methanogenesis. Additionally, amplified CH4 release from burned soils after rainfall events or subsidence may accompany the increased fire frequency projected in tundra regions.

Subsoil methanogenesis as source of stem CH4 emission in upland forest trees: preferential CH4 transport via the root system?

NASA Astrophysics Data System (ADS)

Maier, M.; Machacova, K.; Urban, O.; Friederike, L.

2016-12-01

Quantifying and understanding green house gas fluxes in natural soil-plant-atmosphere systems are crucial to predicting global climate change. Wetland species or trees at waterlogged sites are known to emit large amounts of CH4. Yet upland forest soils are regarded as CH4 sinks and tree species like upland European beech (Fagus sylvatica, L.) are assumed not to emit CH4. We studied the soil-atmosphere and stem-atmosphere fluxes of CH4, and soil gas profiles at two upland beech forest sites in Central Europe. Soil was a net CH4 sink at both. Unusually there was one beech tree with substantial CH4 emissions that were higher than the CH4 sink of the soil. The soil gas profile at this tree indicated CH4 production at a soil depth >0.3 m, despite the net uptake of CH4 observed at the soil surface adjacent to the tree. Field soil assessment showed strong redoximorphic color patterns in the adjacent soil. We think that there is a transport link between the soil and stem via the root system representing a preferential transport mechanism for CH4 despite the fact that beech roots usually do not bear aerenchyma. The gas transport process , either via dissolved CH4 in the xylem water or in the root gas phase, is not yet clear. The observed CH4 stem emissions represent an important CH4flux in this ecosystem, und thus should be considered in future research. AcknowledgementThis research was financially supported by the Czech Academy of Sciences and the German Academic Exchange Service within the project "Methane (CH4) and nitrous oxide (N2O) emissions from Fagus sylvatica trees" (DAAD-15-03), National Programme for Sustainability I (LO1415) and project DFG (MA 5826/2-1). We would like to thank Marek Jakubik, Katerina Svobodova, Sinikka Paulus, Ellen Halaburt and Sally Haddad for technical support.

A novel pathway of direct methane production and emission by eukaryotes including plants, animals and fungi: An overview

NASA Astrophysics Data System (ADS)

Liu, Jiangong; Chen, Huai; Zhu, Qiuan; Shen, Yan; Wang, Xue; Wang, Meng; Peng, Changhui

2015-08-01

Methane (CH4) is a powerful greenhouse gas with a global warming potential 28 times that of carbon dioxide (CO2). CH4 is responsible for approximately 20% of the Earth's warming since pre-industrial times. Knowledge of the sources of CH4 is crucial due to the recent substantial interannual variability of growth rates and uncertainties regarding individual sources. The prevailing paradigm is that methanogenesis carried out by methanogenic archaea occurs primarily under strictly anaerobic conditions. However, in the past decade, studies have confirmed direct CH4 release from three important kingdoms of eukaryotes-Plantae, Animalia and Fungi-even in the presence of oxygen. This novel CH4 production pathway has been aptly termed ;aerobic CH4 production; to distinguish it from the well-known anaerobic CH4 production pathway, which involves catalytic activity by methanogenic archaeal enzymes. In this review, we collated recent experimental evidence from the published literature and documented this novel pathway of direct CH4 production and emission by eukaryotes. The mechanisms involved in this pathway may be related to protective strategies of eukaryotes in response to changing environmental stresses, with CH4 a by-product or end-product during or at the end of the process(es) that originates from organic methyl-type compounds. Based on the existing, albeit uncertain estimates, plants seem to contribute less to the global CH4 budget (3-24%) compared to previous estimates (10-37%). We still lack estimates of CH4 emissions by animals and fungi. Overall, there is an urgent need to identify the precursors for this novel CH4 source and improve our understanding of the mechanisms of direct CH4 production and the impacts of environmental stresses. An estimate of this new CH4 source, which was not considered as a CH4 source by the Intergovernmental Panel on Climate Change (IPCC) (2013), could be useful for better quantitation of the global CH4 budget.

Synthesis and first use of pyridine-2,6-diylbis(pyrazine-2-ylmethanone) in metal cluster chemistry: a {Mn(III)3Na2} complex with an ideal trigonal bipyramidal geometry.

PubMed

Giannopoulos, Dimosthenis P; Wilson-Konderka, Cody; Gagnon, Kevin J; Teat, Simon J; Escuer, Albert; Metallinos, Costa; Stamatatos, Theocharis C

2015-03-07

The successful organic synthesis of a new dipyrazole/pyridine-dicarbonyl organic molecule, namely pyridine-2,6-diylbis(pyrazine-2-ylmethanone) [(pz)CO(py)CO(pz)], followed by its employment in Mn coordination chemistry has yielded the neutral cluster compound [Mn3Na2O(N3)3(L)3] (1), where L(2-) is the (pz)C(CH2COCH3)(O(-))(py)C(CH2COCH3)(O(-))(pz) dianion. The latter group was formed in situ, presumably by the nucleophilic attack of the carbanion (-)CH2COCH3 to the carbonyl carbon atoms of (pz)CO(py)CO(pz), in the presence of Mn(n+) ions under basic conditions and in solvent Me2CO. Complex 1 possesses an almost ideal trigonal bipyramidal topology, with the two Na(I) ions occupying the apical positions and the three Mn(III) ions residing in the equatorial trigonal plane. The bridging ligation about the metal ions is provided by a μ3-O(2-) ion and six μ-OR(-) groups from the L(2-) ligand, while peripheral ligation is completed by three terminal azido groups and the pyridine N and carbonyl O atoms of L(2-). Magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions between the paramagnetic Mn(III) centres; the use of an anisotropic, equilateral Mn(III)3 triangle model allowed us to fit the magnetic data and obtain the best-fit parameters: J = -10.8 cm(-1), D = -5.3 cm(-1), and g = 1.99. The combined results demonstrate the rich chemical reactivity of carbonyl groups and the ability of poly-ketone ligands to stabilize cluster compounds with unprecedented structural motifs and interesting architectures.

Estimating Sources and Sinks of Methane from Soils in the Contiguous United States (CONUS)

NASA Astrophysics Data System (ADS)

Shu, S.; Jain, A. K.; Kheshgi, H. S.

2017-12-01

The global methane (CH4) budget estimated based on state-of-the-art models remains highly uncertain. Sources and sinks of CH4 from soils, including wetlands, are the most important source of uncertainty. Soils are estimated to account for about 45% of global CH4 emissions. At the same time oxidation of CH4 by soils is a significant sink, representing about 10% of the total sink. However, most regional and global scale modeling studies of soil CH4 fluxes have ignored the sink through soil oxidation and the source of CH4 emissions from the wet soils with shallow water tables. In this study, we link a bottom-up soil gas diffusion and CH4 biogeochemistry model to a land surface model, ISAM, to calculate the sources, emissions from both wetlands and non-wetlands, and sinks, soil oxidation, of CH4 from soils for the CONUS over the period 1900-2100. The newly developed soil CH4 model framework consists of a gas diffusion module with the vertically resolved soil hydrology (depth up to 3.5 m soil) and soil organic carbon (SOC) and CH4 biogeochemistry module. SOC profile is estimated by modeling vertical soil mixing and thus can represent the deep SOC content and estimate CH4 production from the deep non-wetland soil. For the diffusion calculations, we separately consider both the dissolved and gaseous O2 and CH4 at each soil layer. For CH4 biogeochemistry, we parameterize the production, soil oxidation, ebullition and aerenchyma transportation of CH4 for both seasonal/permanent wetland and wet soil. The SWAMP inundated fraction dataset with 8-day temporal resolution is incorporated to prescribe the extent of permanent and seasonal wetland extent for the recent decade. The model is first evaluated using a compilation of published CH4 site measurement data for CONUS. We then perform two different model experiments: 1) forced by the CRUNCEP climate data from 1900 to 2010 to estimate the contemporary CH4 emission and 2) forced by a climate projection of IPCC's highest representative concentration pathway (RCP8.5) from 2011 to 2100. Our study shows that soil oxidation has an important role attenuating the estimated natural CH4 source. We also find a wetter and warmer climate affects the dry soil CH4 sink and wet soil CH4 emissions and increases the estimated CH4 source over the CONUS.

Calcium-aluminum-rich inclusions recycled during formation of porphyritic chondrules from CH carbonaceous chondrites

NASA Astrophysics Data System (ADS)

Krot, Alexander N.; Nagashima, Kazuhide; van Kooten, Elishevah M. M.; Bizzarro, Martin

2017-03-01

We report on the mineralogy, petrography, and O-isotope compositions of ∼60 Ca, Al-rich inclusions (CAIs) incompletely melted during formation of porphyritic chondrules from the CH metal-rich carbonaceous chondrites and Isheyevo (CH/CB). These include (i) relict polymineralic CAIs in porphyritic chondrules, (ii) CAIs surrounded by chondrule-like igneous rims, (iii) igneous pyroxene-rich and Type C-like CAIs, and (iv) plagioclase-rich chondrules with clusters of relict spinel grains. 26Al-26Mg systematics were measured in 10 relict CAIs and 11 CAI-bearing plagioclase-rich chondrules. Based on the mineralogy, the CH CAIs incompletely melted during chondrule formation can be divided into grossite-rich (n = 13), hibonite-rich (n = 11), spinel ± melilite-rich (n = 33; these include plagioclase-rich chondrules with clusters of relict spinel grains) types. Mineralogical observations indicate that these CAIs were mixed with different proportions of ferromagnesian silicates and experienced incomplete melting and gas-melt interaction during chondrule formation. These processes resulted in partial or complete destruction of the CAI Wark-Lovering rims, replacement of melilite by Na-bearing plagioclase, and dissolution and overgrowth of nearly end-member spinel by chromium- and iron-bearing spinel. Only two relict CAIs and two CAI-bearing chondrules show resolvable excess of radiogenic 26Mg; the inferred initial 26Al/27Al ratios are (1.7 ± 1.3) × 10-6, (3.7 ± 3.1) × 10-7, (1.9 ± 0.9) × 10-6 and (4.9 ± 2.6) × 10-6. There is a large range of Δ17O among the CH CAIs incompletely melted during chondrule formation, from ∼-37‰ to ∼-5‰; the unmelted minerals in individual CAIs, however, are isotopically uniform and systematically 16O-enriched relative to the host chondrules and chondrule-like igneous rims, which have Δ17O ranging from ∼-7‰ to ∼+4‰. Most of the CH CAIs incompletely melted during chondrule formation are mineralogically and isotopically similar to the CH CAIs surrounded by Wark-Lovering rims and apparently unaffected by chondrule melting. The mineralogy and O-isotope compositions of the CH CAI-bearing chondrules are similar to those of the CH porphyritic chondrules without relict CAIs. We conclude that CH porphyritic chondrules formed by incomplete melting of isotopically diverse solid precursors, including mineralogically and isotopically unique CAIs commonly observed only in CH chondrites. Therefore, the CH porphyritic chondrules must have formed in a distinct disk region, where the CH CAIs were present at the time of chondrule formation. Because most CH CAIs avoided chondrule melting, we infer that chondrule formation was highly localized. These observations preclude formation of CH porphyritic chondrules by splashing of molten planetesimals, by impact processing of differentiated planetesimals, and by large scale nebular shocks, e.g., shocks driven by disk gravitational instabilities or by X-ray flares. Instead, they are consistent with small-scale chondrule-forming mechanisms proposed in the literature, such as nebular processing of dust balls by bow shocks and by current sheets.

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 is essential to: i) quantify more accurately C source/sink fluxes as part of the global carbon budget, ii) improve the current biogeochemical models predicting the effect of drought periods on greenhouse gas effluxes, and iii) identify more sustainable silvicultural practices for tropical planted forests in a context of climate change.

Base free N-alkylation of anilines with ArCH2OH and transfer hydrogenation of aldehydes/ketones catalyzed by the complexes of η5-Cp*Ir(iii) with chalcogenated Schiff bases of anthracene-9-carbaldehyde.

PubMed

Dubey, Pooja; Gupta, Sonu; Singh, Ajai K

2018-03-12

The condensation of anthracene-9-carbaldehyde with 2-(phenylthio/seleno)ethylamine results in Schiff bases [PhS(CH 2 ) 2 C[double bond, length as m-dash]N-9-C 14 H 9 ](L1) and [PhSe(CH 2 ) 2 C[double bond, length as m-dash]N-9-C 14 H 9 ] (L2). On their reaction with [(η 5 -Cp*)IrCl(μ-Cl)] 2 and CH 3 COONa at 50 °C followed by treatment with NH 4 PF 6 , iridacycles, [(η 5 -Cp*)Ir(L-H)][PF 6 ] (1: L = L1; 2: L = L2), result. The same reaction in the absence of CH 3 COONa gives complexes [(η 5 -Cp*)Ir(L)Cl][PF 6 ] (3-4) in which L = L1(3)/L2(4) ligates in a bidentate mode. The ligands and complexes were authenticated with HR-MS and NMR spectra [ 1 H, 13 C{ 1 H} and 77 Se{ 1 H} (in the case of L2 and its complexes only)]. Single crystal structures of L2 and half sandwich complexes 1-4 were established with X-ray crystallography. Three coordination sites of Ir in each complex are covered with η 5 -Cp* and on the remaining three, donor atoms present are: N, S/Se and C - /Cl - , resulting in a piano-stool structure. The moisture and air insensitive 1-4 act as efficient catalysts under mild conditions for base free N-alkylation of amines with benzyl alcohols and transfer hydrogenation (TH) of aldehydes/ketones. The optimum loading of 1-4 as a catalyst is 0.1-0.5 mol% for both the activations. The best reaction temperature is 80 °C for transfer hydrogenation and 100 °C for N-alkylation. The mercury poisoning test supports a homogeneous pathway for both the reactions catalyzed by 1-4. The two catalytic processes are most efficient with 3 followed by 4 > 1 > 2. The mechanism proposed on the basis of HR-MS of the reaction mixtures of the two catalytic processes taken after 1-2 h involves the formation of an alkoxy and hydrido species. The real catalytic species proposed in the case of iridacycles results due to the loss of the Cp* ring.

Serpentinization and the Formation of H2 and CH4 on Celestial Bodies (Planets, Moons, Comets)

PubMed Central

Oze, C.; Mousis, O.; Waite, J.H.; Guilbert-Lepoutre, A.

2015-01-01

Abstract Serpentinization involves the hydrolysis and transformation of primary ferromagnesian minerals such as olivine ((Mg,Fe)2SiO4) and pyroxenes ((Mg,Fe)SiO3) to produce H2-rich fluids and a variety of secondary minerals over a wide range of environmental conditions. The continual and elevated production of H2 is capable of reducing carbon, thus initiating an inorganic pathway to produce organic compounds. The production of H2 and H2-dependent CH4 in serpentinization systems has received significant interdisciplinary interest, especially with regard to the abiotic synthesis of organic compounds and the origins and maintenance of life in Earth's lithosphere and elsewhere in the Universe. Here, serpentinization with an emphasis on the formation of H2 and CH4 are reviewed within the context of the mineralogy, temperature/pressure, and fluid/gas chemistry present in planetary environments. Whether deep in Earth's interior or in Kuiper Belt Objects in space, serpentinization is a feasible process to invoke as a means of producing astrobiologically indispensable H2 capable of reducing carbon to organic compounds. Key Words: Serpentinization—Fischer-Tropsch-type synthesis—Hydrogen formation—Methane formation—Ultramafic rocks. Astrobiology 15, 587–600. PMID:26154779

Preparation, structure, and luminescence of dinuclear lanthanide complexes of a novel imine-amine phenolate macrocycle

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

Matthews, K.D.; Kahwa, I.A.; Williams, D.J.

1994-03-30

Metal-free condensation of 2,6-diformyl-p-cresol with 3,6-dioxa-1,8-octanediamine followed by reduction with sodium tetrahydroborate and addition of lanthanide(III) nitrate salts, in that order, yield (slowly) crystalline dinuclear complexes of a novel imine-amine phenolate macrocycle 2. The decacoordination geometry of the identical Pr[sup 3+] ions in a C[sub 2v] 4A,6B-extended dodecahedron made up of two bidentate NO[sub 3]-ions, two phenolate and two either oxygens, and one imine and one amine nitrogens. Dinuclear lanthanide complexes of 2 appear to be more stable than those of the totally reduced chelate 2 in alcoholic media. The Tb[sub 2]2(NO[sub 3])[sub 4][center dot]1.2CH[sub 3]-OH and (La[sub 0.97]Tb[sub 0.03])[submore » 2]2(NO[sub 3])[sub 4][center dot]1.2CH[sub 3]OH compounds exhibit strong Tb[sup 3+] ([sup 5]D[sub 4] [yields] [sup 7]F[sub J]) emission sensitized by the single state of 2 at both 77 and 295 K. No Tb[sup 3+]-Tb[sup 3+] self-quenching or N-H trapping effects are observed at 77 K (decay rate is 598 s[sup [minus]1]); the coordination cavities of 2 are therefore potentially good hosts for Tb[sup 3+] in luminescent diagnostic agents. At room temperature the complex decay kinetics of Tb[sup 3+] in Tb[sub 2]2(NO[sub 3])[sub 4][center dot]1.2CH[sub 3]OH are similar to those of Tb[sub 2]1(NO[sub 3])[sub 4][center dot]H[sub 2]O. But for the dilute complex, (La[sub 0.97]-Tb[sub 0.03])[sub 2]2(NO[sub 3])[sub 4][center dot]1.35CH[sub 3]OH, unusual thermal equilibration of the ligand triplet and Tb[sup 3+] [sup 5]D[sub 4] states occurs at room temperature; the ligand-to-Tb[sup 3+] energy-transfer rate is [approx]4.36 x 10[sup 4] s[sup [minus]1], while Tb[sup 3+]-to-ligand back-energy-transfer is [approx]7.1 x 10[sup 4] s[sup [minus]1].« less

Fast O2 Binding at Dicopper Complexes Containing Schiff-Base Dinucleating Ligands

PubMed Central

Company, Anna; Gómez, Laura; Mas-Ballesté, Rubén; Korendovych, Ivan V.; Ribas, Xavi; Poater, Albert; Parella, Teodor; Fontrodona, Xavier; Benet-Buchholz, Jordi; Solà, Miquel; Que, Lawrence; Rybak-Akimova, Elena; Costas, Miquel

2008-01-01

A new family of dicopper(I) complexes [CuI2RL](X)2, (R = H, 1X, R = tBu, 2X and R = NO2, 3X, X = CF3SO3, ClO4, SbF6 or BArF, BArF = [B{3,5-(CF3)2-C6H3}4]−), where RL is a Schiff-base ligand containing two tridentate binding sites linked by a xylyl spacer have been prepared, characterized, and their reaction with O2 studied. The complexes were designed with the aim of reproducing structural aspects of the active site of type 3 dicopper proteins; they contain two three-coordinate copper sites and a rather flexible podand ligand backbone. The solid state structures of 1ClO4, 2CF3SO3, 2ClO4 and 3BArF·CH3CN have been established by single crystal X-ray diffraction analysis. 1ClO4 adopts a polymeric structure in solution while 2CF3SO3, 2ClO4 and 3BArF·CH3CN are monomeric. The complexes have been studied in solution by means of 1H and 19F NMR spectroscopy, which put forward the presence of dynamic processes in solution. 1-3BArF and 1-3CF3SO3 in acetone react rapidly with O2 to generate metaestable [CuIII2(μ-O)2(RL)]2+ 1-3(O2) and [CuIII2(μ-O)2(CF3SO3)(RL)]+ 1-3(O2)(CF3SO3) species, respectively that have been characterized by UV-vis spectroscopy and resonance Raman analysis. Instead, reaction of 1-3BArF with O2 in CH2Cl2 results in intermolecular O2 binding. DFT methods have been used to study the chemical identities and structural parameters of the O2 adducts, and the relative stability of the CuIII2(μ-O)2 form with respect to the CuII2(μ-η2: η2-peroxo) isomer. The reaction of 1X, X = CF3SO3 and BArF with O2 in acetone has been studied by stopped-flow exhibiting an unexpected very fast reaction rate (k = 3.82(4) × 103 M−1s−1, ΔH‡ = 4.9 ± 0.5 kJ·mol−1, ΔS‡ = −148 ± 5 J·K−1·mol−1), nearly three orders of magnitude faster than in the parent [CuI2(m-XYLMeAN)]2+. Thermal decomposition of 1-3(O2) does not result in aromatic hydroxylation. The mechanism and kinetics of O2 binding to 1X (X = CF3SO3 and BArF) is discussed and compared with those associated to selected examples of reported models of O2-processing copper proteins. A synergistic role of the copper ions in O2 binding and activation is clearly established from this analysis. PMID:17500512

Inventory of anthropogenic methane emissions in mainland China from 1980 to 2010

NASA Astrophysics Data System (ADS)

Peng, Shushi; Piao, Shilong; Bousquet, Philippe; Ciais, Philippe; Li, Bengang; Lin, Xin; Tao, Shu; Wang, Zhiping; Zhang, Yuan; Zhou, Feng

2016-11-01

Methane (CH4) has a 28-fold greater global warming potential than CO2 over 100 years. Atmospheric CH4 concentration has tripled since 1750. Anthropogenic CH4 emissions from China have been growing rapidly in the past decades and contribute more than 10 % of global anthropogenic CH4 emissions with large uncertainties in existing global inventories, generally limited to country-scale statistics. To date, a long-term CH4 emission inventory including the major sources sectors and based on province-level emission factors is still lacking. In this study, we produced a detailed annual bottom-up inventory of anthropogenic CH4 emissions from the eight major source sectors in China for the period 1980-2010. In the past 3 decades, the total CH4 emissions increased from 24.4 [18.6-30.5] Tg CH4 yr-1 in 1980 (mean [minimum-maximum of 95 % confidence interval]) to 44.9 [36.6-56.4] Tg CH4 yr-1 in 2010. Most of this increase took place in the 2000s decade with averaged yearly emissions of 38.5 [30.6-48.3] Tg CH4 yr-1. This fast increase of the total CH4 emissions after 2000 is mainly driven by CH4 emissions from coal exploitation. The largest contribution to total CH4 emissions also shifted from rice cultivation in 1980 to coal exploitation in 2010. The total emissions inferred in this work compare well with the EPA inventory but appear to be 36 and 18 % lower than the EDGAR4.2 inventory and the estimates using the same method but IPCC default emission factors, respectively. The uncertainty of our inventory is investigated using emission factors collected from state-of-the-art published literatures. We also distributed province-scale emissions into 0.1° × 0.1° maps using socioeconomic activity data. This new inventory could help understanding CH4 budgets at regional scale and guiding CH4 mitigation policies in China.

Effect of homeopathy on analgesic intake following knee ligament reconstruction: a phase III monocentre randomized placebo controlled study

PubMed Central

Paris, A; Gonnet, N; Chaussard, C; Belon, P; Rocourt, F; Saragaglia, D; Cracowski, J L

2008-01-01

Aims The efficacy of homeopathy is still under debate. The objective of this study was to assess the efficacy of homeopathic treatment (Arnica montana 5 CH, Bryonia alba 5 CH, Hypericum perforatum 5 CH and Ruta graveolens 3 DH) on cumulated morphine intake delivered by PCA over 24 h after knee ligament reconstruction. Methods This was an add-on randomized controlled study with three parallel groups: a double-blind homeopathic or placebo arm and an open-label noninterventional control arm. Eligible patients were 18–60 years old candidates for surgery of the anterior cruciate ligament. Treatment was administered the evening before surgery and continued for 3 days. The primary end-point was cumulated morphine intake delivered by PCA during the first 24 h inferior or superior/equal to 10 mg day−1. Results One hundred and fifty-eight patients were randomized (66 in the placebo arm, 67 in the homeopathic arm and 25 in the noninterventional group). There was no difference between the treated and the placebo group for primary end-point (mean (95% CI) 48% (35.8, 56.3), and 56% (43.7, 68.3), required less than 10 mg day−1 of morphine in each group, respectively). The homeopathy treatment had no effect on morphine intake between 24 and 72 h or on the visual analogue pain scale, or on quality of life assessed by the SF-36 questionnaire. In addition, these parameters were not different in patients enrolled in the open-label noninterventional control arm. Conclusions The complex of homeopathy tested in this study was not superior to placebo in reducing 24 h morphine consumption after knee ligament reconstruction. What is already known about this subject The efficacy of homeopathy is still under debate and a recent meta-analysis recommended further randomized double-blind clinical trials to identify any clinical situation in which homeopathy might be effective. What this study adds The complex of homeopathy tested in this study (Arnica montana 5 CH, Bryonia alba 5 CH, Hypericum perforatum 5 CH and Ruta graveolens 3 DH) is not superior to placebo in reducing 24 h morphine consumption after knee ligament reconstruction. PMID:18251757

Antithrombin III blood test

MedlinePlus

... thinning medicine does not work. Normal Results Normal value ranges may vary slightly among different laboratories. Talk ... to the principles of the Health on the Net Foundation (www.hon.ch). The information provided herein ...

Properties of Multiphase Polyurethane Systems.

DTIC Science & Technology

1981-08-01

based on 4,4’-diphenylmethane dilsocyanate (MDI), N -methyl diethanolamine ( MDEA ), and polytetramethylene oxide (PTMO) and were synthesized with four...several levels of ammonium sulfonation (Scheme II) MDI/ MDEA /PTMO Series H04CH2 CH2CH2CH20- H + 0 = C = N -- -CH 2-O- N = C = 0 PTMO MDI 70 C HO OH...catalyst I II11 1 " 0 = C = N "---CH 2 - - N -C-O’-CH 2 CH C2H2 0-4C-’-( >-CH2DMA 1 CH3 70C I * HO - CM2 - CH2 - N - CH2 - CH2 - OH--- MDEA 0 H H 0 CH3H ... H2

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Seasonal cycles of atmospheric methane and its carbon and hydrogen isotopic ratios in the lower and upper troposphere of the western Pacific region

NASA Astrophysics Data System (ADS)

Umezawa, T.; Aoki, S.; Nakazawa, T.; Machida, T.; Matsueda, H.; Sawa, Y.; Ishijima, K.; Patra, P. K.

2009-12-01

Although carbon and hydrogen isotopic ratios (δ13C and δD) of CH4 provide useful information about its sources and sinks, systematic measurements were quite limited. Tohoku University group and NIES group have conducted air-sampling programs by using commercial container ships sailing between Japan and New Zealand and by using commercial airliners flying between Australia and Japan, respectively. Using air samples collected by the programs, systematic measurements of δ13C and δD of atmospheric CH4 as well as CH4 concentration ([CH4]) have been made since 2006. Here, we report their spatial and temporal variations in the lower and upper troposphere (LT and UT). In the LT of the northern hemisphere (NH), the seasonal cycle of [CH4] showed the maximum in winter and the minimum in summer. δ13C varied seasonally almost negatively correlating with the [CH4], and the seasonality of δD showed much more significant negative correlation with the [CH4]. It was also found that CH4 sources with seasonally varying strength, such as wetlands with high emissions in late summer, play an important role in the atmospheric CH4 variations. In the tropics, a seasonally-dependent air exchange between the NH and the southern hemisphere (SH) was found to characterize the seasonal CH4 cycle. When the NH and SH air arrived, high and low [CH4] were observed, accompanied by low and high δ13C and δD values, respectively. In the LT of the SH, the seasonal maximum and minimum of the [CH4] appeared in austral winter and summer, respectively. The seasonal CH4 cycle was mainly ascribed to the seasonality in the CH4+OH reaction, but δ13C and δD showed rather complicated seasonality with larger amplitudes than expected from the CH4+OH reaction alone, suggesting additional contribution of a CH4+Cl reaction in the marine boundary layer. In the UT of the NH, the seasonal maximum and minimum of the [CH4] appeared in summer and winter-spring, respectively, with low and high values of δ13C and δD in corresponding seasons. The summertime high [CH4] was observed when the [CH4] showed the seasonal minimum in the LT. By examining the relationship between δ13C (or δD) and the [CH4], as well as the results of tagged tracer experiments using the CCSR/NIES/FRCGC AGCM-based chemical transport model, we found that biogenic CH4 emissions from India, Southeast Asia and China are responsible for such summertime high [CH4] in the UT. By comparing the latitudinal distributions of the annual average [CH4], δ13C and δD in the UT and LT, we found that [CH4] and δD in the NH were higher and lower in the LT than in the UT, respectively, while the situation was opposite in the SH, due to NH air intrusion through the UT. On the other hand, δ13C showed no different distributions in the LT and UT of the NH, while δ13C in the SH was higher in the LT than in the UT, probably due to the contribution of the CH4+Cl reaction in the marine boundary layer.

Congenital hypothyroidism in neonates

PubMed Central

Anjum, Aneela; Afzal, Muhammad Faheem; Iqbal, Syed Muhammad Javed; Sultan, Muhammad Ashraf; Hanif, Asif

2014-01-01

Context: Congenital hypothyroidism (CH) is one of the most common preventable causes of mental retardation in children and it occurs in approximately 1:2,000-1:4,000 newborns. Aims and Objectives: The aim of this study is to determine the frequency of CH in neonates. Settings and Design: This cross-sectional study was conducted in neonatal units of the Department of Pediatrics Unit-I, King Edward Medical University/Mayo Hospital, Lahore and Lady Willington Hospital Lahore in 6 months (January-June 2011). Materials and Methods: Sample was collected by non-probability purposive sampling. After consent, 550 newborn were registered for the study. Demographic data and relevant history was recorded. After aseptic measures, 2-3 ml venous blood analyzed for thyroid-stimulating hormone (TSH) level by immunoradiometric assay. Treatment was started according to the individual merit as per protocol. Statistical Analysis Used: Data was analyzed by SPSS 17 and Chi-square test was applied to find out the association of CH with different variables. Results: The study population consisted of 550 newborns. Among 550 newborns, 4 (0.8%) newborns had elevated TSH level. CH had statistically significant association with mother's hypothyroidism (P value 0.000) and mother's drug intake during the pregnancy period (P value 0.013). Conclusion: CH is 0.8% in neonates. It has statistically significant association with mother's hypothyroidism and mother's drug intake during pregnancy. PMID:24741519

Arctic tundra and mountain landscapes are persistent sinks of atmospheric CH4

NASA Astrophysics Data System (ADS)

Christiansen, Jesper; Winkler, Renato; Juncher Jørgensen, Christian

2017-04-01

Recent studies have shown significant rates of net uptake of atmospheric methane (CH4) in Arctic tundra soils. Oxidation of CH4 in these cold, dry soils in the Arctic region can counteract CH4 emissions from wetlands and play a potential important role for the net Arctic CH4 budget. However, significant knowledge gaps exist on the overall magnitude of the net CH4 sink in these cold, dry systems as the spatial and environmental limits for CH4 oxidation has not been determined. In particular, the extent, magnitude and drivers of CH4 oxidation in mountains and alpine landforms, which occupy large land areas in the Arctic and High Arctic has not yet been investigated leaving a potential vast CH4 sink unquantified with major potential implications for our conceptual view of Arctic CH4 budget in a changing climate. Here we present the results from two expeditions in the summers of 2015 and 2016 from Disko Bay and in the pro-glacial landscape in vicinity of the Russell Glacier, Kangerlussuaq, Greenland, respectively. The aim of our work is to determine the magnitude and extent of net uptake of atmospheric CH4 across a variety of previously unexplored dry tundra and post-glacial landforms in the Arctic, i.e. marginal moraines and other glacial features at the Greenland ice sheet as well as mountain tops and outwash plains. We used high-precision, mobile cavity-ring-down spectrometers (e.g. model G4301 GasScouter, Picarro Inc.) to achieve reliable flux estimates in sub-ambient CH4 concentration levels with a 4-minute enclosure time per chamber measurement. Our results show a persistent net uptake of CH4 uptake in these dry, extreme environments that rival the sink strength observed in temperate forest soils, otherwise considered the primary global terrestrial sink of atmospheric CH4. In this dynamic glacial landscape the magnitude of the net CH4 uptake is mainly constrained by recent landscape evolution along glacier margins and meltwater systems. Utilizing the high mobility and precision of a new generation of greenhouse gas analyzers, like the Picarro GasScouter, we can explore beyond our traditional field scale the spatial drivers of CH4 oxidation in the harsh Arctic landscape. Thus, our measurements highlight the importance of net CH4 uptake in tundra soils for the Arctic CH4 budget.